Green Chemistry Program Nomination Table | US EPA

This table contains information on each unique technology nominated for the Green Chemistry Challenge from through . Although EPA has received 1,766 nominations during this period, only 912 unique technologies are represented here because sponsors may nominate a technology more than once.

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Traditionally, opaque intumescent coatings were used to reduce, or prevent, the spread of fire on wood substrates, achieving a Class A rating4 (defined as <25 flame spread index [FSI], and < 50 smoke developed index [SDI]) in the ASTM E84 Steiner Tunnel Test. However, the intumescent coatings used melamine formaldehyde chemistry that created a large volume of smoke from char formation, and covered up the natural wood visuals. To improve the visuals, clear intumescent coatings were developed that allowed for a somewhat natural wood visual, but struggled to obtain a true Class A rating in the ASTM E84 Steiner Tunnel Test, and presented as a plastic look to their visuals. In addition to the use of melamine formaldehyde chemistry to form the carbon char, many of the clear intumescent coatings require the use of a solvent-based topcoat to prevent the reabsorption of water from atmospheric exposure. Armstrong World Industries has developed a patent-pending novel, clear, waterborne, fire retardant coating system that has consistently achieved Class A ratings (<25 FSI/<50 SDI) in the ASTM E84 Steiner Tunnel Test on Poplar wood substrates, while still presenting a true wood visual, and using environmentally friendly chemistry. This novel coating system consists of three coatings that can be applied by conventional coating methods, and dried to a water-resistant layer while maintaining fire performance, hardness, adhesion, and coating integrity. The basecoat can be tinted to achieve colored visuals while still obtaining a 25/50 Class A rating. Armstrong&#;s patent-pending, new Class A clear coating system is a significant development in the fire-retardant coating market for wood substrates as it dramatically increases the protection offered by a clear coating against fire and smoke, present true wood visuals, and employ environmentally friendly chemistries in the process.

Petroleum oil continues to be a major player in the global energy portfolio, and oilfield surfactants are essential to its sustainable production, such as in enhanced oil recovery (EOR). The global surfactant market in EOR will hit $1.09 billion in .1 Cationic surfactants have been proven particularly effective in improving oil recovery in carbonate reservoirs. However, today&#;s commercial surfactants pose environmental and cost challenges. Cationic surfactants are toxic to aquatic ecosystems. Regulations are strengthening to address toxicity, so operators must incur costs to treat or store water used in EOR. Also, specialty surfactants are expensive to manufacture and often entail unstable supply chains. Battelle&#;s soy-based alternative can solve EOR and near-wellbore issues at lower cost and with less environmental impact. The non-toxic soy-surfactant, made from natural plant oil derivatives, has all the necessary characteristics of a cationic surfactant: good thermal stability, the capability to reduce oil&#;water interfacial tension (IFT) by 60%, and the capability to change reservoir rock&#;s wettability from oil-wet to mixed-wet, tending to water-wet. The soy-based raw materials are low-cost, and the resulting product requires minimal water treatment costs. The materials are readily sourced, offering a secure, cost-stable, and economical supply chain. This additive outperformed two competitive products in imbibition tests, recovering 35% of the oil originally in place (OOIP) inside reservoir rocks, while the competitors recovered 27% and 18%. These tests served as a qualitative indicator for field-scale performance. The product has potential to displace existing high-cost technologies/solutions, as evidenced by growing industry interest. Battelle and Airable Research Lab are reaching out to commercial partners who wish to capitalize on the opportunity presented by the growing market. Researchers can work with commercial entities to optimize the generic surfactant for specific process parameters characteristic of partner needs (e.g., a targeted reservoir).

Oxidation and reduction reactions are widely used in the synthesis of organic compounds in the pharmaceutical and chemical industries. However, such reactions most frequently require the use of stoichiometric amounts of chemical oxidants or reductants, while simultaneously generating large quantities of wasteful and often hazardous byproducts. Furthermore, the production of potent oxidants and reductants themselves requires energy intensive processes, causing unsustainable carbon footprints to the environment. Toward the goal of fundamentally improving the economic and ecological sustainability of organic synthesis, Professor Lin and his research group developed an electrocatalytic technology, which combines electrochemistry with homogeneous catalysis using earth-abundant metals. This technology enables organic redox transformations without the use of potent chemical oxidants or reductants and with substantially reduced byproduct formation, thus simplifying product purification and minimizing environmental impact. For example, the Lin group reported a broadly applicable protocol for the synthesis of vicinal diamines, a class of synthetic valuable building blocks, via tandem electrocatalytic diazidation and hydrogenolysis. This new synthetic pathway generates minimal harmless byproducts (NaOAc and N2), thus reducing the production of chemical wastes by >80 wt% and decreasing the E-factor by over 3 fold vis-à-vis current processes. In addition, the Lin group developed electrocatalytic C&#;H carboxylation of N-heteroarenes. This new reaction avoids the use of heavy metal catalysts, halogenated heteroarene substrates, and stoichiometric redox agents that are frequently required in current synthetic routes. Professor Lin has partnered with scientists from various industrial companies (Eli Lilly, Merck, Genentech, Snapdragon) to explore strategies toward safe and scalable implementation of electrocatalytic reactions for the discovery and synthesis of pharmaceutical agents. Their work in the development of electrocatalytic technologies for sustainable organic synthesis has garnered funding support from several agencies including NIH, NSF, and ACS Green Chemistry Institute and has resulted in a pending non-provisional patent.

"Inatreq active is an innovative, naturally derived fungicide that combats key plant diseases that rob farmers of yield in critical food crops around the world. Inatreq is better for the environment than alternative, available fungicides because it is effective at low use rates and biodegrades rapidly with low persistence in the environment. With a low use rate, it works with a smaller total amount of active ingredient applied to the field. With an environmental fate profile more favorable than other products, it provides effective disease control with less environmental impact. Inatreq active (ISO name fenpicoxamid) controls Septoria tritici blotch caused by Zymoseptoria tritici in cereal crops and Black Sigatoka, a disease caused by Mycosphaerella fijiensis, in bananas. Inatreq is the first member of a new class of fungicides (picolinamides) and is derived from a natural fungicidal compound, called UK-2A, produced by fermentation of a bacterium naturally present in soil. Scientists isolated the original bacterial strain that produces UK-2A from a soil sample collected at Osaka City University in Japan. A minor synthetic modification of UK-2A produces Inatreq. In the presence of fungi or in plant tissue, Inatreq&#; active converts back to UK-2A, which inhibits fungal respiration. Studies in the field and the laboratory show excellent efficacy of Inatreq against targeted diseases, including plant disease isolates that are resistant to other fungicides currently on the market. Inatreq represents the first new target site of action against Septoria tritici blotch in wheat and Black Sigatoka in banana in over 15 years. With no cross resistance to existing products on the market, Inatreq provides growers an essential tool for effective resistance risk management when used in fungicide spray application programs together with existing active ingredients."

ECOFAST&#; Pure Sustainable Textile Treatment is a commercially available breakthrough technology for cotton dyeing produced in the United States. This innovative product significantly reduces water, dye, energy and process chemical use while decreasing wastewater effluent. A Life Cycle Analysis conducted on the usage of ECOFAST Pure for dyeing cotton determined clear benefits in decreasing global warming potential, reducing carbon dioxide emissions by about 60%. In addition, ECOFAST Pure makes colors previously unavailable on cotton possible and provides brighter, bolder shades overall. These sustainability and performance benefits make ECOFAST Pure a true game changing technology for the textile industry. ECOFAST Pure is designed to radically improve the typical cotton dyeing process by increasing the affinity between cotton and anionic dyes. Both dyes and cotton are negatively charged and thus repel each other. ECOFAST Pure converts cotton into a positively charged material through a pretreatment step, drastically improving its affinity for dyes while maintaining its performance intact. Over the past several decades, the textile industry has received public scrutiny for its sustainability practices, including the intense natural resource demands of growing, processing and manufacturing cotton textiles and the hazardous chemicals discharged to water supplies. Current estimates suggest textile processing is responsible for 20% of industrial water pollution globally, with these negative impacts disproportionally impacting developing countries and raising significant environmental and social sustainability concerns as shown in the &#;Blue Dogs of Mumbai&#; news story from . At a time where our natural resources are rapidly depleting, utilizing technology to save these resources while creating better products is vital to a sustainable future. ECOFAST Pure is the key step forward in solving textile industry challenges and reducing our environmental footprint.

"Dow developed a solventless silicone coating SYL-OFF&#; SL 351 Coating that is expected to deliver significant coat weight savings (up to 29% or more) and will enable use of thinner and more porous substrate liners, when a solventless coating is needed (as we can do this easily with WB Emulsion Coatings). This new coating along with SYL-OFF&#; crosslinker allows manufacturers to realize cost savings by using less expensive paper and less silicone (reduced soak in) with less platinum catalyst (usage down to as low as 15ppm) and reduce oven temperatures when curing the silicone. The hygiene release market is growing at 4.3% globally/annum and even faster in other regions. Machine grade paper is widely used especially in ASEAN for hygiene release market. Features of this new silicone release coating are that it can be run at high line speeds with no silicone mist generated and also offers the capability to run at lower oven temperatures. It provides excellent hold out on porous machine grade substrates used which eliminates up to 29% reduction in silicone usage, equating to kg of silicone in . SYL-OFF&#; 351 coating is a solvent-free solution which is used at low platinum levels with excellent anchorage to the substrate so less loss of silicone after coating. Polymer properties are tailored so that a chemical change in release coating can occur in less than a second. It is commercially viable drop-in alternative for emulsion-based systems. The polymer and resulting SYL-OFF&#; 351 coating, is produced in full scale commercial reactors and meets D4 REACH regulations. This product has exceeded $400,000 sales in and $500,000 system sales. The polymer technology is patented. A commercial roll-out is planned in . This coating can be used in other areas of the pressure sensitive market to improve sustainability."

"The use and interest in &#;Natural&#; products have been on the rise in the beauty care industry. Consumers desire more natural products, with similar or better performance than their synthetic alternatives. This is driven in part by a perception that natural products are safer for the consumer and by an increased awareness around the environmental cost of utilizing petrochemically-derived materials. Today, in the hair styling market, polyvinylpyrrolidone (PVP) is the most widely used styling polymer. As such, there is a critical need to develop more sustainable technologies for this market and polysaccharides are ideal natural replacement candidates for many synthetic polymers. MaizeCare&#; Style Polymer is a sustainable product obtained from non-GMO corn starch, which has a 100% natural origin (ISO ), is readily biodegradable (OECD 301F) and has COSMOS (COSMetic Organic and natural Standard) Certification by Ecocert®. The material is mechanically and thermally processed, through a proprietary extrusion process, into a powder polymer that can be dispersed in an aqueous solution. The key performance attributes of this technologies are as follows: > The polymer forms a bio-based film with an improved environmental profile compared to PVP (manufactured through extrusion, a low environmental impact process vs. free-radical polymerization for PVP, uses a greener feedstock, has an estimated 70% CO2 footprint reduction compared to PVP). It also enables corn valorization in the USA. > In formulations, MaizeCare&#; Style acts as a transparent film-former and styling aid that can deliver superior stiffness all the way to soft-touch styling. In leave-on styling applications, this polymer delivers excellent performance in curl retention compared with PVP and other corn starch product offerings, even at low concentration levels. _ > MaizeCare&#; Style can be easily formulated into various product formats, including gels, waxes, creams and sprays which allows for creative textures and a customized consumer experience."

"With the start of waterbased paints, sustainability of coatings was vastly improved. However, the polymers used in waterbased paints either contain high concentrations of fossil fuelbased raw materials and often require toxic intermediates to achieve high performance properties. Decovery® products use biobased materials for high performing paints, with significantly reduced carbon footprint, and reduced concentrations of toxic materials essential for the excellent performance of waterbased paints. Since long, biobased polymers for use in paints have existed when in the middle ages, painters used natural oils, and later the coatings market has used alkyds, which are derived from natural oils. However, polymers like alkyds and oils have significant disadvantages with slow drying, dark yellowing, and the need of toxic metals, such as cobalt to initiate crosslinking. In the Decovery®-program polymers have been developed that enables the development of fast drying, high gloss, high resistant, and low toxic paints and coatings in architectural, industrial interior, industrial exterior, food packaging, flooring, and inks applications. The eleven biobased products that were developed so far are based on (meth)acrylic copolymer emulsions, styrene-acrylic copolymer emulsions, and urethane-acrylic emulsions. All these products are 14C-certified biobased, have reduced carbon footprints compared to fossil fuel based paints &#; as verified by official institutes &#; with similar performance, and can deliver superior adhesion without the need for toxic amines, or raw materials that require toxic intermediates. Carbon footprint reductions are achieved of between 0.5 and 1.0 kg CO2 per kg of polymer emulsion. Biobased contents, -certified, have been achieved varying between 30 and 50 Carbon14-% for the first products, and of 50 14C -% for the wall paint market. To be successful with the Decovery® program, new biobased monomers were developed with inherently slower copolymerization characteristics. Technologies were developed, and patented that makes it possible to copolymerize these new biobased monomers effectively, nonetheless."

"Odor control is a key component associated with sanitation. Odor masking in end user products such as laundry and air refreshers is a common approach; however, it does not eliminate odor sources and presents potential health risks for humans. Capture of malodorous molecules is a preferred solution to this problem. Itaconix has designed, patented and commercialized a novel water-soluble zinc polyitaconate. This breakthrough technology does not mask odor but instead captures odor molecules removing them from the vapor space so they are no longer detectable by human nose. This 100% biobased polymeric zinc complex offers unique advantages over existing odor control technologies especially those zinc based. Zinc polyitaconate has a good environmental profile showing reduced ecotoxicity compared to commonly used zinc salts. Extensive safety studies proved that the polymer has an excellent human safety profile. Moreover, this sugar derived molecule is produced with high purity through a green and energy efficient process without utilization of any petrochemical feedstock. It has 100% atom efficiency, and relies exclusively on water as a solvent. Synthesis is done in two essential steps, one requiring a unique continuous polymerization in a near-solid state and the other is a simple batch aqueous solution reaction. Both synthesis steps are energy efficient, low-cost and safe. Beyond the direct reduction of Green House Gas (GHG) emissions during synthesis, zinc polyitaconate provide multiple source reduction advantages during application formulation. Compared to alternative zinc complexes used for odor neutralization, it does not require the use of potentially harmful additives such as surfactants, chelants, solvents and anti-foaming agents. Zinc polyitaconate is produced in the USA and is sold worldwide."

"CENTURO was developed to assist farmers and society face the challenges of increasing food production while minimizing impact to the environment. CENTURO contains the first active ingredient for nitrification inhibition registered by the EPA in more than 40 years and has the potential to improve the operational efficiencies and nitrogen-use efficiency (NUE) of the roughly four million tons of anhydrous ammonia and eight million tons of UAN applied each year on corn in the U.S. Human health & handling benefits: o CENTURO has a low toxicological profile particularly for worker exposure and handling, high solubility in water and very high flash point, negating explosion-proof equipment. Environmental benefits o CENTURO significantly reduces the amount of nitrogen needed to achieve the intended yield. CENTURO is proven to increase NUE by up to 25 percent. If similar results were obtained for all nitrogen applied to corn in the U.S., as much as 1.46 million tons of nitrogen could be saved annually, reducing input costs for farmers and greatly contributing to efforts to decrease nitrogen loading in surface waters. o CENTURO keeps ammonium in the soil for longer periods, which reduces nitrous oxide emissions by delaying both nitrification and denitrification processes. Applicability o CENTURO is less corrosive and has a higher flash point than other FIFRA-registered commercially available nitrification inhibitors, which require specific storage and handling conditions including the use of stainless-steel storage tanks and explosion proof equipment. o In the U.S., up to 50 percent of anhydrous ammonia is fall-applied because of the availability of equipment and workers, and generally more favorable application conditions than in spring; however, fall applications are often considered to be less efficient agronomically than spring applications. Third-party data suggests farmers can be just as effective by applying CENTURO with their fall-applied anhydrous ammonia than waiting until spring."

McTron Technologies will be using both Green Chemistry and Source Reduction in their launch of MaxxGold&#; Thermoset resins. Waterproofing thermoset resins are used in the manufacture of Produce and Meat packaging containers that have good physical strength in the presence of moisture. 60 Million pounds/year of acetone formaldehyde (AF) resin is currently sold in North America and Central America for this purpose. Worker exposure inside the mills and emissions from the mills are of concern. While the elimination product (during cure) from AF resin is formaldehyde, the elimination product from our new MaxxGold&#; resin is water. Global production of formaldehyde is 50 billion pounds/year. 40 Million pounds of this is used in AF Resin manufacture for corrugated board. Since AF Resin is consumed in small quantities at several hundred corrugators in the US alone, little is currently being done to curb emissions / worker exposure. McTron has developed novel technology to replace the AF resins with &#;No Added Formaldehyde&#; chemistry. The major feedstock for these new resins begins with US grown plants (sugars). AF Resins contain Methanol and Acetone as VOCs.

"Nexus Fuels, LLC is a waste management and feedstock production company that has developed a commercial-scale process for converting waste plastics into chemical feedstocks for plastics production and fuels, which can be further refined into a full range of products including virgin plastics, fuels, and related materials. Nexus has engineered a process that is economical, scalable, versatile, and environmentally positive. The strategic advantages of Nexus&#; technology include positive energy balance, continuous processing, low operating cost, char minimization, and cutting-edge automation. Nexus is not just a technology, but a business with in-house engineering, training/safety procedures, software, procurement processes, proven vendors, finance systems, operations and maintenance systems, logistics and all regulatory approvals led by an experienced team and guided by financially-driven metrics. On a pound per pound basis, plastic is a valuable hydrocarbon that has 2-3 times the energy content of other materials like coal and wood. Made originally from crude oil and natural gas, plastics can be converted back into high-quality chemical feedstocks and fuels (&#;renewables&#;) at attractive market-based, not premium, prices. After years of attempts, limited successes and some failures by others, Nexus Fuels has developed a proven method for converting plastics that do not have a place in the conventional mechanical recycling system, especially films which are the main source of landfill-bound plastics, that is highly efficient and economic. Nexus uses the established process of pyrolysis (heating in the absence of oxygen) in unique ways to convert feedstock (films, rigid plastics and others) plastics into high-grade oils and waxes, the result of which is a liquid hydrocarbon product that has a dense energy content, high purity, and can further refined to yield a variety of market-ready products, whether as a chemical feedstock or refinery input. This process allows recycling of waste mixed plastics that cannot be efficiently recycled by alternative means and permits recycling of unwashed and soiled plastics. The Nexus operation operates well below established air quality levels within a closed loop that also meets other limits for VOCs, CO and NOXs which means that permitting is not an issue and the environmental impact of the plant is minimal. Nexus has agreements with national and international suppliers of feedstock as well as smaller plastic brokers throughout the Southeast US to secure a steady stream of plastic waste for its current commercial plant. Additional commercial plant sites are being commissioned based on feedstock availability for allow rapid rollout on a domestic and international basis. Nexus has produced over 80,000 gallons of product and has sold this material to a rapidly growing group of satisfied global customers."

"Crude oil plays an important role in the global economy and is one of the major sources of globally-produced energy and chemicals. It comes out as a stable emulsion when extracted from the sea thus requiring &#;demulsification&#; by adding chemical demulsifiers to separate water from the oil before it is transported from offshore oilfields to onshore refineries located miles away. Due to changing environmental awareness including Green Chemistry Principles and regulations like OSPAR for North Sea, demulsifiers that were used for decades no longer meet the new, stricter requirements of biodegradability, low tox and bioaccumulation7. In an effort to design and develop &#;greener&#; substitutions that meet these requirements, Nouryon undertook a study in partnership with an oilfield service company to test the products made in different parts of the world. After a three-year exhaustive study of designing, synthesizing and evaluating nearly 300 samples from 17 different technologies in the lab followed by offshore field evaluations across the world, Nouryon has now launched a new range of best-in-class high-performance, cost-effective and OSPAR-approved oilfield demulsifiers for global exploration with excellent environmental profile1-5. The breakthrough technology not only offers cost-effective products but also satisfies all the 12 Principles of Green Chemistry: (1) zero waste; (2) 100% atom economy; (3) non-hazardous synthesis using safer raw-materials giving only water as byproduct; (4) OSPAR-approved products with excellent eco-profile; (5) no solvents, no work-up and no separations; (6) better energy efficiency vs current Witbreaks8; (7) use of non-food or waste renewable feedstocks; (8) zero derivatizations and zero waste; (9) using catalysts to reduce reaction times; (10) products with excellent biodegradation of >60% with no bioaccumulation or microplastics issues; (11) monitoring the progress of reactions using simple titration method; and (12) no gaseous toxic raw-materials with potential risk of accidental release used in the 1-step production processes."

"Glasdegib (which, as the maleate salt, is the active ingredient in the approved drug product Daurismo®) is a small molecule inhibitor of the sonic hedgehog receptor smoothened (SMO).1 Daurismo® is approved in combination with low-dose cytarabine for the treatment of newlydiagnosed acute myeloid leukemia (AML) in adult patients who are &#;75 years old or who have comorbidities that preclude use of intensive induction chemotherapy. Pfizer&#;s commercial route to glasdegib uses an innovative biocatalytic reaction to remove a classical resolution found in the enabled route. The biocatalytic process reduced the total number of steps, minimized the generation of waste, and drastically lowered the volumes of solvent, including water. The new biocatalytic process has been successfully implemented in a production facility using batch reactors at a 100kg scale. Pfizer has implemented exceptional Green Chemistry innovation by using a biocatalytic reaction, where the application of transamination on production scale in the pharmaceutical industry is rare. Additional process improvements include the use of telescoping high yielding reactions to maximize product output and minimizing side-products (waste). These improvements result in a biocatalytic process that is more sustainable than the completely chemical process it replaced. Key innovations were (i) identifying and implementing a transamination coupled with a dynamic kinetic resolution to set absolute stereochemistry (ii) optimizing a high yielding bond disconnection strategy (iii) demonstrating on laboratory scale a continuous approach to disrupt and innovate the industry for the clinical and commercial manufacturing of medicines. We believe that we have brought an important oncology medicine to the patient in an environmentally responsible manner. Pfizer has published the chemistry in a peer reviewed scientific journal.2 Glasdegib is one of the very few small molecule pharmaceutical agents where reductive amination was carried out in combination with a concurrent dynamic kinetic resolution to establish the two stereogenic centers in a single step. Finally, Pfizer&#;s commitment to green chemistry is further exemplified by the pursuit of an alternative route that employs flow chemistry. Although not implemented on scale for the routine production of glasdegib, this process was developed to explore possibilities for improved sustainability and the reduction of waste."

"ENVIROCRON&#; Extreme Protection Dielectric powder coating is an environmentally-friendly solution that enables electric vehicle manufacturers to maintain battery safety and extend lifetimes while moving to an automated, high-yield process. Key features of our dielectric powder include: &#; Excellent electrical insulation performance and durability for long-term battery safety &#; Engineered with significant recycled PET content, currently saving the equivalent of ~81,000 plastic bottles from landfill per day &#; Powder coatings are solvent-free for essentially zero air emissions during cure and generate almost no waste during application &#; Curable using electric-powered IR ovens that consume over 70% less energy than traditional gas fired ovens. IR ovens save up to 85 lbs CO2 per oven per year using fossil-fuel derived electricity and up to 175 lbs CO2 per oven per year using renewable electricity &#; Easy to automate for high-volume/high-yield manufacturing to support growing demand for electric vehicles ENVIROCRON Extreme Protection Dielectric powder coating was first commercialized with a US automotive customer (who wishes to remain anonymous at this time) in . We are actively working to expand use throughout the automotive industry and into non-automotive products that require lithium ion battery insulation."

PPG&#;s battery binder solution is a more sustainable, cost-effective, and higher performing alternative to conventional lithium ion battery binders. We brought the perspective of coatings scientists to rethink the way the battery binders in use for decades are designed. Through new polymer design and dispersion science, we created a formulated product of safer solvent and a mixture of new binder technology, custom-designed to reduce the total amount of solvent by 20-30% while improving rheology and eliminating the stability issues of traditional battery coatings. This drop-in solution completely eliminates the hazardous solvent N-methyl pyrrolidone (NMP) used throughout the battery industry to solubilize traditional polyvinylidene fluoride (PVDF) binders. It is customizable to work with the range of cathode active pigments and conductive pigments used by battery makers to produce a uniform battery slurry that creates more consistent and higher quality cathodes. The product provides validated benefits to cell manufacturers including better safety, better cell performance, and up to 20% lower manufacturing costs according to our cost models. These are all critical attributes necessary to support the growing global lithium ion battery market and other environmentally-friendly technologies such as electric vehicles. Our NMP-free battery binder solution became commercially available in . It is in advanced stages of qualification at major battery producers with implementation targets in June .

"RiKarbon, Inc., a Delaware company and developer of enabling technologies for the production of renewable and high-performance specialty products to serve the domestic and international market, is commercializing a proprietary technology to produce eco-friendly, sustainable and silicon-free ingredients for cosmetics and Environmentally-Acceptable Lubricants (EALs) products to replace health and environmentally hazardous petroleum-derived emollients and base-oils. Cyclo-silicon compounds (e.g., D4 (cyclotetrasiloxane), D5 (cylcopentacycloxane), D6 (cyclohexasiloxane)) are currently used in emollients for hair-care, skin-care and color cosmetics. These cyclo-silicon compounds are currently regulated by REACH program in Europe because of their bioaccumulation and environmental toxicity. In addition, consumers desirability for silicon-free cosmetics is increasing globally. Similarly, over 98% of current lubricant base-oils are petroleum-derived and their use in marine applications (cruise, ships, marine vessels, hydropower turbines, off-shore turbines etc.) are regulated by VGP regulation in USA. Therefore, cosmetics and lubricants formulators, ingredient manufacturers, distributors, branding companies and environment advocates are seeking technologies for the production of alternative, eco-friendly and Greener emollients and base-oils to mitigate regulatory challenges and meet consumer desirability. RiKarbon is producing innovative renewable oils from sustainably sourced feedstock using Green principles. Our technology allows production of high carbon number oils with tailored molecular architecture and tunable specifications. These products, synthesizing from commercially available low carbon number bio-based raw materials and featuring up to 100% bio-based carbon content, sulfur and silicon-free, high oxidation stability, potential biodegradability, and superior specifications than current products, meet bio-preferred qualification and eco-certification requirements. RiKarbon&#;s addressable market size is over $10 billion with estimated CAGR of >10%. RiKarbon&#;s bio-based emollients (BioKres-SFDTM) have been used in hand-care lotion formulations in collaboration with global cosmetic manufacturing companies, which indicated beneficial performance of BioKres-SFDTM in the end-use cosmetics as compared to the benchmark cyclo-silicon compounds."

FUTERRA products were developed to meet the demands of the wet conditions of marine propulsion equipment. To withstand these conditions, they need to be oxidatively, thermally, and hydrolytically stable while performing as well as products in the field. These products eliminate the risk of using standard mineral oil products which can be harmful to the aquatic life. Made from a renewable resource, there is no risk of petroleum oil spills. Many of the competing products in the field use base oils that after water ingress break down and need to be changed out sooner than normal system maintenance times. FUTERRA has been developed to meet the standard life of the equipment and with proper monitoring, exceed the life maintenance interval. After three years of commercialization, FUTERRA has numerous approvals by original equipment manufacturers and being used in a multitude of vessels worldwide.

"Sironix Renewables&#; Eosix® Surfactant is a multi-functional, bio-renewable cleaning ingredient that reduces the environmental impact of cleaning products and enables betterperforming, more concentrated detergents. The Eosix® Surfactant accomplishes this through 500x improved performance in hard water conditions, which eliminates the need for chelating agent additives in detergent formulations, thereby giving two-for-one performance using the inherent structures of bio-renewable natural oil and cellulosic feedstocks. Current laundry detergent formulators utilize the strong detergency characteristics of surfactants in order to remove dirt and oil particles from soiled fabric. However, in use conditions, the presence of &#;hard&#; water (containing calcium and magnesium ions) deactivates surfactants, necessitating the incorporation of chelating agents to preferentially bind to hard water ions. Chelating agents such as phosphates and EDTA have been shown to be persistent in the environment, bio-accumulate in aquatic wildlife, and draw heavy metal contaminants through wastewater treatment facilities into waterways. The new Sironix surfactant molecule, called the oleo-furan surfactant (OFS), is synthesized from bio-renewable feedstocks including coconut oil and furan, a starch derivative. The simple two-step chemical process is designed to be scalable and inexpensive through an innovative reactive distillation approach. As a result, the Eosix® Surfactant is cost competitive with existing cleaning surfactants and offers cost savings in a detergent formulation by eliminating the need for chelating agents. Implementation of this technology serves to remove over 50,000 tons of chelating agents per year, with at least 10,000 tons discharged from wastewater treatment facilities into the ocean. Additionally, the technology has improved performance in cold water wash conditions compared with existing renewable surfactants, which has the potential to reduce the energy intensity of laundry by 20-30%. Sironix Renewables is operating at a pre-pilot scale and is working through numerous pilot test and JDA partnerships to develop commercial performance data in cleaning products."

"The US shale boom over the last decade has created numerous environmental challenges that must be overcome. For every barrel of oil recovered, three to eight barrels of water are produced. This &#;produced water&#; is high brine and often contaminated with hydrocarbons, fracking fluids, H2S, heavy metals, and radioactive elements. In , the US O&G industry is projected to handle 18 billion barrels of produced water, with most of this water destined for reinjection underground into saltwater disposal wells (SWDs). O&G operators spend between $0.05/bbl and $0.10/bbl on water treatment chemicals to handle produced water, meaning more than $1B worth of chemicals will be consumed in . Acrolein and tetrakis hydroxymethyl phosphonium sulfate (THPS) are two of the most widely used produced water treatment chemicals, especially when metal sulfide scale and corrosion are present. Solugen has developed a chemienzymatic process technology for the selective partial oxidation of dextrose corn syrup (from US corn) to monoacids and diacids via the co-production of hydrogen peroxide. Solugen formulated combinations of these organic acids into its ScavSolTM product line, which was launched in 1Q. Within 1 year of launch, Solugen has successfully replaced THPS and acrolein across more than 20 field trials at each stage of the produced water lifecycle, from waterfloods in CA, to oil:water separators in LA, to water midstream pipelines in TX, to SWDs in OK. In each trial, Solugen outcompeted the incumbent chemistries based on improved efficacy, reduced cost, and improved safety profile for field personnel. Widespread adoption of ScavSolTM would eliminate 100 million+ pounds of hazardous substances (and reduce the associated manufacturing and transportation carbon dioxide emissions) from produced water treatment. Solugen&#;s process technology enables a variety of safer, cheaper, and environmentally friendly organic acid based chelants that outperform legacy incumbent chemistries in agriculture, mining, and rust removal."

"Recognizing market realities, Sylvatex has developed a low-cost, low-carbon, high-impact and easy-to-implement alternative diesel fuel (ADF) using MicroX that will go into production in . MicroX&#;s unique design allows for the formation of stable reverse-micelle microemulsions enabling the integration of ethanol into diesel to form a stable ADF. The MicroX blendstock primarily utilizes ethanol as the oxygenate, which is easily and affordably sourced, and was highlighted as one of the six most promising fuel alternatives out of more than 400 studied by the US Department of Energy&#;s Co-Optimization of Fuels & Engines initiative but technical limitations have hampered ethanol ADFs development. Sylvatex&#;s flagship product, MicroX, is the first to solve these technical limitations and unlocks ethanol&#;s potential as a widely used alternative fuel. Not only is MicroX greener than diesel or competing ADFs, it is manufactured using a green process and is stable across a wide range of concentrations and demanding temperature requirements, making production and use at commercial scale simple and costeffective. Made from renewable, locally sourced feedstocks, MicroX is tested and proven at scale, substantially reduces emissions in the transportation sector, is registered with the US Environmental Protection Agency under the Clean Air Act and is in the process of securing California ADF approval. Furthermore, Sylvatex worked with ASTM to develop the first ever standard for microemulsion fuels in diesel (ASTM D-19), which was approved in and adopted in , and is now the industry standard and covers the use of the Sylvatex technology. Sylvatex has partnered with a California-based ethanol producer and is currently designing and engineering the company's first pilot production facility. It is anticipated that the startup and commissioning of this pilot facility will occur in the beginning of and expand to full operations by the end of ."

"At least as early as , Goodyear has been investigating the viability of soybean oil (SBO) in automobile tires to replace petroleum-based distillate aromatic extract (DAE) and medium extracted solvate (MES) oils. Our team of researchers discovered that the unique properties of SBO compared to petroleum-based oils can be leveraged to provide benefits in tire applications. These findings initially led to the development of an SBO-extended solution styrene-butadiene rubber (SSBR) for tire applications. This SBO-extended SSBR was fully industrialized in our Beaumont chemical facility in . By utilizing this new polymer, as well as SBO as a freely added material in our tire compounds, we have observed significant benefits in both plant processing and product performance. In , these benefits led to the commercialization of the Assurance WeatherReady tire, the industry&#;s first passenger tire to fully replace petroleum-based oil with SBO in the tread. Since then, Goodyear has commercialized two additional SBO-containing tire products, and additional development remains ongoing. The processing and performance benefits achieved with SBO, combined with Goodyear&#;s commitment to the use of sustainable materials in its products, has inspired Goodyear to announce a near-term goal of increasing its SBO usage 25% by , and to declare a long-term goal of fully replacing petroleum-derived oils by ."

"Since its original discovery over a century ago, the water-gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H2 to feed fundamental industrial transformations such as the Haber&#;Bosch synthesis of ammonia and the synthesis of many reducing agents used in organic synthesis. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H2O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation-type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis are largely underdeveloped. Over the past 10 years this laboratory has demonstrated several examples of net reductive carbon-carbon bond forming reactions that can be accomplished by harnessing the reducing potential of the WGRS and thereby obviating the need for stoichiometric amounts of chemical reductants such as sacrificial metals or organic reductants. In so doing, this technology has eliminated the waste stream created by the use of these reductants. These transformations include: (1) reductive allylation of aldehydes, (2) reductive alkylation of active methylene compounds, (3) reductive carbonylation of aryl iodides, and (4) recovery of rhodium from various solid supports, potentially from spent catalytic converters. In all cases, the reaction conditions are mild and compatible with otherwise reducible functional groups. Further modifications allowed for the site- and enantioselective allylation of aldehydes as well as the site-specific deuteration of the formyl group of aldehydes."

The objective of this study was to develop and apply a Bio-molecular/enzyme-based environmentally preferable hydrogen sulfide scavenger that addresses secondary issues caused by current chemical scavengers like triazine and glyoxal. Recombinant DNA and protein expression technologies were exploited to develop this H2S scavenger and confirm its ability to mitigate sulfide in different applications. The bio-molecular scavenger is generated by cloning a cDNA sequence from a thermophilic organism and an expression of the target protein in bacteria and yeast. The bio-molecular based scavenger formulation was developed and manufactured in a Baker Hughes pilot plant. The efficacy of the scavenger was evaluated in sour brine, crude oil, refinery water and mixed production fluids from different sources. Functional studies conducted by treatment of sour brine and oil revealed a 72% and 90% reduction in H2S concentration, respectively. The scavenger showed a 75% reduction of sulfide in simulated mixed production samples containing a 30:70 ratio of brine and oil. Limited testing of this scavenger in the field showed a reduction of headspace sulfide from 400 ppm to 2 ppm. Further, the field data showed less than 0.5% BS&W (basic sediment and water). This bio-molecular scavenger showed acceptable materials compatibility when tested with oilfield metals, plastics and elastomers. The scavenger also showed no significant increase in corrosion during the scavenging reaction. These studies confirm that the novel bio-molecular scavenger can be successfully used to mitigate H2S in various systems without causing adverse effects that are commonly observed with many chemical scavengers. The bio-molecular scavenger has several advantages such as meeting environmental regulations, significantly reducing or eliminating secondary effects like solids formation, corrosion, scaling, and health hazards that are associated with many of the current chemical scavengers.

Hydraulic fracturing is a method used to create subterranean fractures. A high-viscosity fracturing fluid containing a polymer and a proppant is pumped into the well at sufficient pressure to fracture the formation. When the proppant is in place, the formation closes on the proppant, holding it in place. The majority of conventional fracturing fluids are made of guar (galactomannans) or guar gum derivatives such as carboxymethyl guar (CMG), hydroxypropyl guar (HPG) or carboxymethyl hydroxypropyl guar (CMHPG). These polymers can be cross-linked to increase their viscosities and their proppant transport capabilities. Chemical oxidizers such as ammonium persulfate is most commonly used as breaker. Even before state and federal agencies began to focus on the environmental impacts of shale development, responsible service providers like Baker Hughes, were developing new fluids and technologies to minimize environmental, health, and safety risks of hydraulic fracturing operations. This nomination presents evidence that chlorophyll can be used as a novel environmentally preferable polymer breaker for hydraulic fracturing applications. Chlorophyll-treated cross-linked fluids showed a more than 90% viscosity reduction, without any viscosity rebound on cooling. The chlorophyll worked efficiently up to 250°F, but the optimum temperatures were at 175 to 200°F with a narrow pH range of 9.5 to 10. The chlorophyll-treated fluids also showed a reduction of molecular weights of the linear guar polymer from 1,472,000 to 138,000, and the derivatized guar polymer from 3,042,000 to 180,000 as measured by the intrinsic viscosity method. The studies support the hypothesis that chlorophyll can function as a polymer breaker for alkaline fracturing fluids.

Engineered metal nanoparticles are materials with at least one dimension < 100 nm that possess unique properties because of their high surface-area-to-volume ratios. The global market for metal nanoparticles is projected to grow from $12 billion in to $25 billion by . Their end use applications include heterogeneous catalysts, antibacterial agents, diagnostics, and touch displays. Unfortunately, current nanomanufacturing methods for producing high-quality colloidal metal nanoparticles remain at the bench scale, with an environmental impact and cost that reflects the limited throughput and labor intensity of a byhand process. As such, the gains derived from the use of engineered nanoparticles are currently offset by the methods used to manufacture them. The greatest challenge associated with scaling up the synthesis of colloidal metal nanoparticles is that large-volume industrial reactors lack uniform mixing and temperature; they produce low-quality particles with heterogeneous morphologies and are therefore an inappropriate route for scale up. The technology described here successfully scales up the synthesis of colloidal metal nanoparticles by scaling down; that is, the complications of heat and mass transport are solved by using continuous flow reactors with high microchannel surface area-to-volume ratios. In order to produce particles cost-effectively at large scale, we were the first to develop microreactors that can be operated in a parallel configuration, with many reactors working together both simultaneously and identically to produce nanoparticles. Techno-economic analysis of our continuous flow method for metal nanoparticle synthesis estimates a 90% reduction in capital, utilities, and labor costs over the traditional batch process. Moreover, the continuous flow method realizes a 50% reduction in cumulative energy demand over the batch process, resulting in a net savings of > 0.5 metric tons of CO2/kg of nanoparticles produced. The technology is being scaled to produce industrially relevant quantities of metal nanoparticle catalysts for deployment at pilot scale.

Activated SilkTM is a liquid formulation of silk protein developed by Massachusetts-based Evolved By Nature, Inc. with broad utility across industries for the manufacture of silk-based products that are safe for humans and sustainable for the environment. Evolved By Nature&#;s process for purifying and solubilizing silk fibroin protein is free from toxic chemicals, requiring only pure, silk cocoons, non-toxic salts, and water. This replaces harsher hydrolysis methods for the preparation of silk with a green chemistry method that requires no wastewater management as both the salts used and the biodegradable Activated SilkTM are safe to enter waterways. The unique structure of silk fibroins affords silk properties such as remarkable strength and toughness compared to other biomaterials and the ability to adopt different structural conformations. These properties can be leveraged in a variety of applications beyond silk textiles, often replacing hazardous substances with one that is non-toxic, renewable, requires less energy to produce, and generates less waste. In particular, Evolved By Nature has developed a robust line of skincare products with Activated SilkTM as a key ingredient and is developing Activated SilkTM for use as both a finishing agent in textile manufacturing and as an emulsifier. In these markets, the non-toxic Activated SilkTM is replacing harsh or toxic chemicals in products that come into contact with human skin with a natural protein that is biocompatible. Silk Therapeutics, the skincare arm of Evolved By Nature, has been manufacturing and selling products containing Activated SilkTM that are clinically proven to firm and smooth skin since Here, Activated SilkTM is replacing synthetic preservatives while at the same time promoting skin health. Moving forward, Evolved By Nature is developing simple manufacturing processes using Activated SilkTM as a finishing agent in place of synthetic chemicals that can be integrated seamlessly into any textile mill.

Transformer oil, despite not being the first concern, is essential to the electricity sector. With the population expected to expand from 7.4 billion to more than 9 billion in *, power requirements increase and transformer oil consumption rises. Each year, millions of tons of oil reach end of service life. It is deemed unfit because of accumulated contaminants and loss of performance, rendered obsolete and considered a potential hazardous waste. Another danger are PCBs, widely used before being banned in , they still routinely enter collections streams. Used oil management is therefore a major environmental issue due to its hazardous nature. Hydrodec successfully developed a catalytic hydrogenation process that protects the environment by reducing hazardous chemicals. The feed, used transformer oil, is exposed to reducing conditions at elevated temperature and pressure so as to remove contaminants. The reaction occurs in a hydro-treating reactor in presence of a catalyst. The catalyst, a spectator, is neither consumed nor wasted. The excess Hydrogen generated is separated and recirculated back. The refined oil is then quenched, water washed and de-watered to produce SUPERFINE&#; oils. The process was developed in by researchers to find a way to deconstruct potential cancer-causing PCBs from used transformer oil. In Hydrodec was founded to commercialise the technology. The first plant was built in Australia in , followed by Canton, Ohio ten years ago. In , Hydrodec US avoided 6.7 million gallons of used oil to become waste. The total of PCB contaminated oil received between and was 339.377 gallons, equalling to 387.11 pounds of PCBs destroyed. Hydrodec is also a carbon credits generator approved by the American Carbon Registry. The used oil is treated to a quality indistinguishable from virgin oil. SUPERFINETM is a high performing product. It exceeds performance levels required by international standards. *According to the International Energy Outlook --- This technology, &#;Refining of used oil&#; (US Patent number: ) is beneficial to both human health and environment. It reduces toxic pollution by eliminating the hazards of chemical feedstocks and preventing CO2 emissions. It&#;s an effective source reduction process that destroys PCBs, a hazardous substance. The proprietary solution, a hydrogen halide scavenger like for instance an ammonium hydroxide, reacts with the feedstock containing PCBs. This technology step avoids the most generally technique used in oil recycling: a caustic treatment which is a potential health and safety risk. And this results in a mineral oil fully dechlorinated and an ammonia chloride as a salt as by-product, less hazardous then ammonia itself and much preferred than hydrogen chloride seen in other process. The production output since February has been NON detect for PCBs (<1 mg/kg). The technology also addresses one aspect of the increasing energy demand issue and its subsequent waste generation. By restoring used transformer oil back to initial quality to be re-used for original purpose, Hydrodec can be fully circular and improves the use of natural resources. For each ton of oil refined, more than one ton of crude oil is saved, providing waste reduction, resource conservation and reducing the petroleum dependency. The typical used oil waste treatment is to be burnt as fuel, releasing GHG into the atmosphere. By recycling transformer oil, Hydrodec technology avoids CO2 emissions and is a pioneer in the industry in being awarded carbon credits by the American Carbon Registry (ACR). The approved rigorous emissions reduction accounting methodology calculated that so far, more than one quarter of a million carbon credits has been generated. So all taken into account, SUPERFINETM is a truly sustainable and renewable petroleum product. It&#;s also &#;one of a kind&#; technology. Other players re-refine lubricants, albeit not enough to solve the current environmental challenge, but only one direct not very active competitor is known. At Hydrodec, we specialize in only one type of lubricant, used transformer oil re-refining, allowing the process to obtain a superior quality and the possibility for a truly closed loop circular offer. We believe that &#;waste is a resource in the wrong place&#; and that the old mentality &#;new is best&#; isn&#;t valid anymore. We&#;re tirelessly working to shift this attitude. That is why we value the Green Chemistry Challenge Award Program, we are honoured to participate and we hope that this initiative will be another tool to help us overcome our main obstacle: changing mind-sets to a greener path.

These are days of unusual urgency in sustainable products research. The prevailing, worldwide "petroleum economy" is at the center of a contentious debate regarding issues no less weighty than the health of the planet itself. Calls for the rapid implementation of measures to limit the use of fossil carbon for the production of fuels and polymers have made way for sustainable technologies to fill the void. As such, a variety of schemes for the exploitation of cellulosic biomass have been advanced. While these vary considerably in detail, they all seek to achieve the same basic objective, i.e. the efficient production of marketable products that will displace petroleum from the global carbon cycle. One molecule at the center of the debate has been 5-(hydroxymethyl)furfural, or HMF. It is a platform molecule of exceptional synthetic versatility. However, from an industrial perspective, HMF is the revolution in sustainable chemistry that is still waiting to happen. Despite thousands of publications that have appeared involving HMF in one context or another, it is still only practically derived from fructose, a food sugar derived mainly from cereal grains. In a process was developed at UC Davis which overcame the limitations of HMF. The method involves acidic digestion of carbohydrates in a biphasic hydrochloric acid/solvent reactor under mild conditions to give 5-(chloromethyl) furfural (CMF). CMF retains all the synthetic advantages of HMF and yet can be produced in high yield directly from raw biomass. The CMF process is the first step of Origin's technology for producing biobased terephthalic acid (TA), one of the monomers of PET. The following steps, i.e. catalytic reduction to 2,5-dimethylfuran, cycloaddition with bioethanol-derived ethylene, and catalytic air oxidation to TA, complete the synthesis of the NaturALL bottle, which is on schedule to enter into commercial production in .

Since the s, hydrogen peroxide has been manufactured from natural gas using the Anthraquinone Autooxidation (AO) Process. Globally, there are around 100 AO plants in operation, and on average, one plant explodes per year. It has become increasingly expensive to build AO plants in the US and EU (>$100M). As such, new plants are built to less stringent standards in the developing world, increasing the global logistical challenges of shipping peroxide. Although hydrogen peroxide is a green molecule that decomposes into just water and oxygen, the AO process emits more than 2 tons of CO2 equivalences per ton of peroxide. Today, millions of tons per year of oxygenates (e.g. alcohols, aldehydes, sugars etc.) are partially oxidized to high value products. During these processes, molecular oxygen undergoes complete reduction to water, resulting in millions of tons per year of wastewater that must be treated. What if instead of making wastewater, each of these processes produced high-value hydrogen peroxide? This is Solugen&#;s Partial Oxidation Platform (POP), and this is BioperoxideTM. Using a combination of machine learning and directed evolution techniques that formed the basis of the Nobel Prize in Chemistry, Solugen engineers highly stable and inexpensive enzymes that co-produce high value partial oxidation products and BioperoxideTM. These enzymes are incorporated into lean, continuous, and modular chemical process units that enable the onsite production of green chemicals, reducing cost and associated carbon emissions. Solugen&#;s POP can deliver a double-digit internal rate of return even at scales below 5,000 tons per year. By starting from a sugar feedstock and reducing transportation complexity, more than 6 tons of CO2 is removed from the environment per ton of BioperoxideTM manufactured. Solugen operates a fully automated, continuous pilot plant 24/7 in Houston, TX and is constructing its first commercial plant in .

The average industrial production plant uses and discharges between 2,000 lbs and 12,000 lbs of phosphate annually for corrosion and deposition inhibition in cooling water systems. This results in multiple challenges, two of which are: 1, Phosphate deposition reduces heat transfer efficiency, increases energy and water usage, and limits production, costing plants significantly. And 2, discharge of phosphate to natural water bodies upsets the natural ion balance causing massive algae growth, oxygen and critical nutrient reduction, potentially resulting in the death of fish and other biological species. This same 2,000 lb &#; 12,000 lb phosphate discharge can result in up to 1.2-7.2 Million lbs of algae growth in, around, and downstream of the cooling water system. Regulated algaecides are traditionally used to kill the resulting algae growth, requiring hundreds if not thousands of pounds of biocide handling and addition to the water stream. Mitigation strategies have previously used heavy metals, priority pollutants and organo-phosphonates to reduce phosphate usage while protecting production equipment from costly corrosion and deposition. These additives were never able to successfully, wholly replace phosphate and added their own set of concerns in effluent waters. E.C.O.Film (Engineered Carboxylate Oxide) technology, recently developed using surface film engineering, advanced understanding of competing ion and salt saturation on surfaces in aqueous environments, and wide-ranging molecular profiling, eliminates the need for phosphate usage as a deposit or corrosion inhibitor in cooling water systems with the same or improved corrosion inhibition versus phosphate-based programs. This new Carbon-Hydrogen-Oxygen (CHO) Inhibitor approach eliminates phosphate deposition issues, eliminates phosphate contribution to effluent water streams from cooling water chemical products, reduces algae bloom formation and reduces the need for algaecide usage. As of Q4 , E.C.O.Film products are commercially available and have already proven successful in field applications, the results of which are also discussed in this submission.

The nominated technology enables selective recovery of rare earth elements (REEs) and cobalt from waste materials such as magnets, including those contained in e-wastes e.g. hard drives and motors. Neodymium, samarium, dysprosium, praseodymium, terbium and cobalt are critical for advancing modern technologies like wind energy, clean transportation, industrial automation, consumer devices, and advanced manufacturing. However, lack of source diversification and the ever-growing demands for these materials create risks of supply disruptions, price spikes, market uncertainties and limited/lack of deployment of dependent technologies. As the market share of clean energy increases and electrification displaces fossil fuels at the point of use, the demands for these elements will increase faster and more waste stream available for recycling. Recycling can help mitigate supply disruption risk and its consequences. If done well, it can conserve resources, save energy and reduce gaseous, liquid and solid wastes. However, typical hydrometallurgical REEs recycling routes employ acids for dissolving feedstock, which is both hazardous and creates acid-contaminated wastes: an environmental risk. Non-selective strong mineral acids &#; hydrochloric, sulfuric or nitric &#; are commonly used as solvents but they aggressively dissolves metallic components and make subsequent separation steps expensive and inefficient. Even when desired materials can be pre-concentrated, such pre-treatments can be cost-prohibitive and time consuming. The nominated technology overcomes the limitations of conventional hydrometallurgy by selective dissolution of target materials via a simple, robust and reliable process. Instead of acids, magnets are dissolved, including those in devices, by immersing feedstock in water-based neutral solution. The acid-free dissolution process eliminates the need for pre-treatments while producing >99.9% pure REEs. High purity oxides of neodymium, dysprosium, praseodymium, terbium, samarium and cobalt have been recovered from industrial magnet and Terfeonl-D wastes. Recovered materials have been proven suitable for reinsertion into supply chain. All of these outcomes are achieved using an environmentally benign process.

Asymmetric Catalysis in Water: Hydroxyphosphine and Hydroxyphosphinite Ligands for Amino Acid Synthesis: A series of chelating bis-phosphinite ligands with acid sensitive protecting groups were prepared from readily available sugars, a,a-trehalose and D-salicin (2-(hydroxymethyl)phenyl-D-glucopyranoside). Deprotection of the ketal protecting groups in these compounds with acidic resin in methanol eventually gave water soluble cationic Rh complexes that were competent to effect highly efficient hydrogenation of acetamidoacrylic acid derivatives in organic, aqueous or biphasic media. However, enantioselectivities of these reactions in neat aqueous or biphasic media are generally lower than those observed in organic medium.

As a solution to this problem, two different protocols for the preparation of water soluble, enantiomerically pure polyhydroxy-bis-phospholanes from D-mannitol are reported. These procedures circumvent two of the commonly encountered limitations in the synthesis of these potentially important ligands: (a) formation of phosphonium salts from the highly basic phosphines under acidic conditions; (b) the need to start with preformed fully protected cationic metal complexes. Cationic Rh complexes of these ligands have been prepared in a separate step, and they have been found to be excellent catalysts for organic and aqueous phase hydrogenation of dehydroaminoacids. The viability of catalyst recovery has been demonstrated in three different systems, including in two cases where >99% ee can be achieved under recycling conditions (up to six cycles).

"Knockout": A Dynamic Cleaning Experience, In a Colloidal Format, With Pollution Prevention Qualities: "Knockout" brand multipurpose cleaner has been developed and commercialized over the past five years as Earthday Products and their grand rollout of the current identical product under the banner of "Knock Out Products" will occur in January . This mixture of chemicals is non-toxic, biodegradable and for general use around the home or office.

The unique mixture of existing safe chemicals, timing and sequencing of mixing and the built in unique safety of the mix, which contains 98% water will forever prevent pollution due to the extremely small amount of active ingredient necessary to make the product effective. Water is the customers" preferred medium, and it is an excellent solvent and carrier for small amounts of emulsifiers for general cleaning. Currently cleaners contain harsh chemicals with an extremely low or high pH, that are highly bleaching or oxidizing or that create non-degradable by-products in the environment once the product is used. The "Knockout" brand of household cleaners are 100% biodegradable, cause less chemical to be used initially and create no toxic by-products.

2-Methyltetrahydrofuran: A Green Alternative to Oil Derived Ethers and Chlorinated Solvents: 2-Methyltetrahydrofuran (2-MeTHF) is the only aprotic solvent derived from renewable resources. The pentoses from agricultural waste such as corncobs cyclize to furfural in aqueous solution; furfural is further dehydrogenated to 2-MeTHF. As the largest producer of corn in the world, the United States provides a dependable supply of corncobs as waste from the food and bioethanol industries.

Pennakem initiated and developed the global market for 2-MeTHF as a green alternative to petroleum-derived ethers and volatile chlorinated solvents. Pennakem&#;s proprietary technology produces 2-MeTHF with hydrogen from natural gas and water as the solvent. 2-MeTHF can reduce process mass intensity (PMI) to facilitate greener processes in chemical manufacturing. Substituting 2-MeTHF for tetrahydrofuran (THF) can lead to

(1) higher reaction yields (reducing PMI for organometallics by 15&#;30 percent);

(2) increased solubility of organometallic reagents (reducing PMI by 30&#;50 percent);

(3) higher extraction yields during workup (reducing PMI by 15&#;30 percent);

(4) one-pot reactions due to cleaner reactions, increased solvent stability, and easy phase separation (reducing PMI by 50 percent for 2 steps); and

(5) elimination of hydrophobic cosolvents (reducing PMI by 30 percent).

Switching to 2-MeTHF could eliminate 30,000 metric tons of THF per year along with 30,000 metric tons of hydrophobic cosolvents from Grignard workups. Because THF and cosolvent mixtures are often incinerated, substituting 2-MeTHF may reduce carbon dioxide (CO2) emissions up to 90 percent.

2-MeTHF is easier to dry and recycle due to its rich azeotrope with water (10.6 percent) and simple distillation at atmospheric pressure. The energy savings for 2-MeTHF recycling are approximately 70 percent compared to THF. Other advantages for 2-MeTHF are improved process safety, lower chemical oxygen demand (COD) in effluent waters, and lower emissions of volatile organic compounds (VOCs).

Recently, CPS-Chirotech in the United Kingdom reported the first industrial application that substitutes 2-MeTHF for dichloromethane; this expands the potential for 2-MeTHF to substitute for chlorinated solvents.

440-R SMT Detergent Hazardous Solvent Alternative for Printed Circuit Board Stencil Cleaning: 440-R SMT Detergent uses proprietary acidic surfactants which act to buffer the sodium silicate base to bring the useable concentration of 440-R SMT Detergent to within non-hazardous pH limits (11.0&#;12.0 pH). A purple dye and a mild citrus fragrance are added for identity and quality control purposes and to prevent the possibility of unpleasant odors in the workspace.

The surfactant formulations are critical in that they must not only address the flux contaminant, but must also clean effectively at low temperatures (<110°F). It is established that SMT stencils are heat sensitive. The adhesives used to bond the stencil screen to the frame and to the metal etched foil are heat-cured at approximately 160°F. Hot wash solutions will breakdown the stencil adhesive and cause detachment. Temperature fluctuations also cause expansion and contraction of the various metals used to construct a stencil leading to minor distortion of fine-pitch apertures causing misregistration and production misprint problems.

Care was taken not to introduce any additional hazardous or restricted ingredients into an already hazardous cleaning application. By using only non-hazardous and non-VOC ingredients, 440-R SMT Detergent wastewater qualifies for routine liquid evaporation, eliminating the need for drain discharge and liquid hazardous waste disposal.

A Durable Hydrodechlorination Catalyst for Selective Conversion of CCl4 to CHCl3: In , the Montreal protocol was signed, which called for a freeze on the production and use of chlorofluorocarbons at levels with subsequent reductions and complete elimination by January 1, . A similar ban applies to carbon tetrachloride, also due to environmental concerns associated with ozone depletion, global warming, and ground-level smog. However, in the production of methylene chloride and chloroform, carbon tetrachloride is produced as a byproduct. It is estimated that in the United States and Europe, there are about 60,000 tons excess CCl4 produced per year.

The disposal of this byproduct, CCl4, typically by incineration, has become an environmental challenge and major economic burden to manufacturers of methylene chloride/chloroform. Hydrodechlorination of carbon tetrachloride to chloroform is an attractive alternative to the disposal of byproduct carbon tetrachloride by incineration. Until now, the catalytic conversion of CCl4 to CHCl3 has been problematic due to lack of catalyst, selectivity, poor conversion efficiency, and catalyst deactivation.

Akzo Nobel made the elegant discovery of treating an aluminum oxide supported egg shell type platinum catalyst with an ammonium chloride solution. This provides a remarkably durable catalyst, with high conversion of CCl4 to CHCl3 that resists deactivation for over 2,000 hours. In contrast, untreated catalysts were rapidly deactivated with conversions dropping from 90 to 2% within one hour. The treated catalyst provides a cost-effective, efficient method for the conversion of carbon tetrachloride to chloroform. Akzo Nobel BU Base Chemicals is in the process of implementing this technology internally and might offer it for commercial licensing in the future.

A Green Analyzer for Arsenic in Drinking Water: Arsenic is an abundant element that is also a class A human carcinogen. Waterborne arsenic is a problem in drinking water worldwide and is typically of natural origin. In , the U.S. EPA lowered the allowable As content of U.S. drinking water from 50 ppb to 10 ppb. U.S. EPA and U.S. Geological Survey (USGS) assessments show that approximately 32 million people in the United States drink water containing 2&#;50 ppb As. Making accurate measurements of arsenic in drinking water is critical to meeting the new standard. Presently the only techniques approved by the U.S. EPA are those that use atomic spectrometry.

Technology for affordable analysis of arsenic in the field is particularly needed in small water systems in the United States and in developing countries. The most common field analysis method is based on the over-100-year-old Gutzeit reaction chemistry. It uses toxic lead acetate, mercuric bromide (HgBr2), and large amounts of sample to measure As levels near the 10 ppb limit. It also creates costly disposal problems.

Professor Dasgupta invented an affordable field analyzer (costing less than $2,500 for parts) that is unique, USGS-validated, small, robust, and fully automated. It uses an order-of-magnitude less sample, requires no toxic chemicals, and can measure As down to 0.05 ppm, rivaling atomic spectrometers that cost much more. The technology is based on the gas-phase chemiluminescence of arsine (AsH3) and ozone. It uses sodium borohydride, sodium hydroxide, disodium ethylenediaminetetraacetic acid (Na2EDTA), and sulfuric acid as reagents. The technology measures both As(III) and As(V) in 3 mL samples of water within 4&#;6 minutes. Because some water treatments only remove As(V), monitoring and remediation require highly sensitive techniques that can measure As(III) and As(V) separately. Professor Dasgupta filed patent applications in and for this technology.

A Green Process for the Synthesis of Quinapril Hydrochloride: Pfizer emphasized green chemistry objectives in redesigning its process to manufacture quinapril hydrochloride (HCl), the active ingredient in the important cardiovascular medicine, AccuprilTM. The resulting process employs more efficient chemical transformations with dramatic environmental and worker safety improvements. Process yields have increased by 30%; process throughput has quadrupled. The process has eliminated methylene chloride and dicyclohexylcarbodiimide. Operations that caused loss of yield due to the intermolecular cyclization of quinapril HCl have been minimized.

Overall, Pfizer&#;s improvements have eliminated the isolation of one intermediate, two drying steps, and a hydrogenation step. The environmental and safety improvements are dramatic. Pfizer&#;s process has eliminated the use of approximately 30 metric tons per year of dicyclohexylcarbodiimide and the subsequent generation of 30 metric tons per year of solid dicyclohexylurea waste. The process has also eliminated the use of approximately 1,100 metric tons per year of methylene chloride. The volume of solvent has been reduced dramatically; aqueous and organic wastes have been reduced by 90%. Pfizer&#;s process reduces raw material, water, and energy use significantly. The new process was readily transferred to Pfizer&#;s manufacturing facilities.

A Green Revolution with NanostructuredTM Chemicals: Hybrid Plastics&#; has developed and commercialized a revolutionary green building block technology based on POSS(TM) Nanostructured(TM) Chemicals. POSS(TM) can be derived directly from commodity silanes or sand/silica, the most abundant component of the earth&#;s crust. Their nanoscopic size renders them VOC free while their hybrid "organic-inorganic" composition provides them with inherently low flammability and excellent oxidative stability. They dramatically improve the thermal and mechanical properties of traditional polymers while offering turnkey incorporation using existing manufacturing protocols. They are biocompatible, recyclable as silica, and are competitively priced with traditional performance material technologies.

A Microwave Oven Dissolution Procedure for a Ten Gram Sample of Soil Requiring Radiochemical Analysis: A microwave soil dissolution procedure was incorporated into a standard analytical method for testing soils for americium and plutonium. This modification displaces several hot plate dissolution steps by incorporating a microwave oven with new commercially available products. The new procedure uses a commercially available microwave oven that has the capability to monitor and control the pressure and temperature of a control vessel using a feed back system. The ability to repeatedly obtain and control desired temperatures and pressures has resulted in improved analytical precision because the reaction conditions can be reproduced.

This new procedure also reduces the consumption of hazardous substances, the amount of air pollution produced, worker exposure to hazardous substances, and sample preparation time. The use of closed vessels in this modified procedure also results in reduced hazardous reagents use. Less reagents means less hazardous waste and air pollution are produced, and reduced worker exposure to the reagents. In addition, the use of the microwave oven reduces the time requirements from two to three days for the hot plate procedure to eight hours.

A New Corrosion Inhibitor Reduces the Environmental Impact of Industrially Treated Water: Industrial water treatment systems suffer from the dual challenges of mineral scale fouling and ferrous metal corrosion. Scale and corrosion result in loss of flow, leaks, and general wasting that lead to plant shutdowns, high capital costs, and unplanned maintenance charges. To minimize the impact of these failures, chemical scale and corrosion inhibitors are added to the water in industrial cooling systems. Chemicals traditionally used as scale and corrosion inhibitors include phosphates, polyphosphates, phosphonates, and treatments based on zinc or molybdate. Concern for the environmental impact of metals and phosphates has led to increased oversight of the use of these materials. Broader implementation of discharge limitations is one means for reducing the impact of these chemicals on the environment, but it places industrial water users under greater burden to manage scale and corrosion in their water treatment systems.

Nalco developed a new inhibitor for cooling water applications, phosphinosuccinic oligomer (PSO), which has shown superior scale and corrosion protection. PSO also reduces or eliminates the need for zinc, molybdate, and compounds that decompose to phosphate. The scale inhibition of PSO has led to more efficient water use because cooling systems use less water when they can operate at higher mineral ion levels. PSO functions as a cathodic inhibitor. It has replaced molybdate and zinc successfully in traditional corrosion inhibition treatment programs while providing a high level of corrosion protection.

The inhibitor is highly halogen-resistant. It does not revert to orthophosphate under normal conditions, allowing one to operate a cooling system with lower total phosphate levels compared with systems that use degradable polyphosphate. The cost and performance of PSO relative to traditional inhibitors have resulted in substantial reductions in the amount of zinc, molybdate, and phosphate used in water treatment. Between and , Nalco increased its use of PSO by 77 percent.

A New Environmentally Friendly Corrosion Inhibitor: Corrosion is estimated to cost the United States well over $300 billion per year. The industrial water treatment market for corrosion inhibitors is 50 million pounds per year, growing at 5 to 7% annually, with more than 500,000 individual use sites in this industry category. Exposure to corrosion inhibitors is thus a major concern. Conventional corrosion inhibitors used in industrial cooling systems are either hazardous to the environment or have other drawbacks, such as instability in the presence of oxidizing biocides, limiting their applicability.

A new, all-organic corrosion inhibitor, Bricorr® 288, a phosphonocarboxylate mixture, has been discovered and patented. Bricorr® 288 is a highly effective corrosion inhibitor with wide applicability to industrial cooling systems. Bricorr® 288 is an aqueous solution, does not contain VOCs (Volatile Organic Compounds), is halogen free (bromine, chlorine, etc.), is heavy metal free (zinc, chromate, etc.), and does not contribute to dioxin or AOX (Absorbable Organic Halide) formation. Bricorr® 288 has an environmental profile permitting, in many instances, discharge of treated water directly into rivers without any adverse effects.

In many cases, the recommended treatment level is at least an order of magnitude below that which would be toxic to fish. Bricorr® 288 is extremely water-soluble and, therefore, will not bioaccumulate. Bricorr® 288 has excellent handling characteristics due to its low mammalian toxicity, helping to improve safety. Additionally, the manufacturing process for Bricorr® 288 is environmentally benign in that it is solvent-free and does not result in discharges to water or air, nor does it produce any byproducts requiring disposal.

A New Process for Producing Dimethyl Carbonate: The nominated project is a process at the R&S stage for efficiently producing dimethyl carbonate (DMC) and ammonia from methanol and urea. The reaction is promoted by a novel catalyst-solvent system and is run under reactive distillation conditions. An ability to achieve near stoichiometric yields of DMC and ammonia has been demonstrated.

By recycling the ammonia to a urea plant in commercial practice, the net effect is to produce DMC from carbon dioxide and methanol. The commercial potential of the process has been evaluated by estimating capital and production costs for a large-scale plant and comparing the results with current state-of -the-art practice. The latter is based on the reaction of methanol, carbon monoxide, and oxygen in the presence of a copper chloride catalyst. The new process has significant environmental and economic advantages. DMC is a on-hazardous alternative to phosgene currently used to introduce carbonate functionality into a variety of commercial products (e.g., polycarbonates). The projected low cost of the DMC produced by the new process should substantially increase its use as an alternative to phosgene. Further at the projected low price DMC has been proposed as an economic an environmentally benign alternative to MTBE as fuel oxygenate additive.

A New Process for the Manufacture of Pharmaceuticals: In an effort to reduce the amount of waste generated at its East Hanover site, Sandoz Pharmaceutical Corporation has evaluated all site processes in order to make improvements in the utilization of solvents and minimize the waste byproduct while also improving operating efficiency. One process in particular was identified that appeared to offer significant opportunities for such process restructuring. After 2 years of research, all the essential elements of the new process have now been demonstrated.

The new process uses a single new solvent for both reaction medium and separation, which significantly reduces the overall solvent requirements and permits recycling of the used solvent by simple distillation. As a result, the process waste index is reduced from the current 17.5 pounds of waste generated per pound of product to 1.5 pounds, resulting in a projected reduction of 170,000 pounds per year in waste generation. Furthermore, the amount of solvent used per batch is cut in half, thereby significantly reducing the usage of solvent with attendant lower risks of worker exposure and accidental releases to the environment.

The decision to proceed with development of a new process, despite the potential problem of obtaining FDA approval of the process changes, is due primarily to the favorable economics of the new process. Conservative estimates of annual savings are around $775,000, compared to an investment of $2.1 million to develop and implement the new process, which is equivalent to a return on investment of 36.7 percent and less than a 3 year payback time. It is estimated that over 75 percent of the manufacturing savings are due to process improvements rather than disposal costs of unused solvent, illustrating the process optimization benefits characteristic for pollution prevention innovations.

A New, Highly Efficient, Environmentally Responsible Synthesis of Laropiprant (MK-): An environmentally responsible, highly efficient manufacturing process for laropiprant, Merck&#;s phase III prostaglandin D2 (DP) antagonist, has been achieved through significant scientific innovation. The combinations of laropiprant with niacin (MK-A) and with both niacin and simvastatin (MK-B) have shown promising efficacy for the treatment of atherosclerosis and are currently being evaluated in late-stage phase III clinical trials. An enzymatic route was developed to prepare over 25 kilograms of material for early clinical trials.

With optimization, this route would have been a satisfactory manufacturing process. Merck chemists set out to reduce the environmental impact of the process significantly, however, by developing a new, highly efficient, asymmetric synthesis with green chemistry principles in mind. In realizing this goal, Merck researchers discovered two unprecedented transformations. The first was a novel extension to the classical Fischer indolization reaction to prepare indole ene acids in a one-step, highly convergent manner from readily available starting materials. The second was the development of a novel asymmetric catalytic hydrogenation of indole ene acids.

The new synthesis is convergent and highly atom-efficient, involves minimal extractions, distillations, or aqueous washes, and makes minimal use of protecting groups. By implementing its new manufacturing route, Merck reduced its overall aqueous and organic waste production by 90 percent and 65 percent, respectively, compared with the enzymatic route. The technology discovered by Merck is an excellent example of the positive impact of scientific innovation on reducing the environmental footprint of a chemical process. It also embodies the association between innovation in green chemistry and business benefits. Because Merck discovered and implemented the new route early in the development timeline, Merck will be able to realize the environmental and cost benefits of the highly efficient synthesis for the entire lifetime of this important new medicine.

A Non-HAP (Hazardous Air Pollutant) Coating for Extruded Aluminum: The market for coatings of extruded aluminum is dominated by spray-applied, solventcontaining coatings that are heat-cured and are typically used for window frames, door frames, and other building components. This market is estimated to be about 35,000 tons in the United States. BASF has been supplying extrusion coatings to this market for many years. These coatings are based on hydroxy-functional polyester resins and typically contain about 25 percent solvents by weight.

Of this traditional solvent blend, approximately 60 percent is Aromatic 100 (which includes ethyl benzene), 15 percent is xylene, 5 percent is Aromatic 150 (which includes naphthalene), and 5 percent is diethylene glycol monobutyl ether. In addition, the traditional blend contains 5 percent methyl ethyl ketone, which was previously classified as a hazardous air pollutant (HAP), but is no longer considered a HAP. BASF developed a coating composition using a solvent blend without HAPs, which required the company to replace 90 percent of the solvents in the blend it had been using.

The new coating eliminates solvents that are known or suspected to cause serious health effects (such as cancer, reproductive effects, or birth defects) or adverse environmental effects. It replaces a product line formulated with five HAPs that accounted for 8&#;10 percent of the product as delivered. It eliminates xylene, diethylene glycol ethers, and several other materials. The new BASF coating meets the U.S. EPA&#;s standard for being non-HAP as defined in the Miscellaneous Metal Parts and Products Surface Coating NESHAP. The new product has improved application efficiency and quality; it is cost-competitive, with a modest premium of only about $1 per gallon. At market projections, this product will reduce emissions of HAPs by about 500,000 pounds annually. BASF initiated commercial sales of its product in and is phasing out its previous technology.

A Nontoxic Liquid Metal Composition for Use as a Mercury Substitute: Mercury is used extensively in switches and sensors, but is toxic to humans and animals. In addition to being an excellent conductor of electricity, mercury has significant surface tension and, unlike any other metal known, remains fluid throughout a wide temperature range which encompasses 0°C. Because of these properties, mercury is found in numerous commercial products such as automobiles, thermostats, steam irons, pumps, computers, and even in tennis shoes. In each of these cases mercury functions as a liquid electrical switch. Since billions of mercury switches are made worldwide each year, a non-toxic replacement appears highly desirable. A nontoxic, cost effective alternative to mercury that has comparable performance characteristics has been identified at Virginia Tech.

This green technology provides a gallium alloy containing indium, zinc, and copper that conducts electricity, freezes below 0°C, exhibits high surface tension, and possesses a very high boiling point and very low vapor pressure. In addition, non-mercury switches and sensors can replace mercury switches and sensors without modifying existing technology. Mercury also is used in temperature sensors, pressure activated switches, pumps and filters, slip rings, liquid mirror telescopes, fluid unions, dental amalgam, and in medical devices such as sphygmomanometers and bougies. The non-mercury material also can serve as a substitute for elemental mercury in a many of these applications.

A Nontoxic, Nonflammable, Aqueous-Based Cleaner/Degreaser and Associated Parts Washing Systems Commonly Employed in the Automotive Repair Industry: Circuit Research Corporation developed an aqueous based cleaner and associated parts washing system commonly employed in the automotive repair industry that eliminates the generation of hazardous waste associated with current parts washing systems. Currently, the majority of parts washers employ a 'Stoddard Solvent," which, when spent, is manifested as a hazardous waste to a distillation facility that separates the solvent from the petroleum residue. The new technology employs a nontoxic, nonflammable, aqueous-based cleaner/degreaser that can be recycled continuously on site by employing oil/water separation and standard combustion engine filters.

Both the oil separation and filtration apparati are housed within a recently developed parts washer unit, such that the aqueous cleaner/degreaser is recycled in-situ, eliminating the removal or transportation and special treatment of spent cleaner material off site. Testing results have shown that: (1) the resulting oil skimmed from the cleaner can, under current hazardous waste definitions, be managed as a 'spent oil" and combined with spent engine oil for beneficial reuse as a secondary fuel, and (2) the filter can be managed under current methods used to recycle other used combustion engine oil filters. Circuit Research Corporation believes there are in excess of 7,000 parts washers in Minnesota generating approximately 1.5 million gallons of spent Stoddard Solvent annually. Circuit Research Corporation"s alternative technology could significantly reduce the generation of this waste.

A Novel Additive System for Time-Controlled Degradation of Polypropylene: Iron(III)dimethyldithiocarbamate (FeDMC) and Nickel(II)di-n-butyldithiocarbamate (NiDBC) have been used in agricultural applications for their ability to create time-controlled degradation of both polyethylene and polypropylene upon exposure to sunlight. Polymers containing these additives in concentrations ranging from 0.001% to 0.5% by weight demonstrated a period of mechanical stability followed by a period of rapid degradation. However, the system has not been widely recognized as FeDMC decomposes at 180°C, significantly below the standard processing temperature for polyolefins. Experiments were carried out using Iron(III) Acetylacetonate (FeAcAc) in place of the dithocarbamate as part of the iron/nickel system in isotactic polypropylene. FeAcAc is stable under all standard processing temperatures.

A mixture of the additives and polypropylene pellets was extruded and melt pressed to create films. Spectroscopic and mechanical properties of the films were observed during lab exposure to ultraviolet light to follow the degradative process. Similar controllable degradative behavior was noted, indicating that this new additive system should be extendable to other polyolefins and should perform in all ways like the previous system except that it may now be processed under standard conditions, making time-controlled degradation much more accessible to industry.

A Novel Cleaning System Using Less Toxic, Safer Chemicals: The nominated process cleans and sanitizes the poly(ether sulfone) ultrafiltration (UF) membranes used in the dairy industry. The current, commercially available, cleaning process has been a three-cycle alkaline&#;acid&#;chlorinated alkaline system. Conventional alkaline cleaners typically consist of strong alkaline solutions of sodium and potassium hydroxide with a small amount of nonionic surfactants. The acid cleaners typically consist of high levels of phosphoric and nitric acids. The sanitizer contains sodium hypochlorite at 200 ppm in solution. The current procedure also requires large volumes of water to rinse and neutralize the membrane. JohnsonDiversey&#;s technology uses peroxygen chemistry to develop more efficient cleaners and germicides with safer and more environmentally preferable chemicals.

Their technology consists of an aqueous solution of hydrogen peroxide, a phosphorus-based acid, phosphonate, and an anionic surfactant. This new technology yields safer cleaners by formulating them at a more neutral pH. Hydrogen peroxide provides a good bleach alternative that sanitizes more gently than chlorinated alkaline sanitizers. Overall, this technology cleans and sanitizes effectively using less toxic chemicals than current alternatives; it is also safer with respect to human health and the environment.

This technology has a great economic impact by performing the cleaning and sanitization at lower temperatures; it saves energy by as much as 43 percent, reduces plant downtime by as much as 18 percent, decreases water use by as much as 33 percent, decreases wastewater generation, and improves the long-term stability of the UF membrane. During pilot plant studies, JohnsonDiversey&#;s peroxygen products demonstrated superior performance versus the current competitive products. Compared to the typical system, JohnsonDiversey has demonstrated average savings of $700,000 per dairy plant per year. As of the end of , JohnsonDiversey had tested and verified its new technology in a pilot plant membrane module for two years.

A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology for Industrial Biocatalysis: Enzyme-catalyzed reactions that require stoichiometric amounts of reduced nicotinamide cofactors (NADH and NADPH) have great potential in industrial biocatalysis, but many are underutilized because the cofactors are very expensive. Preparative applications require regeneration of the cofactors in situ, usually by a second enzyme with high specificity for a sacrificial substrate. Professor Zhao and his collaborators Professors van der Donk and Metcalf have developed a novel technology to regenerate NAD(P)H that is based on phosphite dehydrogenase (PTDH). Their technology is more efficient than the most widely used technology based on formate/formate dehydrogenase (FDH).

Professor Zhao and his collaborators discovered and characterized a wild-type PTDH enzyme from Pseudomonas stutzeri that catalyzes the nearly irreversible oxidation of phosphate to phosphate with the concomitant reduction of NAD(P)+ to NAD(P)H. Using rational design and directed evolution, they engineered a PTDH variant that exhibits drastically improved stability (its half-life of thermal inactivation at 45 °C is over 22,000-fold greater than that of the wild-type PTDH), activity (6-fold higher), and cofactor specificity (3.6-fold and 1,000-fold higher catalytic efficiencies for NAD+ and NADP+, respectively). Compared with FDH, PTDH has higher specific activity, a higher thermodynamic equilibrium constant (Keq = 1 x ), and a broader pH-rate maximum. In addition, the phosphite substrate is inexpensive; both the substrate phosphite and the product phosphate are innocuous and act as a buffer, and phosphate can be removed readily by calcium precipitation if necessary.

The three professors used a membrane bioreactor to demonstrate the advantages of this mutant PTDH over FDH for cofactor regeneration in the industrially important synthesis of L-tert-leucine and xylitol. Their PTDH system has broad applicability in industrial synthesis of unnatural amino acids, polyols, chiral alcohols, and products labeled with deuterium or tritium. Recently, BASF (Germany) and BioCatalytics (Pasadena, CA) licensed their novel PTDH-based technology.

A Novel Solid-Acid Catalyzed 1-Butene/Isobutane Alkylation Process: Alkylation reactions are employed to convert light refinery gases (C3-C5) into gasoline compounds (C7-C9). Alkylates constitute roughly 15% of the U.S. gasoline pool. At present, industrial alkylation employs either hydrofluoric acid or sulfuric acid as a catalyst. For more than three decades, numerous solid acid catalysts have been explored as environmentally safer alternatives to liquid acids.

However, solid-acid catalysts deactivate rapidly due to coke retention in the pores. In gas-phase media, the heavy coke precursors (such as olefinic oligomers) are poorly soluble. In liquid-phase reaction media, the transport of coke precursors out of the catalyst pores is severely restricted resulting in their readsorption and transformation to consolidated coke. The work of Dr. Bala Subramaniam at the University of Kansas employs supercritical reaction media, which offer a unique combination of liquid-like density and gaslike transport properties for the effective removal of the coke precursors.

Employing carbon dioxide (Pc = 71.8 bar; Tc = 31.1 °C) as an environmentally benign solvent, 1-butene/isobutene alkylation was performed at supercritical conditions resulting in virtually steady alkylate (trimethylpentanes and dimethylhexanes) production in a fixed-bed reactor on solid acid catalysts (HY zeolite, sulfated zirconia and Nafion) for several days. The carbon dioxide-based supercritical process thus offers an environmentally safer alternative to conventional alkylation by eliminating a major technological barrier impeding the application of solid acid catalysts in alkylation practice.

A Novel Waste Minimization Approach: Production of Carbon-Based Catalyst or Sorbent from Biosolids: Biosolids, a byproduct of wastewater treatment facilities, are currently a major environmental concern. Identified problems associated with the management of biosolids are the hazardous content, the large mass produced, the difficulties associated with its treatment, and the few available disposal methods. Furthermore, the production of biosolids has been increasing due to an increase in the world population. In , the United States produced 9 million tons of biosolids and is expected to produce 11 million tons/year by the year . Transformation of biosolids is a novel and innovative idea for waste minimization and recycling at wastewater treatment facilities.

An innovative process was developed to convert biosolids to carbon-based sorbents and catalysts. The feedstocks for the process were biosolids produced at a sewage treatment plant (Spring Brook Water Reclamation Center in Naperville, Illinois) and wastewater treatment sludge produced in the paper mill industry (Fort James Corporation in Green Bay, Wisconsin). The research conducted at the Illinois Institute of Technology suggests two new innovative ideas for the production of activated carbon from carbonaceous waste material:

1) exposure of the chemically activated raw material to light and humidity in a controlled environment can enhance the surface pore structure of activated carbons by about 20%, and

2) the time and energy required for the drying of sludge can be reduced by about 98% if microwave drying is used. The surface properties of the produced carbons were effectively controlled by varying different chemical, surface, and physical activation processes. This project demonstrates a tremendous potential for alleviating serious environmental problems associated with the mass production and disposal of untreated sludge by development of a process for converting sludge to activated carbon and catalyst.

A Practical and Green Chemical Strategy for the Manufacture of Neurokinin 1 Antagonist, LY: Eli Lilly and Company developed an innovative, environmentally benign route for the commercial production of an investigational new drug candidate. This candidate, LY, is an antagonist of the Neurokinin 1 (NK1) subtype of tachykinin receptor. It has undergone Phase II clinical trials for the treatment of anxiety and irritable bowl syndrome (IBS). LY is Lilly"s name for {2-[1-(3,5-bis-trifluoromethylbenzyl)-5-pyridin-4-yl-1H-[1,2,3]-triazol-4-yl]-pyridin-3-yl}-(2-chlorophenyl)-methanone. The improved route of manufacture delivers LY in exceptionally high purity (greater than 99.9 percent), despite its complex structure.

Eli Lilly and Company uses a metric called "e-factor" internally that is similar, but not identical to, Sheldon"s E-factor. The e-factor measures the total mass of all raw materials (including water) that are used to produce each kilogram of active pharmaceutical ingredient (API). Overall, the new route for LY has a net e-factor of 146 kilograms per kilogram API, which is an 84 percent reduction relative to the original route designed for Phase I clinical trials. Key technology developed includes a chemoselective SNAr reaction that has potential broad impact within the pharmaceutical industry. For example, industry-leading antidepressants ProzacTM and CymbaltaTM use SNAr chemistry in key manufacturing steps. In addition, COX-2 inhibitors such as pyrazolopyridines can potentially be prepared by this novel green methodology. Using the novel SNAr chemistry to manufacture these large-volume drugs could eliminate over 100 million pounds of processing waste per year.

Eli Lilly demonstrated the selected commercial route for LY on a pilot plant scale during in Indianapolis, IN. Two prior synthetic routes have been executed at pilot plant scale at Eli Lilly"s Indianapolis, IN and Mount Saint Guibert, Belgium facilities, respectively. Improvement of key green chemistry parameters across the evolution of these routes demonstrates the power of technical innovations and is a testimonial to the importance of incorporating green chemistry into the design and definition of synthetic processes.

A Preproduction System for Re-Refining Used Oil Using Closed-Loop, Patented, Atomization Technology: Only 14 percent of the approximately 2.4 billion gallons of lubricating oil used per year in the United States is recycled to reusable lubricating oil. Many companies that recycle oil use a simple thermal cracking operation that yields a highly unstable, low-grade fuel oil with low consumer acceptability.

FluidPhase is building a preproduction unit based on atomization in supercritical fluids to recycle lubricating oil into a highly stable, purified base lubricating oil in a cost-effective and environmentally friendly manner. Their new, innovative technology is a continuous process that mixes waste fluid with a supercritical fluid. The process exploits the difference in the solubility of the desired and the undesired components in the supercritical fluid. During the process, jet spray micro-orifices atomize waste oil into a supercritical fluid. The atomization process dissolves the reusable elements of the oil, leaving behind impurities and waste particles. Thus, polychlorinated biphenyls (PCBs) are removed early in the process, along with metals, sludge, and water. Undissolved components are separated by gravity, and the dissolved fluid is separated from the supercritical fluid. The system uses supercritical propane or another environmentally friendly solvent that is contained and recycled online. The byproducts from the extraction are used as binder material for asphalt, eliminating their disposal in landfills.

This preproduction system for re-refining used oil reached the pilot plant stage during . The pilot plant has the capacity to process 30 liters per hour of used oil in a continuous process; it has all the components of a larger commercial system. Members of the National Oil Recyclers Association have expressed interest in this technology.

A Safer, Environmentally Superior, High-Performance Acid Inhibitor Designed to Protect Metallic Infrastructure during Industrial Cleaning: Since the early &#;s, additives have been used to prevent base-metal attack by acids during industrial cleaning. These additives have made cleaning highly efficient through reductions in acid use, base-metal attack, and hydrogen generation, but early acid inhibitors were very toxic. Typical current products include heterocyclic amines and sulfur compounds, benzyl sulfonium salts, formaldehyde, naphthalene and pyridine derivatives, thioureas, propargyl alcohol, and alkylphenol ethoxylate surfactants (APEs), combined with solvents isopropanol or methanol and water.

Henkel has recently developed safer inhibitors including a new hydrochloric acid (HCl) inhibitor for steel mills that is free of propargyl alcohol and flammable solvents and is an inhibitor for a variety of acids used in food processing equipment cleaning. This invention involves high-performance inhibition that matches the high performance of the best current product. Henkel&#;s best inhibitor, Rodine® 213, is based on a sustainable raw material derived from pine tree waste. Rodine® 213-SF uses dehydroabietylamine solubilized with glycolic acid. For safety, paraformaldehyde replaces uninhibited 37-percent formaldehyde. The inhibitor reaction takes place in one step with zero waste. The use of poly(alkoxylated propargyl alcohol) and elimination of coproducts including vinyl methyl ketone and several chlorinated organics eliminates flammability and toxicity. Residual formaldehyde is reduced by 90 percent. Finally, alkoxylated natural fatty alcohols replace APE surfactants, which are estrogen mimics.

Replacing all of Henkel&#;s current sales of acid inhibitors with its new product would eliminate 27,300 pounds of propargyl alcohol, 94,680 pounds of alkylphenol alkoxylated surfactants, 68,750 pounds of isopropanol, 30,000 pounds of hydrochloric acid, 74,430 pounds of acetone, 13,480 pounds of vinyl methyl ketone, 28,640 pounds of 37-percent formaldehyde, 2,130 pounds of residual formaldehyde, and 630 pounds of chlorinated organics.

Henkel has completed final formulation improvements, testing, and reviews for full-scale manufacturing. Rodine® 213-SF is currently being advertised and sampled to potential customers.

A Safer, Less Toxic, Reliable, and Green Water Treatment by Smart Release® Technology: Smart Release® Technology is a controlled-release technology designed to prevent scale, corrosion, and microbial proliferation in water systems through the revolutionary delivery and application of existing chemical treatments. Initially, the technology focused on controlling corrosion and scale in cooling towers using tablets coated with a patented polymer that releases the treatment chemicals over a specified time period. In , Dober expanded its Smart Release® product line to include biocides in solid granular form by creating a patent-pending canister membrane that also releases the chemicals over a specified time period, often 30 or 60 days.

Treating cooling towers with Smart Release® technology has many advantages over traditional liquid water treatments. Unlike traditional treatments, Smart Release® technology does not require toxic additives. Smart Release® treatments contain 95 percent active ingredients compared to 10&#;20 percent active ingredients in liquid treatments. The technology uses no pumps and so requires no electricity. Reduced packaging and shipping weight lowers its carbon footprint by 74 percent compared to that of conventional liquids. This technology may also help facilities gain up to eight LEED (Leadership in Energy and Environmental Design) credit points. Benefits to humans include safe handling because the coating prevents contact with active ingredients.

Because the concentration of active ingredients is so high, 100 pounds of Smart Release® chemicals equate to 600 pounds of standard liquid chemicals. The simplicity and reliability of Smart Release® technology means that less service time is required. Smart Release® technology has been endorsed by two of the leading water treatment companies in the United States and a leading global supplier of cooling towers, fluid coolers, and evaporative condensers. During , Dober created an enhanced corrosion and scale-inhibitor tablet that contains no phosphate. Due to increased regulations limiting phosphate products, Dober expects this product to have large sales in the future.

A Systematic Methodology for the Design and Identification of Environmentally Benign Chemicals: Hydrofluorocarbon emissions from the refrigeration and air conditioning sector in the U.S. currently amount to approximately 13 million metric tons of carbon equivalent and are expected to grow to 38 million tons by . Retail food refrigeration accounts for 25% of these emissions: a typical supermarket leaks about 1 ton of refrigerant every year. The fundamental scientific goal of the nominated project is to reduce these major sources of environmental pollution by designing environmentally benign refrigerants. Using his pioneering optimization methods, Professor Sahinidis has invented a powerful way to search the astronomically large space of possible compounds and identify the entire set of compounds that are potentially suitable automotive refrigerants.

By extending this approach to secondary refrigerants, the Sahinidis team has identified over 3,000 potential secondary refrigerants. These secondary refrigeration fluids have an estimated potential of reducing supermarket refrigerant leaks by 90%. This project has yielded a large number of chemical structures that are entirely novel: some of them appear in databases but were never used as refrigerants while others do not even appear in databases of chemicals. Furthermore, the nominated methodology is applicable to the design of a very broad spectrum of compounds, including pharmaceuticals and industrial solvents. Because it produces the entire set of possible compounds that satisfy physical property requirements, this methodology enables the use of environmental criteria to design novel compounds that are environmentally benign.

Accelerated Solvent Extraction with Solvent Saver ModeTM: Reducing Organic Solvent Consumption and Waste in Laboratories: Accelerated Solvent Extraction (ASE®) is a sample preparation system that uses organic solvents at elevated temperatures and pressures to extract analytes of interest from solid or semisolid matrices prior to analysis. Higher temperatures increase the capacity of solvents to solubilize analytes; they also enable analytes to move faster from the boundary layer near the surface of the matrix from which they are extracted into the bulk solvent. Elevated pressures speed up the extractions overall. They also make it possible to keep solvents in a liquid state at temperatures above their boiling points, which is critical for efficient extraction. Dionex developed ASE® to replace traditional extraction techniques such as Soxhlet that require large volumes of solvent. The company&#;s intent was to develop a technique that was faster, safer, and more cost-efficient. Early results for the ASE® technology allowed extraction of a 10 g sample in 15 minutes with only 15&#;25 mL of solvent; a typical Soxhlet extraction requires 500 mL of solvent.

The end result, ASE® 350, is an automated system that greatly reduces the amount of organic solvent required to extract analytes. ASE® technology significantly reduces solvent waste, solvent vapors, and solvent exposure to laboratory personnel. With the introduction of the ASE® 350 system, users can reduce the amounts of solvent even further by activating the Solvent Saver ModeTM. This mode can save up to an additional 33 percent of solvent during each extraction. As one example, the amount of solvent required to analyze a year&#;s worth of 10 g samples is 49 L for the ASE® 350 system in the Solvent Saver ModeTM and 3,120 L for the traditional Soxhlet method. This is a significant decrease in the amount of organic solvent waste generated and the amount of solvent vapors released into the environment. Dionex introduced its ASE® 350 system in .

ACCOLADETM Synthetic-Based Drilling Fluid System: In , Halliburton introduced a revolutionary synthetic-based drilling fluid (SBF) called the ACCOLADETM system. ACCOLADETM is the first SBF to couple superior environmental compliance with exceptional drilling performance, allowing operators to drill with high efficiency while they minimize environmental impact in sensitive offshore areas. Halliburton formulated ACCOLADETM to exceed U.S. EPA&#;s environmental criteria for sensitive areas; ACCOLADETM is the highest rated of all drilling fluids for its low toxicity and high biodegradability. The system far exceeds all regulations governing discharge of cuttings generated with SBF for drilling offshore in the Gulf of Mexico.

ACCOLADETM contains no commercial clay or lignite additives; it is the only organophilic clay-free synthetic fluid on the market. The base oil is a blend of 50 percent vegetable oil esters (from palm and cocoanut oils) and an internal olefin. The ester component of the base fluid makes ACCOLADETM more biodegradable than conventional SBFs. ACCOLADETM is characterized by desirable rheological properties over a range of temperatures from 40 to 350 °F, properties that provide unprecedented control over viscosity and equivalent circulating density. The gel strength of the fluid develops quickly, but is fragile.

With ACCOLADETM, downhole mud losses normally associated with tripping, running casing, cementing, and breaking circulation are an average of 41 percent lower than those in wells using traditional SBFs. To date, ACCOLADETM has saved approximately 350,000 barrels (14.7 million gallons) of drilling fluid and has reduced total drilling additives. This reduction translates into fewer crane lifts, reduced transportation expense, and less exposure of workers to potentially hazardous operations.

Through , 20 different operators had used ACCOLADETM to drill over two million feet of holes for more than 190 oil wells in the Gulf of Mexico. In , ACCOLADETM also had its first international use, in Venezuela.

Acetylene: A Viable Fuel Alternative for the Internal Combustion Engine: Go-Tec has developed an environmentally clean dual- and multi-fuel composition for use in internal combustion engines. It contains acetylene as the primary fuel, along with a secondary, combustible fuel to prevent early ignition and knock. The secondary fuel is often ethanol or methanol, but may include other alcohols, ethers, esters, diesel (to fuel diesel engines), or another suitable fluid, such as mineral spirits. Go-Tec has used its acetylene-based fuels successfully in a number of prototype vehicles with gasoline or diesel engines.

Engines using Go-Tec&#;s acetylene-based fuel produce little or no carbon monoxide (CO), oxides of nitrogen (NOX), oxides of sulfur (SOX), volatile organic compounds (VOCs), or hydrocarbon (HC) emissions; they do not require catalytic converters. In addition, this fuel offers no buildup of residues in the engine, no particulate emissions, longer engine life, and greater fuel efficiency. With the low emissions realized in preliminary tests, Go-Tec&#;s fuel may be suitable for use indoors, opening up many other applications. Go-Tec is proceeding toward commercialization of this technology.

ACRAMITETM - A New Selective and Safe Miticide: ACRAMITE is a new selective acaricide from a unique class of chemistry with a novel mode of action, which was discovered by Crompton Corporation. It is effective on a wide variety of pest mite species while having little impact on beneficial insects and predatory mites. It demonstrates rapid knock down activity on mites while providing long residual plant protection. It is highly compatible with Integrated Pest Management (IPM) programs.

ACRAMITE has a very low acute mammalian toxicity, minimal chronic effects and no adverse reproductive or developmental effects. It poses minimal risk to applicators, handlers, and the general population including children. It has low risk to non-target terrestrial animals and plant species because of its low to moderate toxicity, lack of phytotoxicity, low use rate, and fewer applications. Residues readily dissipate and do not accumulate. It has minimal risk to aquatic animals and plant species because of its low water solubility, very short half-life in water and soil, and low potential for run-off into aquatic environments. Because of this safety, ACRAMITE will replace many less effective, more hazardous acaricides and contribute to lowering the total amount of pesticides used in the US. It contains no halogens or heavy metals.

The entire above mentioned array of attributes make ACRAMITE one of the safest, most selective acaricides for growers to use to produce high yielding crops in both conventional and IPM programs. ACRAMITE has been granted reduced risk status at EPA and is registered for use on ornamentals, apples, pears, stonefruit, grapes, strawberries, hops, and cotton.

Additives for Optimizing Renewable Resources in the Production of Polyurethane Systems and Plastics: As the world maintains its heavy reliance on oil, supply and demand are forcing manufacturers and consumers to find alternatives to petroleum-based products. Replacing petroleum-based polyols with biobased polyols in the polyurethane market is one potential way to reduce the need for oil.

Significant technical difficulties arose in early biobased polyol systems. The available acid groups in soy polyols caused hydrolytic degradation and variable reactivity, leading to polyurethanes with inferior properties. The additive technology from Rhein Chemie overcame many of these difficulties. Now, these green alternative systems are commercially viable products that reduce petroleum dependence, engage renewable feedstocks, and improve the longevity of polyurethane elastomers, adhesives, and foams. Currently, there are no known competing technologies with the same benefits as biobased polyol systems.

Rhein Chemie&#;s soy-based polyol additives have proven effective for producing low-density insulated spray foams. These particular soy-based systems use water as a blowing agent to replace chlorofluorocarbons (CFCs) and use flame retardants to reduce smoke effects as required for Class I Foams. The combination of these Rhein Chemie technologies enables their insulation system to be effective in reducing depletion of the ozone layer.

The Rhein Chemie insulation system comprises an ethoxylated soy polyol mixed with a common polyester, chain-extended with an isocyanate and modified with Rhein Chemie additives (such as Stabaxol® P 200 and Addocat® 102) to form a "green" polymer. The Stabaxol® additive, a carbodiimide, scavenges the acid groups on the biopolyols and improves both the reactivity and the hydrolytic stability of the foam system. The Stabaxol® additive also minimizes the deactivation of the catalysts by reacting out the acids that lead to variable reactivity. By , only two years after Rhein Chemie developed this technology, its additives were being used in low-density insulated spray foams for industrial, commercial, and residential insulation.

ADVAFLEXTM Organic Stabilizer: ADVAFLEXTM Organic Stabilizers (ADVAFLEX) are novel organic polyvinyl chloride (PVC) heat stabilizers primarily geared toward flexible PVC applications. While PVC is a versatile polymer with many useful properties, it cannot be processed without the addition of heat stabilizers. Conventional flexible PVC stabilizer technology relies on complex mixtures consisting of as many as 10 components, with primary active ingredients that include lead, cadmium, and barium compounds with metal contents in the range of 8 to 10%. Most of the components originate from nonrenewable resources, and many are health and environmental hazards.

ADVAFLEXTM is an entirely new concept in PVC stabilizer technology that offers numerous advantages over conventional stabilizers. First and foremost, these are two-com-ponent systems containing new organosulfur chemistry and low levels of metal activators, such as zinc. The performance advantages include excellent thermal performance, competitive costs, good secondary performance attributes, compatibility with coadditives chemistries, and simplicity of PVC formation. The environmental and health benefits include: very low metal content (as low as 0.4%); low odor and volatility; and the absence of barium, cadmium, lead, phosphorous, alkylphenol, and other aromatic chemicals that are used in conventional technology.

ADVAFLEXTM has undergone a thorough toxicity screening that demonstrates that the product is essentially nontoxic and not mutagenic, carcinogenic, or environmentally hazardous. The metal activators in ADVAFLEXTM formulations are generally required at catalytic levels, and the preferred metal, zinc, is a required element of the human diet. ADVAFLEXTM technology is a commercially attractive alternative that improves on all aspects of the conventional technology, especially with respect to human and environmental safety.

Advanced, Ecologically Safe De-inking Technology to Recover High Quality Pulp from Secondary Fibers/or Recyclable Waste : DeCopier possesses a proprietary chemical formulation capable of removing toner, wax, stickies and other contaminants from secondary fibers without damaging attached materials. The technology consists of a series of ecologically safe chemical formulations that separate the contaminants from secondary fibers without dissolving the polymers. This is a problem commonly encountered by de-inking mills.

DeCopier is developing technology for specific, high growth market opportunities in the de-inking of recycled office wastepaper, the complete destruction of high security documents and the recovery of reusable fibers in the manufacture of disposable diapers.

DeCopier plans to commercialize the following technology:
(1) Chemical formulations for use by de-inking mills to remove contaminants from secondary fibers
(2) Chemical solutions for separating absorbent polymer from diaper fibers, enabling them to be reused in diaper manufacturing

In sum, the advanced de-inking technology is an ideal candidate for the President&#;s Green Challenge Award. It enables paper and pulp mills to:
(1) To utilize cheaper grades of secondary raw material to produce high-quality pulp;
(2) Reduce the use of virgin pulp (prevent deforestation);
(3) Reduce the release of toxic effluents into sewage, and
(4) Reduce the waste going into the landfills/incinerators

Adventures in Green Chemistry: Trans-norsertraline is an active pharmaceutical ingredient (API) with promising activity in the central nervous system. Sepracor&#;s Process Research & Development Group devised a green route to trans-norsertraline using a catalytic asymmetric hydrogenation that replaces a process based on a stoichiometric chiral auxiliary. To implement this synthesis, Sepracor had to identify an effective catalyst for a challenging asymmetric hydrogenation. The company also had to develop novel chemistry for two steps surrounding the catalytic transformation.

Because large-scale access to enamides is underdeveloped, Sepracor scientists developed a novel, nonmetal-based methodology to yield a high-quality substrate for the key reaction. A chiral catalyst at low loading delivered the desired diastereomer in superb purity and yield. The amide product was hydrolyzed to yield the drug product.

To improve on its first-generation scale-up and further streamline the process, Sepracor reevaluated each step, creating a second-generation process. Sepracor refined the enamide methodology using toluene as the solvent throughout and eliminating both methanol and the energy-demanding distillation its use required. In partnership with Dow/Chirotech, Sepracor identified a rhodium catalyst that enhanced the selectivity of the reaction to 98:2. And finally, because amide cleavage on sensitive substrates is also underdeveloped, Sepracor designed a facile cleavage of the key intermediate under mild conditions to deliver material in good yield and quality. Compared to the first-generation synthesis, the second-generation synthesis reduces waste by 30 percent, has a 41 percent shorter cycle time, has a 15 percent higher yield, and uses less energy.

Because Sepracor implemented the more efficient process early during the development cycle, the company will receive the environmental and economic benefits for the entire product lifecycle. Sepracor developed this chemistry during and ; the company subsequently used it to produce 75 kilograms of high quality material at plant scale.

AeroClay®: A Green Aerogel for Industry: Expanded polystyrene (EPS) is made from polystyrene (PS), a petroleum product. It is used as a packaging material, thermal insulator, and acoustical insulator. PS is foamed into EPS beads using pentane, a volatile organic compound (VOC), as the blowing agent. The EPS beads are expanded and molded into blocks, which are then cut into specific shapes as required for various applications. Of the 2.62 million tons of polystyrene generated in , only 0.8 percent were recycled and less than 1 percent were incinerated for energy.

AeroClay® is a sustainable, tough, lightweight material that has the potential to replace EPS. AeroClay® is made by mixing clay and biodegradable polymers such as casein or poly(vinyl alcohol) with water, pouring the mixture into molds, and then freezing and freeze-drying it. Water is both the only byproduct and the only processing aid in AeroClay® manufacture, so byproduct water can be incorporated back into the manufacturing process. AeroClay® can be formed into a variety of molded shapes to meet many demanding applications, eliminating the need for cutting or shaping to fit any one application. It is water-soluble and is expected to be biodegradable.

AeroClay® eliminates worker exposure to styrene, a suspected carcinogen, and does not require any blowing agents. Instead, AeroClay® uses poly(vinyl alcohol) and clay, which are essentially nontoxic, nonhazardous materials that would not harm workers who are currently exposed to chemicals during EPS manufacture. AeroClay® would also reduce the amount of waste in landfills. Because it is biodegradable, AeroClay® does not take up space in landfills or cause pollution during production or incineration. AeroClay® is also less flammable than EPS, while providing similar mechanical properties in packaging and insulating applications. During , Aeroclay, Inc. established a pilot facility in Cleveland, Ohio, to produce and test prototypes and to produce small batches.

AGROTAIN® N-(n-butyl)Thiophosphoric Triamide: Urea is now the favored form of solid nitrogen-containing fertilizer and is rapidly displacing anhydrous ammonia in the nitrogen fertilizer market. The market share of world nitrogen consumption has risen from 5% in to 37% in for urea. There are many reasons for this increase. Urea is a source of nitrogen for crop fertilization that is easily handled and transported, higher in nitrogen content than other common solid nitrogen fertilizers, and can be readily bulk blended with other fertilizer components such as potassium chloride, diammonium phosphate, and other materials to prepare multinutrient fertilizers.

While urea has many advantages over other nitrogen sources and has already captured a greatly increasing market share, a major drawback to the use of urea is its tendency to lose a substantial portion of the nitrogen values by ammonia volatilization. These losses can easily exceed 30% of the available nitrogen in urea under certain climatic and soil conditions. AGROTAIN® is a formulation containing N-(n-butyl) thiophosphoric triamide (NBPT) the precursor to the active ingredient, N-(n-butyl) phosphoric triamide (BNPO, the oxygen analog of NBPT). BNPO is far too unstable to be an article of commerce. NBPT serves as an effective precursor to BNPO, a urease enzyme inhibitor that inhibits the hydrolysis of urea by inhibiting the activity of the urease enzyme that catalyzes its hydrolysis.

This activity is the result of an interaction between the urease enzyme and the urease inhibitor. There is no interaction with soil microbes that generate the urease enzyme. Moreover, the recommended NBPT treatment rate is only 0.4 lb/acre, and NBPT is relatively unstable and presents no problems with long-term buildup in the soil. The use of NBPT with urea is also ideally suited for no-till agriculture applications. No-till agriculture is an environmentally friendly approach that involves little or no disturbance of the topsoil, resulting in less soil erosion and less energy intensive operation. Urea, however, has not been well suited for use with surface-applied no-till applications until the advent of NBPT because of the possibility of substantial ammonia volatilization losses.

Airflex® EF811 Vinyl Acetate Ethylene (VAE) Emulsion Polymer: A Binder for Environmentally Friendly, High-Performance, Cost-Effective Architectural Coatings: Air Products Polymers, L.P. has solved a regulatory compliance problem for paint manufacturers by developing a safer chemical. The architectural coatings industry is being challenged to implement strict environmental regulations that significantly reduce the level of volatile organic compounds (VOCs) added to water-based paints as solvents. Vinyl acrylics, the workhorse polymer for architectural coatings, typically require significant levels of added solvent. Many of the polymers used in paints currently require added solvent to form a film that will adequately protect the painted surface. Historically, paint performance has been significantly compromised as solvent levels are reduced.

Air Products Polymers has developed Airflex® EF811 emulsion, a new vinyl acetate&#;ethylene (VAE) copolymer that solves this formulation challenge. Airflex® EF811 emulsion can be formulated at very low solvent levels, replacing vinyl acetate. Airflex® EF811 emulsion provides superior performance and is priced similarly to vinyl acrylics. Prior to the development of Airflex® EF811, the higher cost of VAEs versus vinyl acrylics had inhibited adoption of this technology into the large coatings market and its vinyl acrylic segment. Airflex® EF811 is being purchased or evaluated by most major U.S. paint companies. Broad replacement of vinyl acrylics with Airflex® EF811 emulsion will significantly reduce solvent use, improving indoor and outdoor air quality.

Aldimine-Isocyanate Chemistry: a Foundation for Environmentally-Friendly High Solids Coatings: The single greatest challenge that the chemical industry faces today is the design and manufacture of new chemicals that are not only efficacious, but just as importantly, environmentally friendly. Within the coatings industry, these new chemicals play the additional role of aiding in pollution prevention by reducing the amount of volatile organic compounds (VOCs) in the form of solvents, materials that traditionally have been used at high levels. The need for raw materials that reduce solvent demand and yet maintain or preferably improve coating performance is of primary importance.

Commercial coatings systems based on aldimine-isocyanate chemistry have been developed and are finding widespread acceptance as a solution to VOC restrictions. Current applications exist in the automotive refinish business where aldimines are used to make coatings containing only 20 to 25 percent volatile solvents, replacing products that have 40 to 50 percent volatile solvents by weight. Since the introduction of this technology in , old technology resin systems requiring more than 100,000 kilograms of additional organic solvent have been displaced.

This volume will triple in and approach one million kilograms in . More importantly, the volume of organic solvents displaced as other market areas adopt this technology is expected to increase dramatically. Additional benefits of this technology include: allowing low VOC coatings to be developed, resulting in large solvent savings for a given application without transferring environmental liability to production or use; it is already in significant commercial use, and will become a high volume product line by the end of the century, resulting in nontrivial source reduction of organic solvent emissions; it is compatible with existing and future coatings systems; it does not require significant capital investment to employ; and it increases productivity.

Alkyl Polyglycoside Surfactants: Henkel Corporation"s alkyl polyglycoside (APG®) surfactants are a class of nonionic surfactants that have been pioneered and marketed to the detergent and personal care industries under the Glucopon® and Plantaren® trade names since and , respectively. APG® surfactants are manufactured from renewable resources including fatty alcohol, derived from coconut and palm oils, and glucose, derived from corn starch. APG® surfactants are more innocuous to the environment than petrochemical-based technologies, are readily biodegradable, and have very low ecotoxicity.

APG® surfactants are highly efficient cleaners and have led to a significant reduction in overall chemical consumption in cleaner formulations and ultimately the amount of chemicals released to the environment. APG® surfactants also permit the formulation of concentrated cleaners that require less consumer product packaging and consequently reduce packaging waste. APG® surfactants are considerably less toxic and safer to humans and the environment than other major surfactants. APG® surfactants permit the formulation of less irritating and safer consumer products and significantly reduce the possible environmental impact associated with an accidental spill. Henkel Corporation"s 50 million pound per year APG® surfactant plant has been operating in Cincinnati, Ohio, since . A second plant was started up in Dusseldorf, Germany, in , by Henkel Corporations"s parent company, Henkel KGaA.

All-Acrylic Binders for Low VOC Architectural Coatings: Various regulations require solvent level reduction in paints and coatings in an effort to reduce the VOCs that lead to smog creation. One obstacle to meeting these regulations is the latex binder itself, which has traditionally required a coalescing solvent for adequate film formation. Binders soft enough to form a film in the absence of solvent result in tacky, non-durable films. Strategies for increasing film hardness such as, crosslinking, blending or special additives are too complex and costly for most applications. Alternatively, using non-volatile plasticizers in place of solvents adds cost and complication since the plasticizer remains in the film rendering it still too soft.

Acronal OptiveTM multiphase latex technology from BASF is the first robust and economically viable all-acrylic solution to this conundrum. Multiphase latex technology combines the benefits of a hard, durable polymer and a soft, film-forming polymer into the same latex particle. By using this technology, a paint formulator can reduce VOCs and still achieve the excellent film formation and durability previously accomplished only by incorporating odorous, toxic and environmentally harmful solvents. BASF conducted an eco-efficiency analysis, which demonstrated that Acronal OptiveTM multiphase latex technology significantly reduces VOC emissions and the risk potential associated with handling the solvents and solvent-laden paints that lead to VOC.

Alternative to Methyl Bromide to Overcome Nematode Damage to Crops and Concomitantly Enhance Yield, Crop Quality, and Abiotic and Biotic Tolerance: Worldwide, estimated annual losses of agricultural products to nematode damage total $100 billion. Currently, producers control nematodes by fumigating with methyl bromide, a highly toxic gas. Stoller has developed products to replace methyl bromide for nematode control. These products include Root FeedTM and a host of others. Stoller products are a combination of some or all of three types of materials that occur naturally in plants: minerals, plant hormones, and small molecules.

They are applied exogenously, preferably in water-efficient, drip irrigation systems. Stoller serendipitously discovered that these products not only enhance crop yield and quality (the original objective), but also strongly suppress damaging nematodes, resulting in much larger and more nutritious crops. Stoller has done extensive testing and intuitive modeling to determine which combination of ingredients among 20 minerals, dozens of plant hormones, and hundreds of small molecules is most effective. In , Stoller tested a wide range of its products and noted universal effectiveness. In all cases, crop canopy increased, root mass increased, and nematodes were reduced to varying degrees, but always with very desirable yields and crop quality. Additional studies are in progress.

The emphasis of Stoller products is to improve the hormone balance in the crop plant and thereby enhance crop productivity and suppress pests. Stoller&#;s hypothesis in nematode suppression is that by changing the auxin gradient in plants, Stoller products interfere with the ability of nematodes to form nematode-induced galls. A further mechanism may include the crop plant&#;s cytochrome P450, which might be associated with or co-expressed with the auxin signal.

Stoller continues to work to elucidate the mode of action of its products on nematode suppression. It is currently selling its products in over 50 countries worldwide, and its products work on over 70 different crops under numerous climatic conditions.

Aminopyralid: Increasing Protection of Endangered Species through Improved Management of Non-Native Plants While Maximizing Land Use and Significantly Reducing Herbicide Volume and Application: According to U.S. government policy, endangered plant species have potential scientific, medical, ecological, aesthetic, recreational, educational, and historic value. A wide range of programs has been put into effect in an effort to preserve them from extinction. Noxious and invasive weeds threaten endangered plant species by transforming ever-increasing amounts of habitat into monocultures with little to no biodiversity. Infestation of federal land with invasive weeds is increasing at a rate of 4,600 acres per day. Invasive weeds also reduce the productivity of farm and rangeland by approximately $20 billion per year at a time when pressure for additional agricultural output is mounting.

Aminopyralid belongs to the pyridine carboxylic acid class of auxinic herbicides. It is the first noncrop herbicide ever registered by U.S. EPA as a reduced-risk pesticide; it is registered for use in range, pasture, industrial, and wheat applications. It provides superior control of invasive weeds at rates of application 4 to 20 times less than those for competitive products, while reducing risk to people, nontarget organisms, and the environment. Use of aminopyralid for invasive weed control maximizes land use and helps protect habitat for endangered species. It also reduces the amount of herbicide active ingredient applied to the environment. Aminopyralid degrades relatively quickly; its half-life is approximately 30 days. Its synthesis includes a novel, one-step electrochemical reduction process in aqueous solution that results in substantial, high-purity yields.

Dow AgroSciences projects that once aminopyralid becomes established in the marketplace, it will reduce the total yearly environmental load of broadleaf herbicides applied in the United States by 2.4 million pounds, equivalent to a net 15-percent reduction. Against only one invasive species, Canada thistle, Dow AgroSciences predicts that hay growers will save $14.3 million each year in herbicide costs and eliminate $9.3 million in crop losses.

An Alternative to Aldehyde-Based Liquid Chemical Sterilants and High-Level Disinfectants for Reprocessing Heat-Sensitive, Semi-Critical Medical Instruments: High-level disinfectants (HLDs) are used to decontaminate semi-critical medical instruments. Currently, aldehyde-based HLD solutions such as glutaraldehyde and ortho-phthalaldehyde are widely used to reprocess heat-sensitive, semi-critical medical instruments, such as flexible endoscopes and imaging probes, primarily because they are compatible, reusable up to 14 days, and cost-effective. Aldehydes have a number of disadvantages, however; they are skin and respiratory allergens, they are not easily rinsed from treated instruments, and some organisms are resistant to them.

ResertTM XL HLD High Level Disinfectant is a 21-day, reusable liquid chemical sterilant and high-level disinfectant for safely reprocessing heat-sensitive, compatible medical devices. STERIS developed ResertTM XL HLD solution from Virox&#;s activated hydrogen peroxide (AHPTM) platform technology, a patented combination of 93-percent water, 2-percent hydrogen peroxide, hydrotropes, pH buffering agents to maintain pH 2.4, and other inert ingredients that optimize the hydrogen peroxide stability during storage and use. The rather mild, nonreactive nature of the components in the mixture and the low levels at which they are formulated make the solution ideal both for processing flexible medical devices and for ensuring complete disinfection, even in the presence of organic matter.

The ResertTM solution overcomes all of the negative characteristics of aldehydes. It is cost-effective, virtually odorless, clear, nonstaining, nontoxic, nonsensitizing, nonflammable, noncombustible, and easily rinsed from instruments. Unlike aldehydes, it requires no treatment to neutralize spent solution prior to disposal. Moreover, the ResertTM solution is very fast-acting, achieving tuberculocidal activity in 8 minutes at 20 °C, as opposed to 12 minutes for ortho-phthalaldehyde and 45 minutes at 25 °C for most glutaraldehyde products.

The U.S. Food and Drug Administration cleared this technology for sale in the United States and STERIS commercialized it under the brand name, ResertTM XL HLD High Level Detergent during .

An Economically Advantaged, Green Process, for the Fabrication of Printed Circuit Boards: An environmentally cleaner and a more economical process for the fabrication of printed circuit boards has been developed. Although the end product looks, feels, and performs the same as conventional boards, the process for manufacturing has been significantly changed and enhanced.

A single dispersion has been developed to make the holes conductive and ready to electroplate. An advanced computer/laser imaging system was developed that eliminates the use of conventional photo masks. To clean boards, in preparation for imaging and plating, non-toxic, all aqueous fluids are used that make disposal simple and straightforward. Mask removal uses non-toxic, commercially available fluids. Etching uses the latest re-usable etching bath with chemistries based solely on replenishment. Here again, no hazardous waste disposal is needed.

A new method for the accurate placement of solder mask and letter screen has been developed. Non-toxic ancillary chemicals have been developed to facilitate these steps, while retaining a simple all aqueous developer.

This new process has addressed all steps needed to manufacture boards and implemented wherever possible, aqueous, non-toxic chemicals in contrast with conventional board manufacture.

Since all data is stored in computers, no film or film processing chemicals are needed. The method reduces labor and shortens time and cost of production.

An Environmentally Benign Asymmetric Epoxidation Me: Epoxides are very important chiral building blocks for the synthesis of enantiomerically pure complex molecules. The epoxidation of olefins bearing no allylic alcohol group with high enantiomeric excess has been a long-standing problem with major synthetic significance. Recently we have developed a highly enantioselective epoxidation method for trans- and trisubstituted olefins using a readily available fructose-derived ketone as catalyst and inexpensive Oxone or H2O2 as oxidant. The reaction proceeds via a chiral dioxirane which is generated in situ from the chiral ketone and oxidant. High enantioselectivities can be obtained for trans- and trisubstituted olefins, hydroxyalkenes, conjugated enynes, conjugated dienes, vinylsilanes, and enol derivatives. Generally the epoxidation reaction is quite mild, rapid, safe, environmentally benign, and operationally simple. All these features demonstrate the strong potential of this epoxidation method for practical use.

An Environmentally Friendly Alternative for Cleaning Surgical Instruments in Healthcare Facilities: Cleaning is the single most important step in processing a surgical instrument for reuse. Instrument cleaning, as defined by the Association for Advancement of Medical Instrumentation (AAMI), is "the removal, usually with detergent and water, of adherent visible soil, blood, protein substances, and other debris from the surfaces, crevices, serrations, joints, and lumens of instruments, devices, and equipment by a manual or mechanical process that prepares items for safe handling and/or further decontamination." Inorganic and organic soils that are not removed from surgical instruments during cleaning can negatively compromise subsequent disinfection and sterilization of surgical instruments, leading to patient infection. If surgical instruments are repeatedly exposed to harsh chemicals, their useful life may be shortened, leading to increases in both cost and waste for the healthcare facility. Current, traditional chemistries have several disadvantages: poor substrate compatibility, ineffective cleaning performance, packaging that is not ergonomic, and ingredients that are not environmentally friendly.

STERIS developed Prolystica® Ultra Concentrate cleaning chemistries and introduced them in as an innovative, green alternative. The product line includes a neutral pH enzymatic presoak and cleaner, a neutral pH detergent, and an alkaline detergent with lower alkalinity. All three formulations are phosphate-free. They contain surfactants that are biodegradable, as well as biodegradable corrosion inhibitors (biodegradable polycarboxylic acid), chelating agents (an iminodisuccinate and a methyl glycine diacetate), and sequestering agents (including inulin derived from chicory).

These 10-fold-concentrated cleaning products provide industry-leading cleaning and protection for surgical instruments and are environmentally friendly. The smaller product containers of the Prolystica® Ultra Concentrate products reduce the amount of waste generated for disposal and increase staff safety. Overall, Prolystica® Ultra Concentrate products with biodegradable formulas reduce shipment fuel costs, plastic packaging consumption, and chemicals used per wash cycle. Prolystica® Ultra Concentrate products are now in use at 1,442 healthcare facilities in the United States and Canada.

An Improved Approach to the Preparation of Duloxetine and Atomoxetine: Eli Lilly has developed and demonstrated new, more efficient, synthetic routes for two of its 3-aryloxy-3-arylpropylamine pharmaceutical products. Duloxetine hydrochloride is the active ingredient in the product Cymbalta®, used to treat depression. Atomoxetine hydrochloride is the active ingredient in the product Strattera®, used to treat attention deficit/hyperactivity disorder. Each of these improved syntheses avoids using an N-methyl protecting group and produces the drug substance in a direct fashion using a monomethylamine intermediate.

Eliminating the traditional protecting group to produce these drug substances reduces the combined environmental footprint by an average of 44%, as measured by the weight of materials used to produce one kilogram of product (E-factor). These combined improvements reduce the use of (1) solvents by an average of 27%, (2) water by 58%, and (3) raw materials by 78%. At peak production volumes for both drugs, estimated in the tens to hundreds of metric tons per year, these reductions could provide expected savings of 2.5 to 25.5 million pounds of raw materials per year. Further, manufacturers must often incinerate pharmaceutical aqueous waste streams to destroy the biological activity associated with their trace components, necessitating additional fuel consumption. Water reductions from the new syntheses alone should result in secondary fuel savings of 1.5 to 14.5 million cubic feet per year.

The new synthesis for duloxetine was demonstrated on a pilot plant scale in ; Eli Lilly is now developing its pilot plant process into an improved commercial process. The new synthesis for atomoxetine is currently being used at an Eli Lilly production facility.

An Innovative Approach to Texturizers without Hydrofluoric Acid or Nitric Acid for Multicrystalline Silicon Photovoltaics: Solar cell fabrication includes a texturizing step. A flat surface reflects energy away from the cell, but raised structures on the surface reflect energy into the cell, increasing its energy output. The texturizing step for multicrystalline photovoltaic cells reduces reflectance and improves the efficiency of the cell; it is critical to the cell&#;s ultimate performance.

Current texturizing technologies for multicrystalline silicon wafers require several hazardous chemicals. The photovoltaic industry currently dilutes concentrated 49-percent hydrofluoric acid (HF) and 69-percent nitric acid in an exothermic reaction to a make a bath that contains 10-percent HF and 35-percent nitric acid. The nitric acid oxidizes the silicon and the HF does the bulk etching. The handling, storage, use, and disposal of these hazardous solutions require extreme care and can contribute significant expense depending on local and regional treatment requirements.

Dow&#;s new technology uses an alkaline hydroxide solution with an added oxidant, which behaves isotropically like the HF&#;nitric acid bath and delivers equivalent or better performance while significantly reducing the health, safety, and environmental negatives of the current technology. This alkaline texturizer is compatible with existing equipment configurations. The process also reduces the cost of ownership by reducing operational costs including process energy and waste treatment. The makeup chemistry for the new solution requires about 8-percent active ingredients compared to 45-percent for the HF&#;nitric acid bath. The HF system requires replenishment with three times more reagents than does the new system. The new technology consumes substantially fewer materials, which results in significant cost savings and less chemical waste. Dow will be alpha-testing its new, multicrystalline texturizer in January and expects to make it available commercially later in . There are no other suitable replacements for HF&#;nitric acid on the market today or described in the literature.

An Innovative Replacement for Chromium for Aluminum Coatings: An environmentally benign substitute for Chromium has been discovered which provides excellent corrosion resistance for aluminum surfaces. The material can be formulated both for pigment and conversion coating applications. The material has undergone extensive laboratory tests and demonstrated good adhesion and good corrosion resistance. The material has been patented. The fundamental goal of this project was to find the pigments that could satisfactorily be substituted for environmentally hazardous chromium coatings in use. From the many possibilities that exist, experimental data led to a successful first formula. Since the lithium salts passivate aluminum, they can serve as viable substitutes for chromium in corrosion preventive systems. Also, they can be used in small quantities as a pigment substitute. Aluminum-lithium provided a base for minimal amounts of corrosion inhibitors as nanostructural cores or bases of other systems.

The results of independent laboratory testing confirmed the effective corrosion protection. Although the steel panels corroded seriously, the aluminum panels only had a few pits, as evidenced by the white powder on the surface. The scribes which exposed bare aluminum did not corrode or undercut, and no blisters on the coating were discovered. Closer inspection showed the pits were caused by lumps of pigment which, after being replaced with preheated and screened pigment, had no corrosion. In addition, the top coated primer had no corrosion, even in the scribe to bare metal. The large unfiltered particles caused a circumstance of pitting corrosion which was reduced by the lithium molybdate passivator, but could be eliminated entirely by screening the lumps out prior to painting.

The mechanism of corrosion protection appeared to be a combination of galvanic action by the lithium and passivation by the reaction products. The inhibitor was a complete success on aluminum. In the case of the four steel panels, the galvanic action probably inhibited corrosion, but the reaction products promoted corrosion on cold rolled steel. The technique of corrosion protection by nanostructural inhibitors is still possible, but the sacrificing pigment must not generate a compound which promotes corrosion. Lithium does not function on steel as it does on aluminum. However, it appears that steel substrates may also be protected by similar lithium systems.

Investigations into the mechanism of corrosion protection by the aluminum-lithium pigment revealed another interesting technique. Water slurries of aluminum-lithium pigments were rubbed on the aluminum panels for one-half hour with a subsequent water rinse. The panel developed a permanent corrosion resistant film and a good base for topcoat application. This was consistent with the results using an aluminum lithium pigment in a paint. It was also considered a unique adhesive and showed possibilities as a sealant.

In addition a chemical film which involves precipitation of lithium, molybdate, and cerium on aluminum alloy surface has been found. The film can be formed by both immersion and brushing at room temperature. Different aluminum alloys, including both low copper content and high copper content, were treated with the chemical film and were tested according to ASTM B117. Corrosion resistance of the alloys was greatly enhanced by the chemical film. The chemical film also shows good adhesion to top paint.

Analysis of Liquid Hazardous Waste for Heavy Metals by Energy-Dispersive X-ray Fluorescence (EDXRF) Spectrometry: The laboratory-based elemental analysis of nonaqueous liquid hazardous waste has traditionally been performed using inductively coupled argon plasma (ICP) and atomic absorption spectrometry (AAS). The preparation of samples and analyses using these techniques, however, generates a large amount of acidic, heavy metal-bearing hazardous lab waste. Laboratory-based energy-dispersive X-ray fluorescence spectrometry (EDXRF) is a mainstay analytical technique in many industries, but has received very limited attention in the environmental field. Within the last five years, ASTM Committee D34 on Waste Management has formally approved two Standard Test Methods for the elemental analysis of liquid waste by EDXRF spectrometry.

In many cases, data quality objectives can be easily met using EDXRF spectrometry instead of ICP or AAS. The main environmental benefit of using EDXRF spectrometry is the significant decrease in the generation of laboratory waste in comparison to traditional methods. The primary reasons for this reduction in waste generation are that samples do not require dissolution in concentrated acids and calibration standards are not dissolved in acidic solutions and diluted to large volumes. Samples and standards are simply mixed with a nonhazardous substrate such as carbon or alumina prior to analysis or calibration. Also, the frequency of preparing and running standards is much less than traditional techniques because of the inherent stability of EDXRF systems. It is an environmentally friendly technique because it virtually eliminates the generation of hazardous lab waste.

Antibody Catalysis: A meritorious goal is the production of novel protein catalysts applicable in organic synthesis that can be generated in real time versus hundreds of thousands of years of evolution. Enzymes, in an over-simplified view, are merely catalytic cores embedded in a protein scaffold. It has been demonstrated that a scaffold can be made; the challenge then lies in creating a core with the correct arrangement of amino acid residues and/or cofactors to effect catalysis. Catalytic antibodies meet these goals and challenges. Catalytic antibodies can be procured via animal or in vitro systems in a matter of weeks to a few months. By using such systems, antibodies can be tailored to catalyze the reaction of choice by the designer. Many of the reactions catalyzed by antibodies proceed with high rates and regio- and enantioselectivity. In addition, catalytic antibodies have been made that catalyze disfavored chemical transformations and even reactions in which there are no enzyme counterparts known. Antibody catalysis has also shown great potential in the treatment of both cancer and cocaine addiction. In summary, catalytic antibodies are unique in that they can catalyze both important chemical transformations as well as aid in human health problems.

Antioxidant-Functionalized Polymers: A bio-catalytic technology was developed for the synthesis of antioxidant functionalized polymers. The process consists of two steps. First, a lipase is used to catalyze the highly selective modification of a vinyl monomer with ascorbic acid. Second, horseradish peroxidase is used to catalyze polymer formation. During this two step enzymatic process the ascorbic acid retains antioxidant activity due to the regioselective nature of the enzymatic coupling process and mild reaction conditions employed by these enzymatic methods. This approach represents a novel green chemistry strategy to functionalized polymers that are otherwise difficult to synthesize and require large amounts of solvents or toxic chemicals to make. Furthermore, this novel approach enhances human heath and the environment by avoiding overuse and overexposure to benzene-derived antioxidants in foods, beverages, and materials in general, and provides for enhanced stability of labile and naturally occurring antioxidants to promote lower concentrations during use.

Application of Collagen Nanofibrils in Green Processing and Synthesis: A dilute milling process unravels collagen fibers from waste bovine hides (corium) into nanofibrils less than 100 nm in diameter. The molecular structure of the nanofibrils remains intact as the active surface area increases by several orders of magnitude. Collagen nanofibrils form dispersions in water and can retain water near their charged surface that is many times their own mass. When added to sludge or any material with suspended solids, collagen dispersions cause agglomeration, the formation of large clumps, and settling, all at a very rapid rate. Collagen nanofibrils are effective in the rapid agglomeration of fine solids in all types of sludge: industrial, water treatment, inert suspensions, and kaolin. They have also shown promise in other environmental applications such aiding filtration, separation of pollutants from aqueous streams, selective fractionation of molecules, and oil droplet stabilization. Additional applications include cell culture, tissue engineering, and catalyst manufacture.

Professor Maffia also developed a "lost protein technology" to make porous metals using collagen nanofibrils. In this application, metal dust is blended with the nanofibril dispersion. The resulting material is molded into the desired shape, frozen, lyophilized, and then calcined to produce a porous metal. Professor Maffia is working with the Nanotechnology Institute and Synnovations, Inc. on applications for these porous metals.

Professor Maffia has focused on the production of collagen nanofibrils in ongoing research over the past 20 years. Over the past 5 years, he has shifted the starting material to ground bovine corium, a low-value byproduct of the meat-processing industry. Two patents have been issued for this technology. This technology received a Lindbergh Award in as an example of the balance between technological advancement and protection of the environment. Some small businesses (including Catalyx, Inc.) and government agencies are investigating the technology.

Application of Green Chemistry Principles in the Scale-Up of the Darunavir Process: Johnson & Johnson used green chemistry principles to scale up the synthesis of darunavir, the active pharmaceutical ingredient in PrezistaTM, a new protease inhibitor. PrezistaTM is indicated in the treatment of adults with HIV-1 strains that no longer respond to treatment with other anti-HIV medicines.

The principal objectives of the scale-up were to reduce the cost to manufacture darunavir and to reduce the negative safety and environmental impacts of the manufacturing process. By reducing the manufacturing cost, Johnson & Johnson could reduce the price of PrezistaTM to allow more patients to benefit from it.

The company met three objectives. First, it reduced solvent use by replacing a single reaction in a relatively large volume of solvent with three consecutive reactions in a relatively small volume of solvent. Second, it eliminated the formation of hydrogen gas originally given off when excess hydride was quenched with hydrochloric acid by separating the acidification and quenching steps; it replaced hydrochloric acid with methane sulfonic acid and now adds acetone to react with excess hydride and form isopropanol. Third, it replaced a solvent system containing methylene chloride and triethylamine with a more benign solvent system containing acetonitrile and pyridine. It also eliminated a number of solid-liquid separation steps. Its accomplishments reduced the manufacturing cost by 81 percent and increased the overall yield by 40 percent.

The U.S. Food and Drug Administration granted accelerated approval to PrezistaTM on June 23, . With its improved, scaled-up process, Johnson & Johnson reduced raw materials and hazardous waste by 46 tons, reduced hydrogen gas by 4,800 cubic meters, and eliminated 96 tons of methylene chloride in .

Application of Green Chemistry Principles to Eliminate Air Pollution From the Mexican Brickmaking Microindustry: A new recirculating design for small brickmaking kilns was investigated as an alternative to conventional operations, which are a significant source of air pollution. The bricks used in building many houses and office buildings in Mexico and other parts of the third world are typically made by hand and fired in small kilns using available fuels such as sawdust, treated wood, paper, trash, tires, plastic, and used motor oil. Although these bricks cost about half of standard high-fired construction bricks, they do not meet the minimum strength requirements for commercial construction in the United States.

In addition, a major byproduct of this brickmaking industry is a high level of air pollution&#;both particulates and toxic chemicals&#;that results from inefficient thermal design of the kilns and the use of cheap but readily available fuels. This industry is the third leading cause of air pollution in the El Paso-Juárez area. Redesign of the kilns to allow efficient energy recovery and to eliminate waste from over- and under-firing makes the use of nonpolluting fuels (e.g., natural gas) economically attractive.

The design challenge is to use inexpensive, readily available materials and equipment to avoid significant capital outlay. Laboratory investigations and process modeling were performed at the Los Alamos National Laboratory, and field tests are being performed at ECOTEC in Ciudad Juárez, Mexico, in cooperation with FEMAP, a private foundation in Mexico, and with the El Paso Natural Gas Company. The direct benefits of these improvements in the brickmaking process are reduced air pollution, safer operating conditions, and better bricks. In addition, process modeling indicates that fuel consumption can be reduced by approximately 55 percent and cost analyses project that this will result in an increase in profit of about 35 percent for the brickmakers.

Applying Green Chemistry Principles to Enable Zero-Waste Manufacturing: General Motors (GM) has created an environmentally sustainable process that eliminates GM&#;s use of landfills for waste disposal. GM&#;s process technology addresses environmental footprint reductions, potential long-term landfill impacts, and natural resource depletion. This process includes establishing goals; entering and analyzing data from all operations monthly; adhering strictly to a zero-landfill best practice; monitoring, maintaining, and reporting progress; and collaborating internally and externally. First, the process focuses on source reduction then works to retain all wastes (manufacturing byproducts) in use as long as possible. These priorities correspond to EPA&#;s pollution prevention hierarchy.

On average, GM now recycles or reuses more than 97 percent of its waste materials and converts the remaining less than 3 percent to energy, replacing fossil fuels at waste-to-energy facilities. Within the United States, 13 facilities are landfill-free: they recycle, reuse, or convert to energy all wastes from their normal operations. During , these facilities diverted over 385,000 tons of waste from landfills and avoided emissions equivalent to 2.1 million metric tons of carbon dioxide (CO2e). Currently, GM&#;s process is part of 76 global automotive manufacturing operations that reuse, recycle, or convert to energy all the waste they generate. During , GM recycled or reused 2.5 million tons of byproduct materials worldwide.

Because environmental cross-industry collaboration and community stewardship are important, GM directs its engineers to mentor other companies, industries, and communities. For example, during the Gulf of Mexico oil spill, GM assembled an engineering team to recycle oil-soaked, absorbent polypropylene booms recovered from the Alabama and Louisiana coasts. To retain the chemical value of these booms, GM processed them into parts for the Chevrolet Volt. To date, this technology has prevented over 100 miles of oil booms and the oil retained in them from entering American landfills. It has also prevented 70 metric tons of CO2e from entering the atmosphere.

Aqua FormTM, a water based, odorless, non-emissive, non-styrenated bonding/laminating resin for structural/advanced composites: Aqua FormTM is a self cross linking air drying water based non-emissive polymer which dries/hardens at room temperature. Aqua Form functions as a wetting agent/binder for numerous forms of pre-sized or gray goods-unprepped non-sized textiles, Fiberglas and carbon fiber reinforcement. Aqua Form is used for durable dimensional shapes without post fume or offgassing. It is a translucent light emitting air/heat cure dispersion used for architectural, decorative, sculptural constructions, light fixtures, panels, free form abstract shapes, scenery, graphics/signage, displays, parade float figures.

Aqua Form wets out, mat/veil cloth, burlap, canvas, non-wovens, KevlarTM, SpectrafiberTM, woven roving, Dynel, graphite, carbons, polyester, and numerous E-glass Fiberglas cloths. Aqua Form accepts pigments, dyes, and fillers for viscous gels, Gesso&#;s, putties, and modeling pastes. It is suitable for interior/exterior applications, cleans up with tap water, and is used in small confined areas for vapor/odor free repairs, restoration, stiffening, lining, and structural reinforcement. Aqua Form is a user friendly planet kind "0" VOC consolidating binder for strong impact resistant composites. Aqua Form is for chemically sensitive individuals. Aqua Form can be painted/overcoated with solvent or water based lacquers, coatings, varnishes, epoxy finishes for wet/damp environments such as foliage, props, rain forest, swamp, scenic settings.

Aquagard Waterbase Antifouling Bottom Boat Paint: In introducing Aquagard Waterbase Antifouling Bottom Boat Paint to the market, the initial market impression was that the public had to be educated on the merits of waterbase bottom boat paint.

It was recognized that the education of the public to this new waterbase technology was going to take time, much longer than anticipated. The consumers who attended the trade shows were skeptical of waterbase paint "holding up" on the bottom of boats. However, even during the early stages, boat owners&#;who tried Aquagard&#;began to have confidence in our product.

Aquagard has gained a small market share in the northeast coast of the United States. The strategy has been to create demand through the marinas (boat dealers) and Aquagard sales representation is continually expanding the dealer base.

This strategy is to create enough demand for the product so that a major distributor will pick up the Aquagard product line. The distributors have been hesitant to carry Aquagard since it would affect their relation with their other paint suppliers. As our sales grow, the distributors are more aware of our presence in the marketplace. We must continually promote and educate the public through trade show advertising and our dealer networks.

The next generation of Aquagard products will continue the growth in the marine marketplace: Aquagard II* Waterbase Antifouling Bottom Boat Paint for aluminum outdrives, boats and transducers will not cause electrolysis.

Aquence® Autodeposition Coating: The Smart Coating Solution: Conventional electrodeposition processes for applying coatings to automotive and industrial equipment parts require that the parts be electrically charged. These processes require 12-15 steps, including surface conditioning and pretreatment with metal phosphate coatings. They contain both volatile organic compounds (VOCs) and heavy metals.

Henkel has developed Aquence® coatings as sustainable options to conventional coatings. Aquence® coatings are low-VOC, water-based functional organic epoxy-acrylic-urethane. The formulation includes epoxy-acrylic copolymer, proprietary blocked isocyanate cross-linker, coalescent, surfactant, and pigment. The autodeposition process consists of a mildly acidic bath that contains a negatively charged polymer dispersion, ferric chloride, and deionized water. The mildly acidic, oxidizing bath liberates a small amount of iron from the immersed steel parts resulting in a locally high concentration of positively charged ferrous ions at the steel surface. These ions cause the negatively charged polymer dispersion particles to deposit a coating on the surface. The process has only 7 steps. The absence of electric current from the process shortens the cycle time and lowers the curing temperature of the coating, which saves energy. The low pH of the coating bath discourages bacterial growth, and the elimination of heavy metals reduces time and expense in chemical maintenance and waste treatment.

The water-based Aquence® autodeposition coating technology developed by Henkel recently set a new industry precedent by coating an entire vehicle body in assembly. Aquence® customers can realize a 40-percent footprint reduction, reduced capital expense and paint shop complexity, decreased energy consumption, elimination of heavy metal sludge, and improved inside-out corrosion performance. Henkel launched its Aquence® 925G epoxy-acrylic coating for industrial primers and automotive body primer in and its Aquence® 930 epoxy-acrylic coating for improved cyclic corrosion resistance in the frame and chassis market in . Aquence® is in trials globally at over 150 locations.

Arsenic-Free SPADNS Chemistry for Fluoride Analysis in Water: Many nations around the world fluoridate drinking water to reduce tooth decay. According to the Centers for Disease Control (CDC), roughly two-thirds of Americans are supplied with fluoridated water. Fluoride added to drinking water must be kept within a narrow range of concentrations, typically between 0.5 and 1.5 ppm F¯ to be both effective and safe.

SPADNS is the common abbreviation for sodium 2-parasulfophenylazo-1,8-dihydroxy-3,6-naphthalene disulfonate. The SPADNS method for measuring fluoride is a simple spectrophotometric test used worldwide. Unfortunately, the SPADNS method utilizes high levels of arsenic, a persistent, tightly regulated toxin and carcinogen. Sodium arsenite in the SPADNS method acts as a reducing agent to prevent interference from chlorine and other oxidants that are typically present in drinking water. Although this approach is effective, the arsenic left over from each test is present in sufficient concentrations to be regulated as a hazardous waste in the United States.

Hach Company has developed an arsenic-free SPADNS reagent and commercialized it as SPADNS 2. In place of sodium arsenite, the new method uses a proprietary, nontoxic reducing agent. The waste from using SPADNS 2 can be disposed of safely without the special handling required for arsenic. The arsenic-free SPADNS 2 Hach Method outperforms both EPA-compliant methods (EPA Method 340.1 and Standard Method -F D) in reagent water and matrix spike recovery and precision.

Apart from this change, the core chemistry of the new test is identical to traditional SPADNS. The new SPADNS 2 reagent can be used with any instrument, test procedure, and calibration curve currently used to measure fluoride with the original Hach SPADNS method. Although the SPADNS 2 reagent continues to be acidic and should be handled with care, its use generates no arsenic hazardous waste and operators have no risk of exposure. Hach commercialized this technology during .

Ashless Friction Modifier/Antioxidant for Lubricants: Cars consume roughly half the oil used in the United States and account for about one quarter of the greenhouse gases generated. There are at least two important benefits to improving passenger car fuel economy: conserving natural petroleum resources and improving the environment through reduced volatile emissions. While automobile manufacturers work on improving vehicle fuel economy through upgrading engine efficiency and utilizing lighter weight materials in automobile construction, products that can improve the performance of cars already on the road could have a more immediate impact.

Development of engine oils that improve engine efficiency are in this category. Engine oil is a mixture of petroleum base stock and additives that protect the metal surfaces, expand the useful temperature range of the lubricant, and extend the useful life of the oil. Additives in a typical engine oil include detergents to keep the metal surfaces deposit-free; dispersants to keep the insoluble particles suspended in the oil; viscosity modifiers, which stabilize lubricant thickness at various temperatures; antiwear agents, which reduce metal-to-metal contact; metal deactivators, which reduce friction between metal parts in motion; and antioxidants, which reduce oxidation and breakdown, preserving the lubricant&#;s properties over a lifetime.

Developing a combination friction modifier/antioxidant reduces the number of additives that a lubricant requires. More importantly, it has the capability to extend the durability of the friction modifier, leading to improved lubricants. This in turn can positively influence gas mileage and reduce environmental emissions.

Irgalube F10 is a unique ashless, multifunctional, combination friction modifier and antioxidant. Chemically it is a high molecular weight phenolic antioxidant with hydroxyl functionalities providing friction modifying properties. It has been designed to replace glycerol monooleate, a friction modifier that tends to promote oxidation at higher temperatures, and molybdenum dithiocarbamates (MoDTC), which are metal-containing and can form undesirable, metal-containing inorganic particulates upon combustion. Irgalube F10 is made via the reaction of coconut oil, glycerol, and a phenolic antioxidant and, as such, is the only commercially available, metal-free, multifunctional friction modifier/antioxidant in the world.

Irgalube F10 passed the ASTM fuel economy test procedure, registering a fuel economy improvement of 1 to 1.5% over the standard test oil. A fuel-efficiency improvement of 1% could have an annual impact of reducing carbon monoxide by 1.2 billion pounds, Ox emissions by 240 million pounds, and particulate matter emissions by 17 million pounds (based on National Air Quality and Emissions Trends Reports, ).

AURA® Infusion Technology: A Green Method to Incorporate Color and Performance Additives: Thermoplastics are all around us from housings of electronic devices to household appliances, car interiors, sports equipment, and, increasingly, architectural components. The current technology to incorporate color or other performance additives relies on continuous processes that distribute the additives throughout the plastic parts. This can generate significant solid waste or low-value material during transition into and out of each customized product or when the product does not meet the color specification.

AURA® Infusion Technology customizes a thermoplastic part with a colorant or other performance additive down the supply chain close to the end consumer. The technology uses a batch process that has no transition periods. For example, coloring a part with AURA® Infusion Technology versus using pre-colored resin pellets to make the part can reduce the amount of resin waste by 15&#;25 percent and significantly reduce inventory because part producers can color parts on demand.

AURA® Infusion Technology minimizes the amount of colorant or performance additive needed in the thermoplastic part by concentrating the additive near the surface. The colorant or performance additive is infused by means of a hot bath for smaller parts or a hot solution spraying system for larger parts. The solution typically contains a leveling agent, a plasticizing agent, and water in addition to the desired additive. The AURA® Infusion Technology process generates less than 1-percent waste because it is designed to recover and recycle the unused performance additive for efficient customization and to recycle the water and the small amount of solvent used.

By eliminating the additive in the bulk material, AURA® Infusion Technology makes more virgin resin available for recycling. Part producers can now take back customized products at end-of-life, remove the surface color, and recycle or recolor them. Currently four companies are licensing this technology in the United States.

Automotive Windshield Adhesives: Up until this year all automotive windshield adhesives, used when replacingwindshields, have been made from unblocked isocyanate prepolymers. These products may contain one to three percent isocyanates, which pose a potential severe health hazard to the workers in the manufacture of these prepolymer adhesives. In addition to chemical workers, installers of these products and car owners can be exposed to the isocyanate prepolymers, which can pose a health risk.

Tremco, a BF Goodrich Company, has been able to develop a new sealant/adhesive chemistry that is significantly better than isocyanate adhesives in many respects -- it demonstrates more rapid cure rate, even at low temperatures and low humidity conditions, posses higher lap shear strengths, and is non-moisture sensitive. In addition, this product is nonhazardous, nontoxic, contains no isocyanates, and poses no health risks to chemical workers, installers, or consumers. This new two part chemical system uses acetoacetylated polyol prepolymers.

These prepolymers are made by reacting di and triol polymers with tert-butylacetoacetate (tBAA). Some of these acetoacetylated polyols are aminated with low molecular weight diamines. These acetoacetylated polyol amines are then reacted with acetoacetylated polyols to achieve a cured polymer matrix. This system produces an extremely strong isocyanate type cure and allows for faster "drive away times" for the car owner and more productivity for the installer. In addition, an acetoacetylated roofing adhesive using the same technology is being field tested. This product is completely free of solvents, is 100 percent solid, and is environmentally friendly.

Autothermal Reforming Catalyst for Fuel Cells: Researchers at Argonne National Laboratory have developed an autothermal reforming catalyst that efficiently reforms various liquid hydrocarbons, such as gasoline, into the hydrogen a fuel cell needs to produce electricity. The unique catalyst is the key to a fuel processor (or reformer) the size of a 1-liter soda bottle that will allow fuel-cell-powered vehicles to operate on conventional fuels, rather than on hydrogen stored onboard, making the vehicles much more attractive to consumers.

The catalyst is so efficient that the fuel processor can now be 25 times smaller than any previous types, and therefore less expensive, less of a drain on a vehicle&#;s fuel economy, and easier to integrate into a vehicle. Unlike most conventional catalysts, which are poisoned by sulfur, the Argonne catalyst tolerates the sulfur present in petroleum-derived fuels. The new catalyst could also help make fuel cells more attractive as stationary power sources for homes, commercial buildings, and remote locations. The advantages of using fuel cells in automotive and stationary power applications include their high efficiency and the absence of harmful emissions.

The nominated technology has been researched and demonstrated in the United States within the past 5 years. It is not eligible for either the small business or academic award. It was developed by a U.S. governmental research laboratory in focus area 1: the use of alternative synthetic pathways for green chemistry.

Bacteriocins: A Green, Antimicrobial Pesticide: Pesticides are used worldwide to protect crops and structures, manage pests, and prevent the spread of disease. Pesticides are intended to be toxic, but only to their target organisms. Their intrinsic properties, however, lead these pesticides to pose risks for human health and the environment. There is a continuing need for safer pesticides to replace those that are toxic to nontarget species.

Through evolution, bacteria have acquired the ability to produce molecules such as bacteriocins that inhibit other microorganisms. Bacteriocins are gene-encoded, ribosomally synthesized, antimicrobial peptides that are often small in size (20&#;60 amino acid residues). Bacteriocins combine with negatively charged surface constituents of target bacteria, creating transmembrane pores that make the target bacterial membrane permeable and thus kill the bacteria. Bacteriocins are not toxic to eukaryotic organisms. They are generally recognized as safe (GRAS) by the U.S. Food and Drug Administration.

Moreover, they are currently considered for therapeutic applications such as the development of new vaccines against pathogenic, multidrug-resistant bacteria and as cytotoxic agents against human cancer cells. VH Biotechnology has developed a novel, green bacteriocin composition for use as a microbicide in commercial applications including pulp and paper mills, fuels, biofuels, cooling water systems, and poultry farms. The bacteriocins are obtained by standard fermentation using lactic acid bacteria. Two paper mills using these bacteriocins showed much lower bacterial counts. In diesel fuel, bacteriocins reduced microbial levels by 99.95 percent over controls; in gasoline, the reduction was 89 percent. When used to sanitize water on poultry farms, bacteriocins at 100 grams per cubic meter of water were able to match the performance of chlorine at 12 grams per cubic meter. VH Biotechnology developed this technology in and filed a U.S. patent application for it in March .

Beneficiation and Use of Coal Combustion Fly Ash: A Major Success in Reducing Solid Waste and Increasing Supplies of Construction Materials While Reducing Greenhouse Gas Emissions: Coal combustion generates approximately 55 percent of all electric power in the United States. Over 70 million tons of fine coal ash, known as fly ash, are recovered annually; most of it is disposed of in landfills or settling ponds. Using fly ash as a supplement in concrete reduces the use of ordinary Portland cement, but concrete specifications limit the amount of unburned carbon in the fly ash.

Separation Technologies (ST) has developed and implemented innovative, patented processes to reduce unburned carbon and detrimental ammonia in coal fly ash. The treated fly ash is suitable for use in concrete, and the separated carbon is a fuel for utility boilers. ST takes advantage of the differing surface chemistries between unburned carbon particles and mineral particles in fly ash. When these particles collide, charge transfer (triboelectric charging) occurs and the carbon particles separate from the mineral particles in an electric field. ST has also developed an economical process to remove ammonia as a gas from fly ash.

ST&#;s technology is operating commercially at eight large, coal-fired electric power plants in the United States, Canada, and the United Kingdom to beneficiate coal ash into raw materials for concrete production and to recover unburned carbon in the ash for its fuel value. Cumulatively, ST has produced four million tons of concrete-grade fly ash with a corresponding reduction in solid waste and emissions of greenhouse gas (CO2).

BFRACTM and BPXTM: Launching the Biorefining Revolution: Ethanol is one of the most economical and viable alternative fuels. Broin is the second-largest producer in the industry, making more than 600 million gallons of ethanol per year. Broin has been working to usher in the biorefinery revolution by increasing the efficiency and sustainability of ethanol production.

BFRACTM is a Broin technology that fractionates corn or other cereal grains into bran, germ, and endosperm. It then uses the optimal fractions for ethanol production and refining. Broin developed this technology in collaboration with Satake USA, Inc., a world leader in rice and flour milling. BPXTM is a complementary Broin technology that removes the cooking step in traditional dry-mill ethanol production and replaces it with simultaneous saccharification of raw starch and fermentation of the resulting sugars in an advanced enzyme technology.

Broin developed this technology in collaboration with Novozymes North America, Inc., a world leader in enzyme development and a major enzyme supplier. BFRACTM and BPXTM not only increase ethanol production efficiency by enabling higher alcohol levels during fermentation and during beer production, but also result in the production of a higher-protein distillers dried grain from the no-cook plant material. An added environmental benefit is reduced dryer stack emissions.

The BPXTM process is currently in use at ten plants managed by Broin. In May , Broin started up BFRACTM and BPXTM operations at a retrofitted 50-million-gallon-per-year ethanol biorefinery in Coon Rapids, IA. Broin is currently marketing the majority of its over-40-percent protein distillers grains from the BFRACTM and BPXTM processes as Dakota Gold HP (HP = high protein). This low-fat, high-fiber, high-protein product is opening new markets to distillers grains in the swine and poultry feeding industries.

Biobased Adipic Acid for Renewable Nylon and Polyurethane Resins: Adipic acid (C6H10O4) is an important industrial dicarboxylic acid with an estimated global market of $6.5 billion. It is a feedstock for nylon 6,6 and polyurethane resins. It is currently produced from petrochemicals by the nitric acid catalyzed oxidation of cyclohexane. This process generates a waste gas stream including nitrous oxide, non-methane volatile organic compounds (VOCs), carbon monoxide, and nitrogen oxides.

The production of adipic acid from renewable resources would result in substantial reductions of environmental pollutants. Verdezyne has engineered an industrial strain of the yeast Candida to produce adipic acid from natural plant-based oils. This yeast normally grows on fatty acids as its sole carbon source by cyclic degradation through its ß-oxidation pathway. A Candida strain in which this pathway is completely blocked can convert these substrates to the corresponding dicarboxylic acids by selective oxidation of terminal methyl groups through its ?-oxidation pathway to produce diacids with a chain-length distribution that precisely mimics that of its plant-based oil feedstock.

By engineering both the ß-oxidation and ?-oxidation pathways of yeast, Verdezyne has enabled the highly selective production of adipic acid from any plant-based oil. This engineered strain tolerates saturating concentrations of adipic acid in the fermentation broth, growing at the same rate and to the same density as in its absence. In addition, Verdezyne has developed fermentation and downstream purification processes to recover polymer-grade bioadipic acid from the fermentation broth and has synthesized nylon 6,6 fibers and pellets from bioadipic acid. The advantages of Verdezyne&#;s biobased technology over petroleum-based manufacturing include lower cost, sustainable feedstock supply, and a smaller environmental footprint. Verdezyne estimates that its production costs will be 30&#;35 percent lower than the petrochemical process.

Verdezyne recently opened a pilot plant in Carlsbad, CA to demonstrate the scalability of its process, validate its cost projections, and generate enough biobased adipic acid for commercial market development.

Biobased Adsorbents for Desiccant Coolers: Revised standards for acceptable indoor air quality have doubled ventilation requirements for commercial buildings and retail establishments. The need to dehumidify the additional air flow, combined with concerns about the phase-out of freons and the need to control costs of dehumidifying and cooling air, have led to an increase in the use of desiccant wheels.

When combined with heating, ventilation, and air-conditioning systems, desiccant wheels save both capital and operating costs, according to a Gas Research Institute funded study. Since desiccant wheel systems can dry and cool large volumes of air, they have the potential to supplant CFC and HFC refrigerants associated with compression-type air-conditioning systems. The current production of desiccants is about 180 million pounds per year. Approximately half of this is attributed to molecular sieves, and 25% are silica gels.

The potential of starch and cellulose as drying agents for fuel alcohol was reported in Science in and scaled up for industrial use by . Ground corn is used in an adsorption process that replaces azeotropic distillation to dry approximately 750 million gallons of fuel ethanol annually. The corn-based adsorbent proved to save energy while avoiding the need to use benzene as the drying agent. The fundamental research and demonstration of the potential of starch- and cellulosebased adsorbents for desiccant air coolers, is an on-going research project at Purdue University that evolved from the first application of corn grits to the drying of fuel alcohol.

Cross-disciplinary research at Purdue University has shown that starch, cellulose, and corn-based materials are potentially suitable for desiccant wheels. These adsorbents are biologically based (biobased). Unlike silica gels and other inorganic adsorbents, biobased desiccants are less expensive, biodegradable, and are derived from a renewable resource. Their low cost and wide availability could hasten adaptation of environmentally friendly air-conditioning systems for residential as well as commercial uses.

BioBased Tile®: A Non-PVC Flooring Made with Rapidly Renewable Resources: Historically, resilient vinyl composition tile (VCT) flooring has been manufactured with binders derived from fossil fuel. Poly(vinyl chloride) (PVC) is the primary binder used to combine plasticizers, processing aids, stabilizers, limestone, and pigments into resilient flooring. Other binders include polyolefins, ethylene acrylic resins, and synthetic rubbers. In , Armstrong commercialized BioBased Tile® flooring, a revolutionary flooring product that uses natural limestone and a proprietary polyester binder made from rapidly renewable materials. Armstrong developed BioBased Tile® specifically to provide a PVC- and phthalate-free alternative to VCT for K-12 education applications.

Armstrong is the first manufacturer in over 100 years to develop a biobased polymer as a binder for a hard-surface flooring product. The new binder created a new category of floor tile that couples improved indoor air quality and environmental benefits with improved performance and affordability. The polymer binder contains 13 percent biobased content from rapidly renewable corn, which reduces reliance on fossil fuels and lowers the carbon footprint. It was built on technologies that previously won Presidential Green Chemistry Challenge Awards (i.e., biobased polylactic acid and 1,3-propanediol) to replace phthalate-plasticized PVC. The consumer product also contains 10 percent preconsumer recycled limestone.

Each year, replacing VCT with BioBased Tile® flooring could save 140 million pounds of virgin limestone, eliminate 336,000 pounds of volatile organic compounds (VOCs) from manufacturing, capture 44 million pounds of carbon dioxide (CO2) from the atmosphere in biobased components, and reduce energy consumption equivalent to 475 billion Btu (or 56 million pounds of CO2). BioBased Tile® flooring is certified by Floor Score with no detectable VOCs. It contains no materials listed in the table of Chronic Reference Exposure Levels (CRELs) established by California&#;s Office of Environmental Health Hazard Assessment (OEHHA). For green building initiatives, BioBased Tile® contributes up to four points toward LEED certification and will be NSF 332 certified in January .

Biocatalytic and Biomimetic Process for the Synthesis of Nitroaromatic Intermediates and Destruction of Nitrocompounds, Including Explosives: Nitroaryl and nitroheterocyclic compounds&#;found in antibiotics, radio sensitizers, explosives, dye intermediates, herbicides, and pesticides&#;require a technology to synthesize and destroy nitrocompounds. The massive stockpiles of explosives alone and the contamination they cause in water, soil, and sediment around the world pose a serious threat to humankind, health, and the ecology. Currently, there are no acceptable technologies or resources to demilitarize aging stockpiles and clean up their contamination. Current stockpiles of energetic materials requiring resource recovery or disposition (RRD) weigh in at about 449,308 tons. Through , over 1.2 million tons will pass through or reside in the RRD account (Joint Ordnance Commands Group, ).

A totally different, but significantly similar challenge exists in cleaning up the sites where soil and ground water are contaminated with TNT, RDX, HMX, and other nitro-based explosives. Today technicians use incineration, open burning, and open detonation technologies to eliminate explosives. The cost of incineration is beyond our means and resources, and open burning and detonation are environmentally unacceptable. Researchers at Pacific Northwest National Laboratory (PNNL) have developed a technology solution that is environmentally friendly, offers economic benefits, and can be easily implemented over incineration, open burning, open detonation, and several other technologies.

The PNNL destruction technology uses enzymes (biocatalysts) and biomimetic processes; the synthesis technology uses biocatalysts. The enzymes for these applications were discovered to be ubiquitous in plants, microorganisms, and dairy products. Nitro reductase enzymes from these sources are used to synthesize nitroaromatic intermediates such as hydroxylamines and aminophenols, and were used successfully to synthesize phenylhydroxylamine and p-aminophenol from nitrobenzene, an important industrial chemical for dye and headache medicine using nitroreductase enzymes from spinach.

Spinach enzymes also were used to synthesize 4-hydroxylamino-2,6-dinitrotoluene from 2,4,6-trinitrotoluene, TNT, which can be used in the production of antioxidants. This TNT conversion process provides a "zero" cost alternative for disposing of unusable TNT stockpiles located worldwide. Unlike incineration, the PNNL biomimetic process, based on potassium superoxide, destroys explosives under mild reaction conditions. Contrary to other processes, this technology synthesizes and destroys nitrocompounds at room temperature&#;without leaving and using organic solvents. These emerging enzyme and biomimetic technologies provide an environmentally benign, safe, and cost-effective method to synthesize and destroy nitrocompounds&#;including explosives.

Biocatalytic Production of 5-Cyanovaleramide: The first step in the manufacture of DuPont&#;s new herbicide azafenidin (Milestone®) is the catalytic hydration of adiponitrile to 5-cyanovaleramide. Chemical catalysts were not regioselective for 5-cyanovaleramide production, and generated significant amounts of byproduct adipamide. Rapid catalyst deactiviation when using manganese dioxide required the use of large amounts of this catalyst, resulting in the production of 1.25 kg catalyst waste/kg 5-cyanovaleramide.

A flammable organic solvent, toluene, was also required for product separation and recycle of unconverted adiponitrile. As an alternative to chemical catalysis, a biocatalytic process was developed for the highly regioselective hydration of adiponitrile. 5-Cyanovaleramide is produced in aqueous solution under mild conditions with 96% selectivity at 97% conversion, and at concentrations comparable to standard chemical processes (19 wt%).

The biocatalyst, Pseudomonas chlororaphis B23 cells immobilized in alginate beads, is a naturally-occurring bacterium containing a nitrile hydratase enzyme. This biocatalytic process reduces catalyst waste production by 99.5%, and no longer requires the use of toluene for product purification. To date, 77 metric tons of 5-cyanovaleramide have been manufactured by this method, eliminating the production of 97 metric tons of catalyst waste. At full commercialization, it is predicted that several hundred metric tons/year of catalyst waste will be avoided.

Biocatalytic Production of Biobased Personal Care Products: Heightened awareness of the skin-damaging effects of ultraviolet (UV) radiation by the public has lead to robust growth in the market for sun and skin care personal products. The market for active ingredients in these products is $100 million in the United States. Approximately 90 percent of the sunscreens in the U.S. market rely on synthetic organic chemicals as their active ingredients. The most common active ingredients tend to bioaccumulate and persist. They also show estrogenic activity in mice and may be endocrine disruptors in humans.

SoyScreenTM is a highly innovative product that meets all the criteria for a green chemical and a green production process. It is made by biocatalysis of renewable feedstocks: ethanol, ferulic acid, and soybean oil. Ferulic acid is 4-hydroxy-3-methoxycinnamic acid, a phenolic compound widely distributed in plants. The biocatalyst is immobilized Candida antarctica lipase B in a solvent-free, packed-bed reactor. This enzyme efficiently transesterifies the ethyl ester of ferulic acid onto the glycerol backbone of vegetable oil. The result is a mixture of feruloylated monoacyl- and diacylglycerols. The biocatalyst retains good activity for months under continuous operation. The desired feruloylated acylglycerols are separated from unreacted ethyl ferulate and ferulic acid by molecular distillation or liquid carbon dioxide extraction. Recovered ethyl ferulate and ferulic acid are returned to the process, resulting in very high atom efficiency. The manufacturing process does not use any organic solvents.

The resulting nontoxic, biodegradable product has excellent properties as a UV-A and UV-B absorber, free-radical trap, and antioxidant, making it a superior substitute for conventional petroleum-based sunscreen active agents and skin care ingredients. Human sensitivity skin testing of SoyScreenTM has confirmed its safety and lack of allergic response. In November , iSoy Technologies constructed a pilot plant for commercial synthesis. It plans to introduce SoyScreenTM into the market in a variety of skincare products in .

Biocatalytically Synthesized High-Performance Novel Antioxidants for Materials: Industrial antioxidants are an increasingly important and fast-growing market. The antioxidants market in the U.S. is currently $1.4 billion, comprised of several low-molecular- weight antioxidants. Dr. Cholli and his group have developed high-performance macromolecular antioxidants that are synthesized in a one-step process using biocatalysts and biomimetic catalysts.

These antioxidants have shown superior oxidative resistance (1- to 30-fold) and higher thermal stability compared to current low-molecular-weight antioxidants. This novel class of antioxidant technology is now ready for commercialization through Polnox Corporation. Dr. Cholli and his team at the University of Massachusetts Lowell originally developed Polnox&#;s technology. Polnox&#;s antioxidants have demonstrated superior performance in a wide range of materials and applications including, but not limited to, foods, oils and lubricants, fuels, plastics, and packaging. An acute oral toxicity (LD50) test for these materials meets the requirements of other FDA-approved antioxidants. Scale-up to multikilogram scale has been demonstrated.

Biochemical Hydrolyzation of Organics in Food Wastes into a Liquid Fertilizer and Soil Amendment: Most agricultural growers use a variety of petrochemical fertilizers, pesticides, and fungicides. There is, however, growing concern that these chemicals in the air, soil, and groundwater are harming the health and safety of humans and wildlife.

Organic Recovery has developed a rapid, batch process to convert food waste into organic-based liquid fertilizers as a less-expensive, environmentally safe alternative to petrochemical fertilizers. The process uses a proprietary mixture of enzymes that may include xylanase, asparaginase, cellulase, urease, protease, lipase, and carbohydrase. The enzymes degrade the lignocellosic cell walls, proteins, lipids, and starches present in the food wastes. Food-grade phosphoric acid or other acid is added to stop the enzymatic digestion before completion; this stabilizes the enzymes and nutrients in the concentrated fertilizer. For use, the fertilizer is mixed with water, adjusted to neutral pH, and applied to soil.

The enzymes resume activity, breaking down proteins and releasing the nutrients and trace minerals that are locked up in the soil. The liquid fertilizer is biodegradable; applied to soils, it adds nutrient- and water-holding capacity. The biochemical hydrolyzation process requires significantly less effort and energy than other methods of recycling food and other organic wastes or producing petrochemical fertilizers.

Organic Recovery"s process prevents the formation of carbon dioxide and methane; it is the only known way to sequester carbon from food waste. This technology can be used in communities needing to minimize carbon emissions, improve their recycling rate, and increase the capacity of their waste disposal facilities. The technology requires significantly less space than competing technologies. Because it is scaled to meet community needs, it keeps the procurement of feedstock and selling of the liquid fertilizer products local, further minimizing adverse impacts on the environment.

During , Organic Recovery constructed a 60-ton-per-day, full-scale processing facility in Florida. It also filed for a patent on its technology.

Bioconversion of Carbon Dioxide into Organic Feedstocks: It has been established that emissions of carbon dioxide gas is responsible for about half of the increase in global warming. Efforts to decrease the consumption of fossil fuel are limited by increasing human population and industrialization and the fact that alternatives to fossil fuel all have important limitations. It is a matter of considerable urgency not only to conserve fossil fuel reserves, but also to search for means to recycle their main combustion product, which is carbon dioxide.

In this regard, a unique bioprocess has been developed which is capable of converting waste carbon dioxide gas into algae, which is subsequently fermented into a variety of organic feedstocks, such as methane and acetic acid. Previous attempts to utilize phototrophic bacteria for fixation of carbon dioxide gas were limited by the following facts: photosynthesis by phototrophic bacteria require anaerobic conditions, which requires that carbon dioxide gas be separated from oxygen, which is an expensive process; unlike algae, phototropic bacteria require a wide spectrum of light, which limits their light source to sunlight. In this technology, a marine algae, Tetraselmis Suecica, has been used successfully in a photobioreactor using light emitting diodes (LEDs) with a specific wavelength of 680 nm and a gas residence time of a few seconds.

More than 98 percent removal efficiency of carbon dioxide gas from typical coal fired power plant stack gases was achieved experimentally at 3 seconds gas residence time at ambient temperature and pressure. The algae was separated from the aqueous phase by settling in a clarifier, and then converted under anaerobic conditions using electrodialytic fermentation to acetic acid and methane in a batch reactor with yields of over 85 percent to acetic acid and 89 percent to methane gas.

Catalytic conversion of methane gas to methanol and other organic feedstocks has been established in the literature. Thus, this process offers several advantages: bioconversion of waste carbon dioxide gas to useful organic feedstocks at ambient temperature and pressure; high conversion efficiencies of carbon dioxide gas to algae and subsequently to acetic acid and methane; and rapid reaction rate in the photobioreactor to produce algae. Economic estimates of the technology have shown that this technology can be easily implemented at power plant sides and acetic acid can be manufactured at less than half the current costs of manufacturing acetic acid from natural gas or crude oil resources.

Biodegradable Copolyester: An integrated resource management approach to the use of materials such as paper, metals, and plastics considers the entire life of a product from raw materials to final disposition. After the useful life of some products, the final disposition depends on various options. The products can enter the municipal solid waste (MSW) stream to a landfill, an incinerator, or an incinerator with electricity/steam production. They also can be discarded on land or at sea, be recycled by industry, or be reused for another purpose by the consumer. One growing option, which Eastman Biodegradable Copolyester is designed to complement, is composting.

This is a process that essentially mimics nature"s biodegradation process (i.e., carbon cycle) and has been used over the ages to various degrees. The process is now recognized to have various benefits, one of which is the reduction of the amount of waste to landfills or incinerators (both of which are expensive to build and maintain, not to mention the problems inherent with siting a new one). In addition, the compost resulting from biodegradation is a soil amendment that adds water retention and other benefits to soils. In fact, such a compost is more beneficial to agricultural soil regeneration than chemical fertilizers. Eastman Biodegradable Copolyester , a patented aliphatic/aromatic copolyester of adipic acid, terephthalic acid, and 1,4-butanediol, was engineered to decompose under proper conditions into water, carbon dioxide, and biomass.

This innovative new product also exhibits such features as low cost, tensile properties similar to low density polyethylene (LDPE), and a soft feel, and is blendable with natural polymers such as starch. Extensive biodegradation and toxicity evaluations demonstrated definitively that Eastman"s new product biodegrades completely at rates comparable to paper without negatively impacting the ecosystem. The material can be extruded into blown film, extrusion coated, and spun into fiber. A plethora of applications is envisioned for Eastman Biodegradable Copolyester including compost bags, personal hygiene items, medical products, and coated paper and board.

Biodegradable Thermoplastic Material (Mater-BiTM): Mater-BiTM is a completely biodegradable and compostable resin that has the physical and mechanical properties of conventional plastics. Mater-BiTM is designed to be used in the manufacture of a wide range of disposable products such as trash bags, shopping bags, food serviceware, and packagings.

Mater-BiTM is a product technology that offers enormous advantages for dealing with the problems of solid waste disposal. Disposal of conventional plastic products, which constitute the largest share of disposable products, has a significant negative impact on the environment. Typically, disposal products are landfilled and rapidly diminish landfill capacity. Being compostable, disposable products made of Mater-BiTM are fully recyclable. Biodegradable food serviceware, for example, presents a significant opportunity for reducing the volume of the solid waste stream. In , nearly 39 billion pieces of disposable cutlery (knives, forks, and spoons) were used in the United States.

More than 113 billion disposable cups and nearly 29 billion disposable plates were used. Biodegradable products are being developed for medical products, textiles, and other new and significant applications. Such products can be transformed into much needed composts and soil amendments for agricultural and horticultural use. Mater-BiTM resin used for films and sheets is made of starch and a polymer, polycaprolactone. Biodegradation time is between 20 and 45 days in composting conditions. Mater-BiTM resin used for dimensionally stable injection molded items is made from completely natural products, including cotton seeds and cornstarch. Biodegradation time is between 75 and 120 days in normal composting conditions.

Biodegradable, Chemically Modified Starch Polymers for Protective Foam Packaging and Insulation Applications: Almost all electronic, commercial, and industrial products come packaged with a protective foam plastic, which is generally petroleum-based polyethylene, polystyrene, or polyurethane foam. This plastic foam is not biodegradable; because it is lightweight, bulky, and not profitable to recycle, it presents a major disposal problem. There is also growing pressure to reduce the carbon footprint of packaging by switching to biorenewable feedstocks. As one example, the U.S. Government program for procurement of biobased products has targeted biobased, biodegradable foams with minimum 50-percent-biobased content for Federal procurement.

Starch is a readily available anhydroglucose polymer. It exhibits hydrophilic properties and strong intermolecular association via hydrogen bonding due to the hydroxyl groups on the granule surface. The strong hydrogen bonding association and crystallization lead to poor thermal processing, however, because the Tm is higher than the thermal decomposition temperature; degradation sets in before thermal melting. The hydrophilicity and thermal sensitivity render the starch molecule unsuitable for thermoplastic applications.

Professor Narayan has synthesized biodegradable, chemically modified thermoplastic starch polymers by reacting starch with maleic anhydride and glycerol using a twin screw extruder as the reactor. The chemically modified starch reacts with biodegradable polyesters like polybutylene adipate-co-terephthalate in the extruder to give starch-polyester graft copolymers. The modified starch polymer and graft copolymers can be processed like any other thermoplastic polymers to produce foam and insulation packaging products that can replace existing petroleum-based products. In addition, the starch-polyester graft copolymers can be formed into films and injection-molded articles.

KTM has successfully commercialized the biodegradable, starch foams under the trade name of GreenCellTM. KTM is manufacturing GreenCellTM in its 23-million-board-foot-per-year facility in Lansing, MI and recently topped $1,000,000 in sales revenues. Corn Products International has licensed Professor Narayan&#;s technology for use in films and molded articles; it is partnering with BASF to manufacture ECOBRASTM products.

Biodegradable, Water-Soluble Anionic Polymers, Prepared in an Environmentally Benign Process, Enhance the Efficiency of Phosphorus Use by Plants: Historically, fertilization of crops with phosphorous has been problematic. When phosphorous is applied to the soil, reactions with various cations including calcium, magnesium, aluminum, and iron fix 75&#;95 percent of the phosphorus. Because this leaves only 5&#;25 percent of the phosphorus available to crops, farmers must apply excess phosphorus. Erosion washes residual phosphorus into waterways, where it causes eutrophication. Specialty Fertilizer Products (SFP) engineered and patented a family of dicarboxylic copolymers that increase the efficiency of phosphorous fertilizers and reduce the environmental impact of fertilization.

The technology includes manufacturing low-molecular-weight itaconic&#;maleic copolymers for use with phosphorous fertilizers. The high negative charge of these polymers sequesters the cations that would otherwise fix the applied phosphorus. SFP sells these polymers under the trade name AVAIL®. SFP uses a green process to synthesize its nontoxic, water-soluble, biodegradable polymers. Itaconic acid, the main component in these polymers by weight, is produced by fermentation of renewable agricultural products. Polymer synthesis occurs in water, with oxygen gas as the main byproduct. The process is highly atom-efficient and does not use organic solvents.

Using AVAIL® polymers with granular or fluid phosphorous fertilizers greatly increases phosphorous availability in soils, resulting in 80&#;90 percent of the phosphorous being available to crops. Benefits include reduced phosphate accumulation in soil, reduced phosphate runoff, and reduced contamination and eutrophication of waterways. AVAIL® produces an average increase of 10&#;15 percent in crop yields at minimal cost. This technology lowers the environmental impact of biomass-derived fuel such as ethanol, butanol, and biodiesel. Because the phosphorus supply is much more energy-efficient, far less fuel is consumed to grow useful biomass and produce plant-derived liquid fuels. AVAIL® has been marketed in the United States and Canada since . Currently, SFP is selling 40 million tons of AVAIL® per year internationally.

Bio-Derived Green Primary Polyvinyl Chloride Plasticizers with Improved Thermal Stability and Plasticization Efficiency: Globally, over 13 billion pounds of plasticizers are produced annually with 90 percent of all plasticizers being used to soften or flexibilize PVC for use in myriad applications such as vinyl flooring, films, blood bags, wall paper, inks, plastisols, shoes and others. Additionally, 90 percent of all plasticizers are phthalates, certain classes of which have come under severe scrutiny due to their suspect endocrine disruption activity. In July , the European Union permanently banned the use of phthalates in all children&#;s articles.

In October , the California Assembly AB signed into law banning the use of phthalates in certain applications. President Bush signed the Consumer Product Safety Improvement Act (CPSIA) in August , which led to the banning of three phthalate ester plasticizers in toys. Thus there is an immediate need in the PVC industry to replace phthalates with cost effective and safe "green" plasticizers based on renewable resources. Besides the health concerns surrounding the phthalate plasticizers, vinyl resins tend to have poor thermal stability that would typically require the use of metallic heat stabilizers, any of which have their own environmental concerns. Several of these new bioplasticizers provide improved thermal stability and may result in a reduction or elimination of these metallic stabilizers, another environmentally friendly benefit. Replacing 25 percent of the global plasticizer production with a bio-based product derived from renewable resources offers significant energy savings in the range of 5 trillion Btu per year with reduced carbon dioxide emissions of about 1 lb less of CO2 emission per pound of plasticizer consumed.

Battelle patented technology addresses the need for a safe and cost effective alternative to phthalates. Battelle has developed several novel plasticizer compounds based on extensive modeling studies to identify chemical structures derived from renewable feedstock to optimize compatibility of the plasticizer molecule with PVC resin to enhance thermal stability and plasticization efficiency. In , the patented technology was licensed to PolyOne, based in Ohio and Nexoleum, based in Brazil, respectively. In /, PolyOne working with their partner Archer Daniels Midland successfully scaled up and introduced to the industry reFlexTM 100, a first generation bio-derived green plasticizer for PVC.

This product has been sold commercially for use in plastisol formulating (liquid vinyl systems) as a co-plasticizing accelerator replacing fast-fusing plasticizers such as BBP (butylbenzyl phthalate) and DBP (dibutyl phthalate). Nexoleum has sold several hundred tons of bio-derived NexoTM E1 plasticizer in Brazil. Market feedback indicates that the new bio-plasticizers are nearly a "drop-in" replacement for phthalates in many applications requiring minimal, if any, changes to current practices in the PVC industry. In , a new 200 ton/ month plant was commissioned in Brazil to meet the growing demand for the new bioplasticizer.

Bioderived Solvents, Surfactants, Fuel Additives, and Monomers: Many applications of renewable resources require the transformation of these resources into platform molecules, which then are readily converted into commercial products. Levulinic acid is one such platform molecule. Biofine, Inc. (winner of the Presidential Green Chemistry Challenge Award in the Small Business Category) discovered a manufacturing process to make levulinic acid from cellulosic biomass. This process is currently moving toward large-scale commercial production. DuPont is taking the next step by developing commercially viable processes to convert levulinic acid into a host of desired products. DuPont uses novel catalytic transformations along with other techniques of green chemistry to develop products derived from levulinic acid that can replace petroleum-derived solvents, monomers, and transportation fuels.

The largest opportunity for biobased feedstocks is the production of bioderived fuel additives. DuPont has discovered several new, high-yield routes to levulinic acid esters that are attractive additives to either diesel fuel or gasoline. As another example, DuPont can catalytically hydrogenate levulinic acid and primary amines in a single, high-yield step to a variety of pyrrolidones; these are widely used as solvents and surfactants. Levulinic acid can also be hydrogenated in very high yield to ?-valerolactone, which has several uses including as an intermediate for "green" nylon 6 or nylon 6,6 and as a potential replacement for ?-butyrolactone, the intermediate for a variety of polymers. Using levulinic acid in ways such as these can reduce dependency on petroleum while consuming cellulosic waste.

Bioderived Succinic Acid as a Platform for a Carbohydrate Chemistry: The biologically derived succinic acid process produces succinic acid by fermenting glucose sugar from corn at present and mixed sugars from lignocellulosics in the future. After separation and purification, the succinic acid is a chemical intermediate that is converted into a wide assortment of environmentally friendly products. This process makes a new platform chemical (a versatile dicarboxylic acid) based on renewables in a process that is itself energy efficient and more environmentally friendly than petrochemical-based products. The company, Applied CarboChemicals, Inc, has also developed an attractive suite of environmentally friendly initial market products. These products will compete directly on price and features.

These products include a biodegradable deicer, which has low corrosivity and ice-melt properties equivalent to NaCl. There is a family of succinate-esters that functions as a biodegradable, recyclable degreaser for machinery. Another formulation enhances the efficacy of certain herbicides, allowing less to be used on the fields. The process is being actively implemented, with a 150,000 L fermentation demonstration scheduled for early . This platform has developed from an active collaboration by all parties. The combination of biotechnology, efficient separation technology and novel chemical synthesis provides economics enabling commercialization of a broad range of products.

Biofiltration Technology: Biofiltration has been used for decades in the United States in towns and cities for odor control, and has also been used in Europe. American companies, however, have been hesitant to consider the natural process because it is so different from the widely accepted conventional control technologies. As part of Tennessee Eastman Division"s (TED) Odor Identification and Control Program, a 1,400 cubic feet per minute gas stream was determined to be a 'priority&#; odor source. Though the vent was, at the time, treated by a 12C-20 caustic scrubber, a hydrogen sulfide odor was detected. One obvious solution to the odor problem was to increase the frequency of the caustic changeouts.

This increased frequency would greatly increase the operation expenses for the scrubber as well as expose operations to greater risks of caustic burns resulting from the increased handling requirements. As an alternative to caustic treatment, biofiltration was investigated as a possible solution. In biofiltration, micro-organisms supported on a stationary porous media bed are used to destroy pollutants from waste gases flowing through the bed. The micro-organisms commonly occur in nature, and various media are excellent candidates for sustaining the micro-organisms and harboring their nutrients. In July , a pilot biofilter was set up to test its effectiveness on hydrogen sulfide removal.

The pilot biofilter proved that biofiltration was a technically feasible and economically attractive alternative to the 12C-20 caustic scrubber for hydrogen sulfide removal from the vent gas stream. Due to this success, a fullscale biofilter, 12C-, was installed in December to replace the 12C-20 caustic scrubber.

Bioinspired Thymine-Based Photopolymers: A Green Chemistry Platform for Innovation, Research, Education, and Outreach: Thymine-based photopolymers mimic the UV-light-induced formation and splitting of dimers in DNA. Vinylbenzyl thymine (VBT), a styrene derivative, offers unique polyfunctionality for polymerization, derivatization, hydrogen bonding, p-stacking, and photocrosslinking. The applications of thymine-based photopolymers are benign, atom-economical, energy-efficient, water-soluble, and processable under ambient conditions.

VBT prototypes combine these features, demonstrating the technical feasibility of commercial applications of benign, prepolymerized photoresists: as a nontoxic, reversible hair fixative; for ambient, aqueous lithography of recyclable printed wiring boards; and for light-modulated pharmaceutical formulations. These highlight safety at the point of use with light as a reagent, avoiding the danger of reactive monomers and emissions of volatile organic solvents.

Antimicrobial surfaces made with VBT copolymers can be substituted for chlorinated disinfectants, reduce the overuse and release of antibiotics, and preclude bacterial resistance. Success with VBT for surface-patterning conjugated-polymer nanocomposites and the facility of VBT for specific host-guest chemistry to embed analytes in sensor coatings offer links to the emerging fields of plastic electronics, functional inks, and smart textiles. VBT prototypes have driven 14 collaborations and 36 student projects; they have served approximately 27 courses and 70 outreach events. This technology has been awarded four patents; three more patents are pending.

Biomimetic Reductive Processes: Biomimetic reductive processes via organic base-catalyzed 1,3-proton transfer are conceptually different from purely chemical processes. They replace a conventional, external reducing reagent with the relatively cheap reagent, benzylamine, or its derivatives, both as a source of nitrogen and as a reducing reagent. This allows the development of environmentally benign, metal-free, organocatalytic reductive processes.

This technology has three significant advantages over other contemporary reductive methods. First, biomimetic transamination can be conducted under operationally convenient conditions at ambient temperatures in commercial-grade solvents, without any solvent, or thermally. It also has attractive economics and is applicable to large-scale production. Second, correct choice of the structural and electronic features of starting compounds allows transamination to occur with complete chemical yield and complete control over the stereochemical outcome. Finally, the organic base catalyst for the transamination can be used on a solid support that allows its complete recovery and reuse as well as the ultimate development of a synthetically and economically efficient continuous-flow process. The available purely chemical reductive methodology does not allow such a process.

The nominated biomimetic technology has already proven superior for several industrially important reductive processes. These include (1) reductive amination of carbonyl compounds (aldehydes, ketones); (2) consecutive 1,3-proton-shift-dehydrohalogenation reactions that provide a general approach for the preparation of 2-aza-1,3-dienes (versatile intermediates in the syntheses of nitrogen heterocyclic compounds); (3) hydrodehalogenation of alpha-halogenated carbonyl compounds; (4) reduction of carboxylic acids to aldehydes; (5) reductive amination of carboxylic acids to amines; (6) enantioselective, organocatalytic, biomimetic, asymmetric, reductive amination of ketones and ketoacids to the corresponding amines and amino acids; and (7) ultimately efficient, continuous-flow, reductive processes using a column packed with an organic base catalyst (chiral or achiral) bound to a solid support. The American Cyanamid Company is currently using this technology for the large-scale synthesis of several amines containing trifluoromethyl groups.

Biomimetic Transition Metal Complexes for Homogeneous Catalytic Reductive Dechlorination of the PCBs/One-Step Extraction-Detoxification in Subcritical and Supercritical Fluids: Polychlorinated biphenyls (PCBs) are ubiquitous in the global environment, toxic, and generally nonbiodegradable. A family of homogeneous catalysts has been developed at the University of Georgia for the conversion of PCBs to dechlorinated congeners and nontoxic biphenyl by a hydrogenolysis process known as reductive dechlorination (RD).

This unique green chemistry has been demonstrated to occur at room temperature due to the high reactivity of the homogeneous transition metal catalysts used for activation of the carbon chlorine bond. The organophosphorus transition metal complexes used for catalysis also are extractable in subcritical solvents used for PCB extraction from soils, sediments, and animal and human tissue matrices. Hence, coextraction of PCBs and the transition metal catalyst has been demonstrated, leading to dechlorination and detoxification of the PCB mixture in one step. This process is compatible with chemical engineering unit operations for countercurrent continuous liquid extraction, as practiced in the chemical industry.

Biosynthetic Production of p-Hydroxybenzoate Improves Regiospecificity and Minimizes Byproduct Generation: The work of Steven W. Peretti at North Carolina State University illustrates the utility of biocatalysis in effecting green chemistry by focusing on the development of an innovative, alternative, biosynthetic pathway for the production of p-hydroxybenzoate (HBA). Biocatalytic production of HBA provides improved regiospecificity over the two step Kolbe-Schmitt carboxylation of phenol, the current state of the art. Due to the specificity of enzyme catalyzed reactions, significant source reductions in the generation of waste byproducts are obtained. Increased levels of safety for both the environment and human health are achieved due to the mild reaction conditions employed. HBA production can now be achieved by a single processing step, a unique feature which cannot be accomplished using traditional chemistry.

HBA production is achieved by contacting an active cell mass with toluene. The toluene passively diffuses into the cells and is transformed through a series of intracellular enzymatic reactions to HBA. Since the pathway for HBA catabolism is blocked through the use of chemical mutagenesis, the HBA generated from toluene conversion is neither incorporated into cellular material nor oxidized for energy, but instead is secreted out of the cell and into the culture media. The HBA can then be recovered by precipitation from an acidified process stream following removal of cell mass.

Biotechnological Routes to "Tailored" Polymeric Products of Environmental and Industrial Importance: Microbial polymerizations offer the potential for the discovery of important new routes to polymers and materials from renewable resources that involve all aqueous, green chemical routes. A critical problem limiting the utility of such methods is the inability to control product structural variables that ultimately determine functional properties. The work of Richard A. Gross has led to the development of a family of technologies that demonstrated unprecedented levels of control for nonribosomal mediated microbial polymerizations.

Lipoheteropolysaccharides have been prepared from renewable resources, and innovative methods were developed to control the product&#;s fatty acid structure and the degree of substitution. This has led to a diverse family of new biodegradable bioemulsifiers that have wide applicability for the stabilization of oil/water emulsions in cleaning and degreasing formulations, biocosmetics, green coating technologies, and bioremediation of organic pollutants. A second technology area has used polyethylene glycols to regulate microbial polyester molecular weight, repeat unit composition, and alter repeat unit sequence distribution. Furthermore, this strategy can be used to form microbial polyester-polyethylene glycol diblock copolymers.

It is now possible, therefore, to consider the in-vivo preparation of synthetic-natural diblocks. This technology created a number of opportunities for the preparation of completely biodegradable interfacial agents for blends, the termination of chains with reactive end-groups for coupling pharmacologically active molecules, and the engineering of surfactant molecules. A third technology area has been the development of new fermentation routes to anionic g-poly(glutamic acid) from renewable resources such as glucose. These routes have the potential to replace millions of pounds of anionic polymers, such as polyacrylic acid, which is nonbiodegradable and persistent in nature.

BioTrans® Soybean-Based Transformer Fluid: BioTrans is a transformer dielectric fluid based on soybean oil. The viscosity and volatility of vegetable oil triglycerides are naturally suited for use as a dielectric fluid and provide extremely low volatility leading to reduced flammability. The oil is hydrogenated to tailor the fatty acids in the triglyceride to optimize oxidative stability and low temperature fluidity. Chemical factors, which negatively impact the dielectric performance of BioTrans were identified. Processing, beyond that normally used for food grade vegetable oil, was developed to minimize their impact on insulating properties. The base oil is further formulated with an additive package specially designed to maximize the low temperature fluidity and minimize toxicity to marine life.

The ester functionality of the triglyceride in BioTrans enables the remarkable extension of transformer life relative to that found for a petroleum oil fluid. Transformer life is limited by paper degradation &#; which is catalyzed by water present in the paper itself. The ability of BioTrans to solubilize water, thus dehydrating the paper extends the paper life by four times.

Naturally derived properties, special formulation, and optimized processing are combined to provide a safe, biodegradable, and non- toxic fluid with significant performance advantages in BioTrans .

Bipolar Membrane Electrodialysis for Greener Processing of Chelates: Chelates are chemical agents that interact or complex with metal ions, often increasing their solubility. Liquid redox sulfur recovery (LRSR) uses chelates to remove poisonous hydrogen sulfide (H2S) from gas streams. A chelate called N-hydroxyethyl ethylenediamine triacetic acid (HEDTA) is conveniently used in LRSR to complex iron and to keep it in solution, where it reacts with H2S.

Several years ago, AkzoNobel developed two novel products containing HEDTA for use in this LRSR process. At that time, the manufacturing process for these novel products included treating the sodium salt of HEDTA (HEDTA-Na3) with ion exchange (IE) technology where Na+ ions are exchanged with H+ ions. Although IE offers favorable exchange of Na+ for H+, it does so at the expense of generating a significant waste stream during regeneration of the IE resin. The Na+ ions present on the resin combine with the regeneration acid, forming a waste salt solution. In addition, IE is inherently a dilution step: energy is required to boil and concentrate the HEDTA product streams after IE processing.

AkzoNobel has now developed and implemented a greener manufacturing technology to replace IE. Bipolar Membrane Electrodialysis (BMED) is a technology that uses ion-permeable membranes and electricity to exchange Na+ for H+. Unlike IE, the BMED technology does not generate a waste stream of salt; rather, it generates a stream of useable sodium hydroxide (NaOH) and requires no regeneration acid. BMED actually concentrates the processed HEDTA chelate solution and eliminates IE&#;s energy-intensive concentration step, saving approximately 360 kilograms of steam per metric ton of HEDTA products.

AkzoNobel believes the BMED technology, implemented at its plant in the United States, is the first major, if not the only, commercial use of this technology to process chelates. Since the technology&#;s introduction, AkzoNobel has identified other opportunities for BMED, allowing greener processing of chelates and other electrolyte products.

Bonderite® TecTalis: Next-Generation Coating: The conventional zinc phosphate pretreatment process promotes adhesion and corrosion resistance on painted surfaces. It has been the automotive standard for over 60 years, but it contains regulated heavy metals, requires expensive wastewater treatment, and uses large amounts of energy.

Zinc phosphating also requires accelerator compounds such as nitrite, hydroxylamine, or nitro-compounds. The process produces approximately as much sludge as it does coating: only about one-half of the zinc ends up as coating; the remaining zinc is lost as sludge that contains Zn3(PO4)2 and FePO4. Zinc phosphate baths require continuous removal of sludge.

Henkel developed TecTalis, the automotive industry&#;s first non-phosphate conversion coating, as an efficient, sustainable replacement for traditional zinc phosphate treatments. Henkel developed TecTalis from its earlier-generation, ambient-temperature Bonderite® NT-1 technology. In the TecTalis process, fluorozirconic acid reacts with the metal substrate to form a zirconium oxide layer approximately 20&#;50 nm thick; this layer is much thinner than a zinc phosphate layer, which measures 2,000&#;10,000 nm.

The TecTalis process deposits over 95 percent of the zirconium onto the coating, so there is essentially no sludge formation. The Bonderite® TecTalis process is simpler than a traditional zinc phosphate process in that TecTalis requires no conditioning or final seal stages. In addition, the new technology can fit into an existing zinc phosphate plant. Customers can design a smaller pretreatment footprint that uses less water and energy than a traditional system. TecTalis provides the corrosion performance necessary to meet automotive standards.

TecTalis is an environmentally sustainable technology that eliminates pretreatment sludge, reduces landfill requirements, and simplifies wastewater treatment. The conversion coating is free of phosphate, volatile organic compounds (VOCs), and carbon dioxide (CO2) equivalent emissions. The process operates at ambient temperature, reducing utility and natural resource requirements. Henkel&#;s TecTalis has been in use in the United States and internationally since .

Bromine Free, TEMPO Based Catalyst System for the Oxidation of Alcohols: The selective oxidation of alcohols to the corresponding carbonyls is one of the more important transformations in synthetic organic chemistry. A large number of oxidants have been reported in the literature, but most of them are based on transition metal oxides such as those of chromium and manganese.

Because most of these oxidants and their reduced compounds are toxic, their use creates serious problems in handling and disposal, especially in large-scale commercial applications. An alternative for the oxidation of alcohols is the Anelli process, which replaces the metal oxides with NaOCl and 2,2,6,6-tetramethylpiperidinyloxy (TEMPO). The Anelli process uses a two-phase (CH2Cl2&#;H2O) system with TEMPO as a catalyst, KBr as a co-catalyst, and NaOCl as the oxidant.

Dr. Augustine&#;s oxidation procedure is a modification of the Anelli process. His procedure decreases TEMPO by a factor of eight and decreases the volume of buffer by 96 percent. It also replaces KBr with a very small amount of the more benign Na2B4O7 (borax) and does not require organic solvents. The reactant alcohol comprises about 38 percent of the total reaction volume compared with only about 2.5 percent in the classic reaction with dichloromethane as the solvent. This has positive advantages in environmental and process safety as well as cost. The procedure isolates the product aldehyde in excellent yield by phase separation from the aqueous solution, which saves energy. Dr. Augustine&#;s procedure can oxidize a number of primary alcohols, producing the corresponding aldehydes in very good to excellent yields. His procedure also oxidizes secondary alcohols to ketones in very good to excellent yields.

The Center for Applied Catalysis collaborated with the NutraSweet Corporation to scale up this reaction. NutraSweet currently uses Dr. Augustine&#;s procedure to manufacture 3,3-dimethylbutanal on a commercial scale. This aldehyde is a feedstock for Neotame, an FDA-approved N-alkyl derivative of aspartame.

BURN-OUTTM Durable, Green, Nontoxic Flame Retardant: Each year, an estimated 4 billion pounds of polybrominated diphenyl ethers (PBDEs) are used in flame retardant (FR) applications. There is growing evidence, however, that PBDEs are toxic. Performance Chemical has developed Burn-OutTM FR, a totally green, nontoxic, durable replacement for PBDEs and other persistent, bioaccumulative, toxic FRs. The Burn-OutTM compound is made of materials that comply with U.S. Food and Drug Administration (FDA) regulations for indirect food contact and are safe for disposal.

Phosphorus and nitrogen are its active ingredients; it is formaldehyde-free. In a fire, Burn-OutTM FR forms an intumescent, thermal-insulating carbonaceous char that acts as a barrier between the burning and unburned material. Inert gases, mostly carbon dioxide (CO2) and water, dilute the combustion gases and cool the surface. Phosphorous-containing compounds react to form phosphoric acid and cause charring. The Burn-OutTM compound releases nitrogen gas and dilutes the flammable gases in synergy with the phosphorus. Burn-OutTM FR resists water, alcohol, oil, and grease, yet cleans up with soap and water. Burn-OutTM FR contains ingredients that resist the growth of bacteria and fungi. In insulation materials, Burn-OutTM FR resists the formation of airborne Legionella bacteria, which can multiply in water systems and are a source of Legionnaires&#; disease. I

n customer formulations, Burn-OutTM FR compounds offer potential cost savings of 20-50 percent compared to current FRs containing halogen and PBDE&#;antimony. Performance is equal to or exceeds that of other products. Burn-OutTM FR reduces landfill disposal costs associated with hazardous materials. Burn-OutTM FR may be used in virtually all aqueous systems and many polymer systems. Applications include paper, corrugated packaging, woven and nonwoven textiles, insulation, ceiling tiles, construction materials (e.g., wood, urethane insulation, and steel intumescent coatings), adhesives, paints, and other FR coatings, especially in the automotive, military, and marine markets. Performance Chemicals is planning to test Burn-OutTM FR in bedding and mattresses. Performance Chemicals commercialized Burn-OutTM FR in .

Cadmium Replacement in Mechanical Coating: Madison Chemical Company manufactures specialty chemical compounds used in numerous applications throughout general industry, and in the metal manufacturing industry. We custom design our products to meet specific needs. Many times these include elimination of highly toxic materials from a customer&#;s facility. In the mechanical plating industry, platers use powdered metal rotated in a barrel with impact media to mechanically plate parts.

Frequently cadmium is the metal of choice in mechanical plating applications, because it adheres to the substrate metal to form a corrosion-resistant coating while giving the coated part a lustrous finish. Cadmium is also highly toxic, a proven carcinogen, and listed under Section 313 of SARA. Chemists at Madison Chemical developed a method of replacing large concentrations of cadmium with trace amounts of nickel in zinc mechanical plating. Zinc and nickel exhibit far less toxicity than cadmium, and our product shows greater corrosion resistance than the cadmium compounds generally used. This formula change was considered unique enough to warrant two U.S. patents.

Carbon BlockerTM Fly Ash Conditioning Treatment: Coal combustion in the United States produces over 70 million tons of fly ash each year. Fly ash is made up of the finely divided, non-combustible materials from coal combustion including silica, aluminum, iron, and a variable amount of unburned carbon in a highly adsorptive form. The silica materials in fly ash can combine with the calcium hydroxide in hydrated cement to form calcium silicate hydrate, the mineral glue in cement. Unfortunately, the carbon in fly ash tends to adsorb the special chemicals added to form the matrix of tiny air pockets in cement that provide the cement&#;s freeze/thaw durability. As a result, many specifications limit the carbon content of fly ash, usually to somewhere between 3 and 6 percent, and much of the fly ash produced in the United States is discarded in landfills.

If the carbon interference can be eliminated, fly ash can be used as a mineral admixture in concrete products to replace up to 30 percent of the cement in concrete. FlyAshDirect, a Cincinnati-based company, has invented a process called Carbon BlockerTM. This is a patent-pending chemical treatment for fly ash that coats the carbon and prevents it from adsorbing air-entraining chemicals. Carbon BlockerTM contains no metals or inorganic salts; its active ingredient is an ester derived from renewable raw materials. It is readily biodegradable, does not add to volatile organic compounds (VOCs), and is generally recognized as safe (GRAS) for food applications. It is used in its pure state without any solvent or other additives. There are currently five commercial Carbon BlockerTM systems installed at three power plants: one each in Ohio, Indiana, and Pennsylvania. The use of Carbon BlockerTM could allow thousands of tons of fly ash to be used in concrete rather than landfilled.

Catalysts for the Copolymerization of Carbon Dioxide and Cyclic Ethers: Generating monomers and polymers from CO2 is a task that green plants accomplish daily on a global scale, yet is one that remains difficult for polymer scientists. Nature has developed an efficient system for extracting an abundant raw material (CO2) from dilute solution and generating a variety of monomers and polymers from it. Professor Beckman&#;s group has created a series of sterically hindered aluminum catalysts (SHACs) that efficiently copolymerize carbon dioxide and cyclic ethers to form ether-carbonate copolymers.

Unlike previously reported catalysts for CO2/oxirane copolymerization, SHACs allow complete conversion at 10-50 °C in only hours, permit incorporation of a variety of cyclic ethers (including ethylene and propylene oxides), generate copolymers with narrow molecular weight distribution, and permit generation of products where the percentage carbonate can range from zero to a completely alternating copolymer. The Beckman group has employed simple alcohols as chain transfer agents during copolymerization; the molecular weight of the copolymer dropped as predicted, yet the polymerization proceeded to 100% yield in the same time as that without the transfer agent.

Effective chain transfer in a living polymerization is crucial, in that if one is to use the catalyst to generate low molecular weight polymers, it is important that one catalyst fragment generate more than one polymer chain, minimizing the amount of catalyst required. Further, dry-box procedures are not needed to employ SHACs for copolymerization. This is significant from a practical perspective, as commercial oxiranes are usually contaminated with up to 0.1% water, and exhaustive drying is not feasible.

These catalysts allow the use of a renewable resource, CO2, in the generation of aliphatic polycarbonates, replacing phosgene. Further, the copolymers themselves contribute to green chemistry through their uses. The Beckman group observed that these ether-carbonate copolymers are more "CO2-philic" than fluorinated polymers and, hence, can be used as low-cost CO2-philes in processes employing CO2 as a solvent and as additives in all CO2-blown foam. Finally, ether-carbonate copolymers will hydrolyze enzymatically and, hence, can be used in degradable polymers and soaps.

Catalytic Extraction Processing (CEP): Catalytic Extraction Processing (CEP) is a proprietary technology that uses secondary materials and byproducts (that might otherwise be considered 'wastes") as raw materials in a manufacturing process. CEP manufactures commercial products (i.e., industrial gases, alloys, and ceramics) from heterogeneous organic, organometallic, and inorganic materials using a molten metal bath as both a catalyst for elemental dissociation and a solution for reaction engineering. CEP feed materials go through two stages in the metal bath: dissociation and dissolution of molecular entities to their elements and reaction of these elemental intermediates to form products. The waste minimization and environmental performance of CEP is ensured by the separation of feed from product through elemental dissociation and the predictable partitioning afforded by the control of thermodynamic operating conditions. Employed as an offsite, closed-loop process unit, CEP maximizes environmental performance for a broad spectrum of secondary materials and byproducts through pollution prevention, waste minimization, and decreased demand on ever-diminishing natural resources.

Catalytic Treatment of Hydrogen Peroxide in IBM Semiconductor Wastewater: Semiconductor manufacturing produces a large ammonia and hydrogen peroxide wastewater stream that requires treatment. Through , the industry standard for treating this wastewater stream was to reduce the hydrogen peroxide with sodium bisulfate then to neutralize it with sodium hydroxide. The next step was separating ammonia by distilling the wastewater to remove ammonium hydroxide. The added sodium bisulfite and sodium hydroxide contributed high levels of total dissolved solids (TDS) to IBM&#;s wastewaters and final effluent discharge, and both were also becoming increasingly expensive. In , IBM&#;s East Fishkill plant (EFK) began an initiative with the New York State Department of Environmental Conservation to reduce the TDS in the site&#;s effluent discharge to a small receiving stream.

Over the next six years, IBM EFK investigated alternative technologies to remove sources of TDS from its manufacturing wastewaters and wastewater treatment processes. In early , IBM qualified a catalytic enzyme process to replace the existing sodium bisulfate process for removing hydrogen peroxide from the ammonia wastewater. This process uses a small quantity of a catalase derived from Aspergillus niger fermentation to decompose peroxide into water and oxygen. It does not contribute TDS to the site&#;s effluent discharge and costs a fraction of the previous treatment. The new process incorporates existing building equipment as much as possible and integrates flawlessly into the existing treatment system.

IBM started and completed design and construction of the full-scale peroxide treatment system in , with startup continuing through March . Annually, this new process eliminates the use of 510,000 gallons of 38 percent sodium bisulfite and 135,000 gallons of 50 percent sodium hydroxide for acid neutralization. It reduces chemical costs by $675,000 per year. The catalytic reduction of hydrogen peroxide process has been online continuously since the beginning of and is currently patent-pending.

Cellulose-Based Fuels and Intermediate Chemicals: ZeaChem&#;s pioneering biorefinery technology uses a hybrid of biochemical and thermochemical processes to make liquid transportation fuels and industrial chemicals. Other approaches have thermodynamic restrictions that limit ethanol production to practical yields of 60&#;90 gallons per dry ton of biomass. The ZeaChem technology has a practical yield limit of 135 gallons per dry ton. This higher yield dramatically improves process economics, allowing farmers to get more ethanol from their biomass crops.

Unlike other processes, the ZeaChem process uses all fractions of the plant: cellulose, hemicellulose, and lignin. Their process allows both fermentable and nonfermentable fractions of the biomass feedstock to contribute chemical energy to the product. First, they fractionate biomass into a sugar-rich stream and a lignin-rich stream. Homoacetogenic bacteria convert the sugars to acetic acid, which is esterified to ethyl acetate and recovered from the fermentation broth. The ethyl acetate is then hydrogenated to ethanol using hydrogen derived from the lignin fraction. The lignin fraction also undergoes thermochemical processing to generate steam and power, making the plant self-sufficient in energy.

Two environmental advantages of ZeaChem&#;s technology are reduced fossil-derived carbon dioxide (CO2) emissions and smaller land-use footprints. The ZeaChem route generates roughly 1.45 pounds of fossil-derived CO2 per gallon of ethanol compared to 3.63 pounds and 12.54 pounds of fossil-derived CO2 per gallon of ethanol from sugarcane and corn dry milling, respectively. Projections on the combination of ZeaChem&#;s high-yield factory technology with high-yield energy farms and improvements in automobile efficiency suggest that as much as 30 percent of America&#;s light-duty fuels could be produced from the amount of agri¬cultural land currently used to produce corn ethanol. Such projections fundamentally change the policy debate on the environmental aspects of ethanol as a liquid transportation fuel. Dur¬ing , ZeaChem began construction of a 10-ton-per-day cellulosic ethanol facility.

Cerenol® Polyol Technology Platform for a Sustainable Bio-Based Economy: With its vision for a sustainable, biobased economy, DuPont has developed an innovative technology platform based on renewably sourced polyols. This platform integrates biology, chemistry, materials science, and engineering to develop renewably sourced products with performance equal to or better than the petrochemical products they replace.

DuPont Cerenol® is a family of high-performance poly(ether diols) made in a sustainable, unconventional, self-condensation polymerization process that primarily uses a renewably sourced ingredient, 1,3-propanediol (Bio-PDOTM). The process uses a soluble acid catalyst at less than one percent by weight that is subsequently removed during purification. The benefits of the Cerenol® platform include (1) a large number of polymers and products from renewably sourced polyols, (2) high-value uses for agricultural feedstocks, and (3) manufacturing processes that not only eliminate hazardous chemicals and process conditions but are also more energy-efficient and generate reduced levels of greenhouse gas emissions versus competing petroleum-based products. Although it has no in-kind competitors, Cerenol® has a significantly lower environmental footprint than does the related petroleum-based compound, poly(tetramethylene ether glycol), as determined by an ISO -compliant life cycle analysis (LCA). From cradle-to-gate, Cerenol® provides 30-percent savings in nonrenewable energy and a 40-percent reduction in greenhouse gas (GHG) emissions.

The exceptional properties of Cerenol® make it attractive for a variety of end-use applications, including performance coatings, inks, lubricants, functional fluids, plasticizers, and personal care products. Cerenol® polymers are also ideal building blocks for several value-added thermoplastic elastomers such as polyurethanes, spandex, copolyether esters, and copolyether ester amides. DuPont&#;s Cerenol® products include two high-performance industrial Imron® polyurethane coating products and Hytrel® RS thermoplastic elastomers for the automotive and sporting goods markets. Over the last two years, more than 20 customers have adopted Cerenol® polyols in their product development with guidance and technology licensed from DuPont; six customer products are in the marketplace today.

C-FREETM Pulp Ozone Bleaching Project: For decades, ozone has been acknowledged as the most promising alternative to chlorine in the bleaching of wood pulp in the forest products industry for the protection of our environment. Despite this recognition, no satisfactory technology was commercially available that met both cost and quality criteria of pulp producers until the early &#;s. Union Camp Corporation, a world leader in pulp and paper production, embarked on a research and development program to solve the problems identified with ozone delignification, including the erection and operation of a $6 million, 25 TPD pilot plant. Based on the results of its R&D and pilot plant studies, Union Camp became convinced that an environmentally friendly bleaching process could be developed on a commercial scale.

The result was the full scale implementation of the world&#;s first high consistency ozone OZ(EO)D bleach line for kraft pine pulp in Union Camp&#;s Franklin, Virginia, fine paper mill during the fall of . The ozone pulp bleaching process is patented under the trade mark C-Free TM. While the C-FreeTM pulp bleaching technology has significantly lower bleaching costs at equivalent product quality compared to conventional chlorine based bleaching, the most important benefit is the significant reduction in effluent properties, volume and fresh water requirements. The effluent biological oxygen demand (BOD), chemical oxygen demand (COD), color, absorbable organic halides (AOX) and chloroform have been reduced by 73 percent, 83 percent, 98 percent, 99 percent, and 99 percent respectively compared to conventional chlorine CEDED bleaching. In addition, dioxin and the 28 chlorophenols identified by the EPA are nondetectable.

ChemBondTM EC An Alternate Printed Circuit Board Oxide Process: Multiple layer printed circuit boards (PCB) require an oxide layer on the Copper circuitry on the internal layers (innerlayers) to promote bonding of the layers of the PCB. This is done conventionally today using a process, which generates one gallon of spent oxide producing solution per 25 square feet (2.5 square meters) of PCB innerlayer. This spent solution must be treated to remove the dissolved Copper in it, which averages 25 grams per liter, before it can be disposed of. This process of Copper removal is difficult, and made yet more difficult because the technology to treat these solutions use an organic precipitant which is interfered with by the concurrent Hydrogen Peroxide in the spent waste. ChemBondTM EC technology avoids all of this by creating a spent oxide producing solution which is readily and economically recycled. Further this process uses atmospheric Oxygen instead of Hydrogen Peroxide, and thus is much lower in cost, and avoids the environmental impact of Hydrogen Peroxide production. The new process is environmentally more benign, economically more attractive, easier to run and control, and produces superior results, over existing technology.

Chemical Conversion of Biomass into New Generations of Renewable Fuels, Polymers, and Value-Added Products: The gradual decline of the prevailing, worldwide petroleum economy is creating an extraordinary need for alternative technologies and, hence, bioenergy research. Consequently, researchers are developing schemes to exploit lignocellulose, the most abundant organic material on the planet. These schemes vary considerably, but each aims to cleave lignocellulose into its monosaccharide components, then derive useful products from the monosaccharides efficiently and inexpensively. The most successful schemes will be those that (1) produce the highest yields, (2) minimize capital and operating expenses, and (3) allow feedstocks from the most sources.

In , Professor Mascal and his group described a process that meets all three objectives. Their method involves digestion of cellulose in a biphasic aqueous acid&#;organic solvent reactor to give remarkably high yields of the novel organic platform chemical, 5-(chloromethyl) furfural (CMF). The method works equally well on raw biomass, producing not only CMF from the cellulose of the feedstock, but also furfural itself from the C5 sugar fraction (i.e., hemicellulose). It uses all of the carbohydrate in the biomass without requiring that lignin first be stripped from the lignocellulose.

Recently, Professor Mascal has upgraded his technology: it now produces an overall 89 percent yield from cellulose consisting of CMF (84 percent) and levulinic acid (LA, the well-known carbohydrate breakdown product) (5 percent) . The new process requires 20-fold less solvent and recycles solvent after use.

The same method processes sucrose into CMF and LA in a remarkable 95 percent overall yield. The method also works well on oil seed feedstocks and leads to a 25 percent increase in biodiesel production from safflower seeds. No other method produces simple organic products directly from cellulosic materials with comparable yields. Important CMF derivatives include biofuels, renewable polymers, agrochemicals, and pharmaceuticals. The green tech companies Micromidas and Incitor have adopted the technology with backing from major chemical and energy company partners.

Chemical Conversion of Post-Consumer Recycled Polyethylene Terephthalate Waste into Sustainable Valox iQTM and Xenoy iQTM Engineering Thermoplastic Products: Polyethylene terephthalate (PET) resin for soft drink bottles is made from virgin, petroleum-based terephthalic acid (TPA) and ethylene glycol (EG). After use, most PET bottles are discarded as waste. U.S. consumers generate approximately five billion pounds of PET bottle waste each year. Another resin typically made from virgin, petroleum-based TPA is polybutylene terephthalate (PBT). PBT is an important engineering thermoplastic commonly used in durable applications such as automotive components and electrical devices. PBT is usually comingled with other polymers and is not practical for recycling. PET scrap, however, is a good source of TPA for use in making polyesters such as PBT.

SABIC Innovative Plastics has developed a novel approach to chemically "up-cycle" PET waste into durable PBT-based products. The PET waste is chemically decomposed to oligomers using excess ethylene glycol, a catalyst, and heat. The recovered TPA oligomers are transesterified with butanediol and repolymerized; ethylene glycol, excess butanediol, and other volatile components are recovered by distillation. The result is Valox iQTM PBT neat resin. The Valox iQTM PBT neat resins and the molding compositions containing them exhibit performance equivalent to materials made by conventional methods. This chemical up-cycling process converts single-use, nondurable PET objects like water bottles into molding compositions containing Valox iQTM PBT neat resins for durable applications.

SABIC has commercialized these environmentally sustainable products under the trade names Valox iQTM and Xenoy iQTM resins. These resins have up to 65-percent carbon content from recycled waste. The environmental benefits of Valox iQTM and Xenoy iQTM resins include up to 55&#;75-percent reduction in both carbon dioxide emissions and process energy. These benefits are accomplished without sacrificing the quality of the final product. During , the first full year of commercialization, the materials were used successfully in more than 20 applications, generating $3.5 million in sales.

Chemical Treatment Modeling and Optimization Software: The French Creek Software Calculation Engine: Most of the water taken out of the environment is used for cooling of industrial and power-generating operations. Some of the water is returned to the environment through evaporation, but most is returned after being heated and treated with persistent chemicals. Any reduction in the amount of water used or the quantity of treatment chemicals discharged has a major impact on the quality and long-term availability of water.

The user-friendly French Creek Software Calculation Engine provides scale prediction, corrosion modeling, and dosage optimization for cooling water treatment. Before French Creek Software introduced its line of software in , few tools were available to predict scale and corrosion problems or to optimize treatment. The available tools such as simple indices and rules-of-thumb contained inaccuracies that resulted in operation at lower-than-desired concentration ratios, in increased water use within plants, and in higher-than-necessary discharges of treatment chemicals to the environment.

Using a sophisticated ion-association model, the French Creek Software Calculation Engine pinpoints the operating conditions at which scale and corrosion become problems and prescribes the most effective dosage of chemicals to inhibit or prevent them. These dosages are often far less than those suggested by typical rules-of-thumb.

In , one of the largest water treatment service companies used the Calculation Engine to save over 21 billion gallons of water by implementing an award-winning automated cooling system controller and companion software. Through applications by other major companies and approximately one-third of the smaller regional companies, French Creek&#;s commercial and private-label programs are estimated to have saved additional billions of gallons of water. In typical applications, French Creek technology has optimized dosages of water treatment chemicals and reduced treatment rates by up to 50 percent.

Chemically Modified Crumb Rubber Asphalt: A process was developed for producing Chemically Modified Crumb Rubber Asphalt (CMCRA). The Chemically Modified Crumb Rubber (CMCR) was produced by using H2O2 ( free radical generator; in this case, carbonium ion generator) to produce carboxylic sites on the surface of crumb rubber by utilizing the oxygenated sites of carbon black [these oxygenated sites will obtain hydrogen from a source, and then be converted into carboxylic acid (COOH) groups]. These sites in crumb rubber could possibly be the cause of devulcanization and could interact with functional groups available in asphalt, resulting in a homogenous modified asphalt.

Compared to controls, asphalt modified using this process has improved rheological properties at both low and high temperatures, as well as improved separation and homogeneity characteristics. Several asphalts were tested and were found to have improved rheological properties (high and low temperature), homogeneity, and separation characteristics. Since rubber, the main component of CMCR, is known as a poor conductor of heat, it is probable that CMCRA can be used in constructing asphaltic pavements at lower pavement temperatures than other neat or modified asphalts. The first pavement test installation was successfully made at a lower pavement temperature than that recommended by the Connecticut Department of Transportation, suggesting that CMCRA can extend the pavement construction season.

Cheminformatics: Faster, Better, Cheaper Chemical Analysis Software: A total of 10 million environmental samples were analyzed last year by 900 independent testing labs, manufacturing companies, and government and university-owned laboratories. Although no estimates exist for samples analyzed in support of drug discovery programs, growth in the biomedical and life science markets is expected to dramatically increase the number of samples analyzed by liquid chromatography/mass spectrometry (LC/MS). Analyses made in support of state and federal regulatory programs and for research, development, manufacturing, and quality control in these two markets alone use more than two million gallons of solvent annually. The spent waste solvent must be discarded as hazardous material at a cost of $51 million.

The primary objective of the proposed technology is to dramatically reduce solvent consumption at the source, namely, during the sample preparation process and in the analysis itself. The data analysis software, called Ion Fingerprint DetectionTM(IFD), makes ultrafast GC/MS and LC/MS possible. The patented peak deconvolution algorithms identify and quantify target compounds in the presence of other target compounds and highly contaminated matrices without extensive sample cleanup. IFD should eliminate approximately 90% of the solvent needed to prepare and analyze samples by GC/MS and as much as 50% for LC/MS.

The proposed technology, Ion Fingerprint DetectionTM(IFD) software, should reduce solvent consumption in the two fields dealt with by approximately two million gallons annually and save $50 million in hazardous waste disposal costs. If forensic, petrochemical, drugs of abuse, quality control, and other routine types of analyses are included, solvent consumption and cost savings may be ten times the estimated numbers.

Toward this end, Professor Robbat has shown that IFD, when combined with large volume gas chromatography (GC) inlets, provides quantitative analysis of EPA pollutants in minutes. The data produced have been verified by state and federal regulators and used to determine contaminant risk to ground water and to delineate the extent of contamination at twenty-five Superfund sites. The proposed technology increases measurement precision, accuracy, and sensitivity, and reduces the per-sample analysis costs.

Chlorantraniliprole: Increased Food Production, Reduced Risks, More Sustainable Agriculture: The caterpillar larvae of many lepidopteran species are major agricultural pests, defoliating plants and attacking fruit and root systems. Lepidopteran pests are likely responsible for 30&#;40 percent of insect damage to crops; they consume 50 percent of all crops in many developing countries. Although insecticides are available to control these pests, many present significant risks to humans or the environment. DuPont redesigned its discovery process for new pesticides by integrating chemistry and biology with toxicological, environmental, and site-of-action studies to optimize safety and product performance simultaneously.

The resulting product, chlorantraniliprole, has excellent safety and environmental profiles yet is one of the most potent, efficacious chemical insecticides ever discovered. Chlorantraniliprole selectively interferes with muscle contraction in insects by activating a site in ryanodine receptor channels that is highly divergent between insects and mammals. Because it selectively targets insects, chlorantraniliprole is inherently safer to people and other nontarget organisms. EPA classifies chlorantraniliprole as a reduced risk pesticide. It may be the safest of all lepidopteran insecticides, including those derived from natural sources. Chlorantraniliprole is usually one to two orders of magnitude more potent against target pests than are pyrethroids, carbamates, and organophosphates.

Its lower use rates mean less pesticide gets into the environment with a corresponding reduction in the exposure of workers and the public. Chlorantraniliprole&#;s proven safety to bees and other beneficial arthropods allows its use in integrated pest management (IPM) programs. In addition, its mode of action provides an important new tool for managing insecticide resistance. DuPont manufactures chlorantraniliprole in a convergent commercial process that minimizes organic solvents, recovers and recycles the solvents it does use, minimizes waste, eliminates regulated waste products, and establishes inherently safer reaction conditions. Chlorantraniliprole is rapidly displacing less desirable products from many key markets. In alone, more than 20 million farmers and 400 crops benefitted from insect control by chlorantraniliprole.

Chloride Free Processing of Aluminum Scrap: According to the U.S. Geological Survey, U.S. year to date aluminum scrap consumption totaled 724 million pounds. Other than can scrap, which is processed separately, the bulk of the aluminum is consumed by the secondary aluminum industry. In spite of the fact that scrap is carefully selected so that a specific charge will meet product specifications, the molten charge typically contains up to 1.0% magnesium (Mg). Because the specifications for most diecast aluminum alloys call for a Mg level of less than 0.1% Mg, the charge must be demagged. The excess Mg is removed through the addition of chlorine (Cl2) gas, or occasionally through the addition of AlF3. Most of the demagging reaction schemes use Cl2 and in practice require 6 lb of Cl2 gas to remove 1 lb of Mg as MgCl2 (approximately 4,500 lb of Cl2 per batch). Both techniques require both careful handling of the materials to insure operator safety and air pollution controls to insure the protection of the environment. If wet scrubbers are used in the air pollution control systems, then the fugitive chlorides that are captured in the water require additional treatment to meet clean water standards.

A more ideal approach is to remove and recover the Mg from the melt using a technology that is inherently safer and cleaner because it does not require additions of Cl2 gas or AlF3 and requires a minimum of processing steps. The Albany Research Center (ALRC) has conducted very successful research to investigate the synthesis and scavenging properties of ionically conducting ceramic oxides such as lithium titanate (Li2Ti3O7) for demagging the aluminum scrap melts. The process known as engineered scavenger compound (ESC) technology offers an alternative to the conventional demagging technology that has distinct safety and/or environmental advantages over previously employed methods. The ESC technology neither generates fugitive chloride emissions nor hard to dispose of drosses or slags. The ESC reaction is easily reversible so that the recovered species is available for recovery and reprocessing as a metal product rather than as a salt in the older process.

Chrome-Free Single-Step In-Situ Phosphatizing Coatings: Economic losses resulting from corrosion of metals have been said to amount to billions of dollars per year and to be of the magnitude of 4 percent of the gross national product. In commercial practice, organic polymer coatings have been used in both commercial coating industries and the military to protect metal substrates against corrosion. The current organic coating on metals involves a multistep process and considerable energy, labor, and control. The traditional phosphate treatment process for preparing metal prior to painting is a costly and error-prone process. For example, information provided by Caterpillar Tractor&#;s Montgomery, Illinois, plant for the cost per year of its hydraulic tube phosphating line is $330,000 (water/wastewater treatment = $70,000; chemicals = $36,000; labor = $166,000; steam = $50,000; and electricity = $8,000).

In addition, the use of corrosion inhibitors, the phosphating line baths, and the chromate sealing process in the current multistep coating practice generates toxic wastes such as chlorinated solvents, cyanide, cadmium, lead, and carcinogenic chromates. The innovative green chemistry technology of chrome-free single-step in situ phosphatizing coatings (ISPCs) is a one-step self-phosphating process. The unique chemical principle of ISPCs is that an optimum amount of in situ phosphatizing reagents (ISPRs) are predispersed in the desired paint systems to form a stable and compatible one-pack coating formulation.

The formation of a metal phosphate layer in situ will essentially eliminate the surface pretreatment step of employing a phosphating line/bath. The ISPRs form chemical bonds with polymer resin that act to seal and minimize the porosity of the in situ phosphated substrate. The use of chemical bondings to seal the pores of metal phosphate in situ should enhance coating adhesion and suppress substrate corrosion without a post-treatment of final rinses containing chromium (Cr6+).

Chrome-free Single-step In-situ Phosphatizing Coatings: Anti-fingerprint Coatings on Galvanized Steel: Current corrosion-inhibiting paints (such as the nominated anti-fingerprint coating for galvanized steel) rely heavily on the use of chromates in surface pre-treatments and primers. These chromates are carcinogenic and must be eliminated. The nominated ISPC technology is a one-step process that uses no chromates, and eliminates a number of expensive and potentially hazardous process steps from the current state-of-the-art technology. This is achieved by pre-dispersing an optimum amount of in-situ phosphatizing reagents (ISPRs) in the desired paint system.

The ISPRs are designed to produce a metal-phosphate layer in situ, and at the same time to form covalent linkages with the polymer resin that ensure excellent coating adhesion and inhibition of substrate corrosion without using chromates. In the nominated technology, a water-borne ISPC acrylic emulsion is developed, free of chrome and hazardous air pollutants (HAPs), and is applied to a galvanized steel sheet with a roll coater to achieve a dry film thickness of less than 1.0 micrometers. This coating passed all the required alkali resistance and salt (fog) spray tests, and gave excellent results in both fingerprint resistance and earthing property. It thus uses safer chemicals and eliminates enormous amounts of chromates and HAPs from the industrial waste stream.

Clean Diesel Breakthrough: Simultaneous Decrease in Emissions of Both Particulates and Oxides of Nitrogen During Combustion: One of today&#;s most challenging environmental problems is air pollution by oxides of nitrogen (Ox) and particulates, created largely by diesel engines, particularly in urban areas. Ox and particulate emissions from diesel engines are a major source of urban air pollution. Particulate matter contains organic compounds that may potentially cause cancer or mutations. Nitrogen oxides contribute to the formation of acid rain, ground-level ozone, and smog. Although the availability of oxygen enrichment in diesel engines has long been known to reduce particulate levels, it has not been a feasible technology because it increased the Ox levels. By using only a modest increase in oxygen level in engine intake air and optimizing fuel conditions, Argonne National Laboratory (ANL) has broken through the technical barriers to create an oxygen enrichment technology that simultaneously reduces both particulates and Ox.

The breakthrough came when ANL tested a new combination of three changes to engine operating conditions: 1) increased oxygen content in the engine air supply, 2) retarded timing of fuel injections, and 3) increased fuel flow. ANL tests were the first to adjust all three parameters. Previous strategies had changed only one or two of these conditions. This breakthrough technology is made practical by the development of a compact advanced polymer membrane that is a passive design and can be retrofitted to existing engines. The mass-production cost is expected to be modest ($75 to $160) compared with particulate traps ($200 plus 2 cents per gallon to operate) and Ox treatment catalytic converters ($300 plus periodic maintenance).

This is the first oxygen enrichment technology to simultaneously reduce both Ox (by 15%) and particulates (by 60%). It is an all-in-one, in-cylinder treatment that solves the emissions problem at the source, does not drain engine power (in fact, increases gross power by 18%), and improves fuel efficiency (2 to 10% improvement in brake-specific fuel consumption across the entire load range in a locomotive notch schedule). This breakthrough technology will be important to diesel engine manufacturers, who are faced with helping their customers meet lowered regulatory standards beginning in model year .

CleanGredientsTM: Systems-Based Information Technology for Green Chemistry: CleanGredientsTM is an online database of environmental fate, toxicology, and other data on cleaning product ingredients. CleanGredientsTM uses a peer-reviewed framework to evaluate and compare chemicals within functional classes. It enables manufacturers to showcase ingredients with lower inherent environmental or human health hazards. It also enables formulators to identify ingredients for environmentally preferable products easily.

CleanGredientsTM facilitates the ongoing development and implementation of green chemistry in the cleaning products industry. It has the potential to expand into other industry sectors. CleanGredientsTM grew out of recommendations of the Unified Green Cleaning Alliance and a partnership between GreenBlue and the U.S. EPA&#;s Design for the Environment (DfE) Program. The steering and technical advisory committees for the Alliance drew members from leading organizations in industry, government, and the nonprofit sector. The committees established the overall format and identified the specific attributes for the CleanGredientsTM database. Interested participants, now numbering around 600, serve as peer reviewers.

CleanGredientsTM presents carefully selected information on chemical raw materials including performance properties, environmental fate, human and environmental health, safety, and sustainability in a format that helps formulators easily identify candidate ingredients for environmentally preferable product formulations. CleanGredientsTM lists only chemicals that have been characterized adequately and meet key human and environmental characteristics. Formulators can search the database by general ingredient information and physical properties to identify suitable candidate ingredients for particular applications. The first CleanGredientsTM module (surfactants) was launched in . Within 2 months, 11 raw material suppliers and 50 formulators had subscribed to list ingredients or access information. Modules for solvents, chelating agents, and other product classes are under development.

Cleaning and Disinfecting with Ozone: Making Green Chemistry with WhiteWaterTM Ozone: In recent years, bacterial contamination in food processing plants has caused a significant increase in food recalls and demands for improved sanitation. Traditional sanitation procedures include direct treatment of food with disinfectants during production plus multistep cleaning and disinfecting of food-handling equipment during downtime. Most disinfectants used in food processing facilities have been based on oxidizers containing chlorine.

In , the FDA approved the use of ozone as a disinfectant in food plants. Ozone is a potent oxidizer; compared to chlorine-based disinfectants, ozone has higher atom efficiency and is used at lower concentrations. Replacing only conventional disinfectants with ozone was not a commercial success, however, because cleaning and sanitation still required significant plant downtime and the ozone equipment was expensive.

Ozone International has researched, developed, and commercialized new technology that enables the effective, safe use of ozone in food plants, not only for disinfecting but also for cleaning during and after production. The technology, WhiteWaterTM ozone, generates ozone on-site as needed and applies it in dilute aqueous solutions. WhiteWaterTM ozone replaces both conventional cleaning chemicals, such as surfactants and degreasers, and conventional disinfectants, such as chlorine-based products. WhiteWaterTM ozone also continuously cleans and disinfects food handling equipment during production, enhancing food safety while reducing downtime for sanitation. WhiteWaterTM ozone saves energy because it does not require heated water as do traditional sanitation procedures. WhiteWaterTM ozone also offers substantial cost savings.

Used as directed, WhiteWaterTM ozone does not expose workers or the environment to hazardous levels of ozone gas. Discharge from a food plant using WhiteWaterTM ozone contains water, oxygen (O2), and oxidized bacteria and organics that are more readily biodegradable and less likely to contain chlorinated organic compounds such as chloroform. Ozone International&#;s most recent patent was issued in . WhiteWaterTM ozone is in use by approximately fifty food-processing facilities nationwide.

CleanSystem3 Gasoline: Internal combustion engines produce considerable amounts of nitrogen oxides (Ox) as a combustion byproduct. Ox are an air pollutant in their own right and react with atmospheric organic compounds in the presence of sunlight to form ozone, a powerful respiratory irritant. Despite a 76 percent reduction in allowable Ox emissions from light-duty gasoline vehicles over the past 25 years, U.S. motor vehicles still emit 3 million tons of Ox each year. Source reduction in the context of vehicular Ox means less Ox generated in the engine.

Steps in this direction have been few (primarily exhaust gas recirculation) and, being a design feature, are not applicable to older vehicles. There is, therefore, a genuine opportunity for technology which can reduce the Ox generated in vehicle engines on the road today. Texaco has developed and introduced a patented additive technology based on novel chemistry which reduces Ox formation in gasoline engines. This additive is present in all CleanSystem3 gasoline sold in the United States. Controlled vehicle testing has demonstrated reductions in tailpipe Ox up to 22 percent. This additive fulfills the role of traditional deposit control ('detergent") additives in keeping fuel system components clean, and provides additional performance in the area of preventing and removing combustion chamber deposits. Cleaner combustion chambers retain less combustion heat from one engine cycle to the next, and the resulting lower temperature leads to the formation of fewer Ox.

ClearMate: Process chemicals used in the electroplating industry are subject to a number of harmful contaminants that ultimately decrease the usable capacity of a process solution. Once a bath is no longer usable it must be waste-treated, usually in the form of an expensive batch dump. In particular, the clear chromate bath is most susceptible to harmful contaminants and its life can vary in length from one week to one month based on heavy to moderate use, respectively. The major contaminant of the clear chromate solution is iron, which is introduced to the system when raw metal parts are submerged during processing or dropped and left at the bottom of a chromate tank.

Clearmate developed a process for recovering a spent clear chromate solution and then developed an additive that prevented premature iron contamination in the first place. The ClearMate chemical additive is an innovative, yet simple, chemical combination that drastically extends the longevity and quality of the clear chromate conversion solution for the metal finishing industry. It can extend the lifetime of conventional clear chromate solutions by a factor of 12. The additive protects raw metals from the acidic nature of the chromate solution. On initial contact with raw metal substrates, iron begins to dissolve into solution as an ion. The additive contains highly charged cationic polyelectrolytes that surround and impede any attack on the substrate by the acidic chromate solution. Extending the bath life by a factor of 12 has the potential to reduce the 70 million gallons of clear chromate waste produced annually in the United States to 6 million gallons.

Closing the Loop with "Benign by Design" Biobased Fabrics and Backings: Interface Fabrics has successfully developed and introduced into the market a sustainable quality textile fabric that uses biobased fibers, environmentally preferable textile finishing dyes and chemicals, and a biobased textile coating. Technical innovations in yarn development, dyeing, weaving, and finishing of biobased fibers were necessary to produce a fabric that meets the stringent standards of the commercial interiors market. The base material for the biobased Terratex® fabric and the BioBacTM textile coating is a homopolymer of polylactic acid (PLA). The fabric is woven from IngeoTM PLA fiber; BioBacTM is made from NatureWorksTM PLA resin. PLA Terratex® is an alternative to petroleum-derived fibers like polyester; BioBacTM replaces traditional acrylic or styrene-butadiene rubber latex coatings. The biodegradability of PLA allows its reassimilation into plants as a nutrient, thereby closing the loop on raw material utilization. PLA Terratex® composts successfully in a commercial composting facility under standard operating conditions.

Interface Fabrics has developed a stringent dye and chemical protocol to screen all ingredients used to dye and finish PLA Terratex® fabric; the company then selects only those that are not harmful to health or the environment. To date, Interface Fabrics has screened 279 chemicals used in about 147 dyes, finishes, and auxiliaries, approving only about 30 of these chemicals. The protocol excludes ingredients that are carcinogens, mutagens, persistent, bioaccumulative, or toxic chemicals (PBTs), skin sensitizers, etc. Many of these are in common use in fabrics today. To validate the benign nature of its protocol, Interface subjected fabric samples of six different color palettes to hazardous waste characterization and synthetic precipitation leaching analysis. It screened for 179 chemicals of concern, including volatile organic compounds (VOCs), semi-volatile organic compounds, metals, polychlorinated biphenyls (PCBs), pesticides, and carbonyls. It detected only copper, fluoride, nitrate, and sulfate, all at concentrations only marginally above the reporting limit.

Commercialization of NXT Z®: An Ethanol-Free, Low-VOC, High-Performance Silane for Silica Tires: Silica tires have experienced remarkable growth in the last decade because of their superior performance. Silica tires incorporate silane coupling agents to disperse the silica in the rubber matrix and reinforce the matrix, a key to reduced rolling resistance and other aspects of performance. Reducing rolling resistance can translate into improved vehicle fuel efficiency. Tire tread life relates to tire value and scrap rates, and traction is important for automotive safety.

Traditional silane coupling agents contain triethoxysilane moieties that hydrolyze to release ethanol. Tire manufacturing releases some of this ethanol, and tire companies must dispose of it at substantial cost. A significant amount of ethanol remains in the tire, however, and is released into the atmosphere while the tire is in use. Ethanol from silica tires can account for a measurable portion of the volatile organic compounds (VOCs) released by a vehicle. In California, the California Air Resources Board (CARB) enforces legislation that regulates background emissions of VOCs.

NXT Z® silane is a new coupling agent designed to improve the wear, traction, and rolling resistance of silica tires, without the ethanol emissions imparted by traditional silanes during tire manufacture and use. It builds on previous discoveries of blocked mercaptosilanes. NXT Z® silane contains both mercaptan and thiocarboxylate functionalities linked by high-boiling diols in place of the ethanol-derived alkoxy groups used in traditional silanes. The high-boiling diols have similar or faster hydrolysis rates than ethoxy groups, depending on whether they are bound to one or two silicon atoms. Once hydrolyzed, however, the high-boiling diols remain in the rubber compound, presumably bound to silica. NXT Z® silane also helps reduce manufacturing costs through hotter, harder, faster processing; single-step mixing; long-shelf-life silica compounds; and lower use levels. Several major tire companies tested NXT Z® for fast-track commercialization during .

Compostable Multilayer Food Packaging: Most conventional food packaging consists of a multilayer film structure comprised of polyolefin or polyamide resins and adhesives. The layers include barriers, colorful print, and adhesives to bond all the layers together. Because conventional packaging is neither recyclable nor compostable, landfills are the only disposal option. When organic material goes into a landfill it degrades over time, releasing landfill gas (LFG), which is a mixture of the environmental pollutants methane gas and carbon dioxide (CO2). Because less than 30 percent of the landfills in the United States collect LFG, the majority of organic material placed into landfills eventually releases LFG.

In , BASF&#;s Biodegradable Polymers Group successfully made a completely compostable multilayer food packaging structure with high barrier properties. The structure consists of six layers: an Ecoflex® and Ecovio® outer layer, Joncryl SLX (printing ink layer), Epotal P 100 ECO (adhesive coating), a metallization layer, Versamid® (pre-met primer), and an Ecoflex® and Ecovio® inner layer. Ecoflex® is a bioplastic copolyester and Ecovio® is a compound of Ecoflex® with polylactic acid (PLA). This packaging structure meets the barrier requirements for a large number of packaged consumer goods.

For the first time, food packaging wastes can be diverted to industrial composting facilities that create end-of-life value far beyond putting the packaging in landfills. Composting and the subsequent use of the finished compost produce beneficial factors for the environment and resource management. BASF compostable multilayer packaging will allow landfill diversion for programs throughout the United States that are working toward Zero Waste. One of the benefits of diverting organic waste from landfills is increasing landfill lifespans. This reduces the need to build new landfills or expand existing ones, which will save energy, reduce emissions to water, and reduce air pollutants from building new landfills. BASF is partnering with the Seattle Mariners in their zero waste initiative through the Green Sports Alliance to replace trash cans with recycle and compost bins.

Computational Design of Corrosion Resistant Steels for Structural Applications In Aircraft: The program&#;s objectives are to design, prototype, and characterize a new corrosion resistant steel that can significantly reduce DoD&#;s use of cadmium during rework, maintenance, and the manufacturing of structural steel components for aerospace applications. The new steel will be developed by applying advanced computational tools, models, and design methodology and will demonstrate the potential of a new method suitable to develop alternative processing paths and materials to replace processes and materials posing increasing environmental concerns.

There are four primary technical Tasks within the program. The specific activities within each Task result from the application of Materials by Design approach, which integrates processing, structure, property, and performance relations within a multilevel systems structure. The first task, Analysis, will generate a systems flow-block diagram and calibrate models for the design process. The second task, the Design/Synthesis Task, will determine an alloy composition and the processing variables. During the third task a 300 lb. heat of the prototype material will be acquired and characterized; and the during the final task a technical report will be prepared detailing the program activities and analyzing the feasibility of the alloy design and its potential for further development and commercialization. A prototype of an entirely new corrosion resistant steel will be delivered that will posses similar mechanical properties to those of 300M and be compatible with current and emerging aerospace coating processes such as high-velocity oxygen fuel (HVOF) technology.

The benefits of mechanistic computational design technology is that it is now possible to rapidly develop entirely new materials and processes at costs that are orders of magnitude below the historical application of trial and error discovery methodology. Use of this alloy will eliminate the need for chromium and cadmium plating for wear and corrosion resistance in sensitive, critical aircraft structural components.

QuesTek is working to develop joint venture agreements with alloy producers and aircraft landing gear manufacturers to execute a first article demonstration/validation program. The specifications for the alloy and the protocol for material testing and evaluation have been designed to meet the end-user standards of Boeing and BFGoodrich in the U.S., and of Messier-Dowty in Canada.

Concrete-FriendlyTM Powdered Active Carbon (C-PACTM) to Remove Mercury from Flue Gas Safely: Coal-fired power plants emit 45 tons of gaseous mercury into the air and produce 65.5 million metric (MM) tons of fly ash annually in the United States. Fly ash has a composition similar to that of volcanic ash and is an excellent replacement for cement in concrete. Currently, about half the concrete produced in the United States contains fly ash. Of the 65.5 MM tons of fly ash generated in , more than 11.5 MM tons were used in concrete and 16.0 MM tons were used in structure fills, soil modification, and other applications.

According to EPA&#;s report to Congress, federal concrete projects used 5.3 MM tons of fly ash in and to replace cement, saving about 25 billion megajoules of energy, saving 2.1 billion liters of water, and reducing carbon dioxide (CO2) emissions by about 3.8 MM tons. Powdered activated carbon injection (ACI) is a conventional technology that injects mercury sorbents into flue gas in power plants and captures the mercury-laden sorbents in fly ash. Although this reduces mercury emissions, the resulting fly ash is unsuitable for concrete and requires disposal in landfills.

If mercury contamination made all fly ash unsuitable for use in concrete, the 11.5 MM tons now used in concrete each year would require more than 33 million cubic feet of new landfill space at a cost of about $196 million. Albemarle designed, synthesized, developed, and commercialized its novel Concrete Friendly mercury sorbent, Concrete-FriendlyTM Powdered Active Carbon (C-PAC(TM)). C-PAC(TM) is activated carbon with tailored pore structures and surface properties. Albemarle manufactures C-PAC(TM) from renewable carbon sources using a greener synthesis that includes gas-phase catalytic bromination. C-PAC(TM) removes large amounts of mercury from air, preserves the quality of fly ash for concrete use, safely sequesters the mercury in the concrete, and eliminates the need for new landfill space. Several power plants across the United States currently use C-PAC(TM).

Continuous Processing Enables a Convergent Route to a New Drug Candidate: LY*H3PO4: The commercial production of LY*H3PO4, an investigational new drug candidate currently in phase II clinical trials, illustrates the importance and impact of designing green processes. Lilly acquired this drug with its purchase of Hypnion, Inc. The original synthesis enabled early development, but was not amenable to large-scale manufacture. Lilly identified several major environmental and safety issues with the original chemistry. Among them were: (1) dimethylformamide/sodium hydride (DMF/NaH) in step 1, (2) methylene in various steps, (3) a molten step with observed self-heating, (4) an aldehyde purification that would be unsafe at increased scale, (5) phosphoryl chloride (POCl3) in large excess, (6) chromatographic purification.

After brief explorations, Lilly discovered a convergent variant of the original route. Flow processing proved critical to this new route&#;s success. First, an extremely efficient carbonylation replaced an inefficient oxidation catalyzed by TEMPO (tetramethyl pentahydropyridine oxide). Subsequently, hydrogen replaced sodium triacetoxyborohydride (STAB) in a reductive amination. Although both operations require high pressure (1,000 psi) that is unsafe in traditional batch tanks, both proved amenable to flow processing, resulting in safe, efficient syntheses. Lilly uses process mass intensity (PMI) in its process development. PMI is the total mass of raw materials (including water) put into a process for every kilogram of drug produced.

The original route had a PMI of over 1,000 before chromatography. Lilly&#;s new route has a net PMI of 59, representing a 94 percent reduction (96 percent reduction including chromatography). This PMI is extraordinary given the complexity of the drug and its nine-step synthesis. Lilly implemented its new route for LY*H3PO4 on a pilot-plant scale in Indianapolis, Indiana, during and on a commercial scale in Kinsale, Ireland, during . Lilly&#;s application of green chemistry, as well as its development and use of flow chemistry, led to an efficient, convergent synthetic route and a significantly improved manufacturing process.

Convergent Green Synthesis of Linezolid (ZyvoxTM), an Oxazolidinone Antibacterial Agent: Pfizer has developed a novel, convergent, green, second-generation synthesis of linezolid, which is the active ingredient in ZyvoxTM. Approved by the U.S. Food and Drug Administration in , ZyvoxTM is the only member of the oxazolidinone class of antibacterials. This is the first new class of antibacterials approved in over 30 years. ZyvoxTM is approved for the treatment of antibiotic resistant gram-positive bacterial infections, including vancomycin-resistant Enterococcus faecium (VREF), methicillin-resistant Staphylococcus aureus (MRSA), and multidrug-resistant Streptococcus pneumonia (MDRSP). These antibiotic-resistant bacterial infections have become an ever-increasing threat to public health.

Pfizer initially developed a linear synthesis for ZyvoxTM; the company is currently using this launch process to manufacture the drug. Rapid growth in global demand for this valuable life-saving drug, however, led Pfizer to develop a greener, more efficient, convergent synthetic process to meet future needs, as well as reduce the cost and environmental impact of production. The second-generation process will replace the launch process after approval by appropriate regulatory agencies. It has numerous green chemistry benefits: overall yield is increased by 8 percent; total waste is reduced by 56 percent; nonrecycled waste is reduced by 77 percent; methylene chloride waste is reduced by 78 percent; and a pressurized ammonia step is eliminated. At current production volumes, total waste will be reduced by 1.9 million kilograms per year, and 1.7 million kilograms per year of nonrecyclable waste will be eliminated.

The greater efficiency of the new synthesis will greatly reduce the use of natural resources. The greatly reduced waste will significantly reduce the transport of hazardous waste and consequent potential for accidental exposure of humans and the environment. Reducing the cost of linezolid production will make this life-saving drug more readily available to a larger proportion of humanity.

Conversion of Municipal Solid Wastes to Drop-In Fuels and Chemicals: Terrabon&#;s MixAlco® process converts any anaerobically biodegradable material (e.g., proteins, cellulose, hemicellulose, fats, and pectin) into a variety of chemicals (e.g., ketones and secondary alcohols) and fuels (e.g., gasoline, diesel, and jet fuel). The conversion occurs by nonsterile, anaerobic fermentation of biomass into mixed carboxylic acids and salts by a mixed culture of naturally occurring microorganisms, followed by conventional chemistry to convert the mixed acids and salts into desired chemicals or fuels.

Feedstocks for the MixAlco® process include a number of wastes that typically end up in landfills: municipal solid waste (MSW), sewage sludge, forest product residues (e.g., wood chips and wood molasses), and non-edible energy crops (e.g., sweet sorghum). The process can also use liquid wastes such as leachate from landfills and raw sewage. Terrabon&#;s process will increase landfill life and replace nonrenewable petroleum. A life cycle analysis (LCA) using the GREET model (Greenhouse gases, Regulated Emissions, and Energy use in Transportation) shows that the MixAlco® process will reduce greenhouse gas emissions by over 174 percent compared to conventional gasoline. With high-water effluents as the water source along with MSW, this process does not compete with local water resources. Terrabon currently operates a demonstration plant in Bryan, Texas to confirm the commercial scalability of this process.

This plant can potentially ferment the equivalent of about 5 dry tons of biomass per day to produce 100,000 gallons of biogasoline per year. The on-site conversion to biogasoline includes dewatering the fermentation salt product by evaporation and drying, thermally converting it into ketones, and catalytically converting the ketones into alcohols and hydrocarbons. Terrabon has successfully produced good-quality gasoline at this plant. In , the company will begin constructing a 220 dry ton-per-day biorefinery at the Waste Management landfill in Alvin, Texas. This plant will convert MSW into 5 million gallons of gasoline per year.

Conversion of the Herbicide, Metolachlor, to S-Metolachlor in the U.S. Marketplace: Metolachlor, a racemic mixture of two diastereoisomers, was used in the US for over 20 years on > 30 crops at about 65MM lbs./yr. Syngenta discovered increased herbicidal activity of the optically active S-isomer pair in the s (US patent 5,002,606). A practical synthesis route could not be found until the mid-s, when Syngenta discovered a chiral diphosphine catalyst route for enantioselective hydrogenation of an imine intermediate for S-metolachlor synthesis (US patents 5,463,097; 5,563,309; and REE). Syngenta developed an optimized process and designed and constructed a high volume manufacturing plant capable of supporting commercialization. All metolachlor products have been replaced, at equal grower cost, with 35% reduced-rate S-metolachlor products.

Charles Benbrook (see citation) estimated that in the conversion years, S-metolachlor reduced total US corn herbicide use by 12-14MM lbs./yr. With complete conversion, an 18-22MM lbs. annual reduction has been achieved. S-metolachlor is used by >135,000 US farmers annually. It reduces environmental and human exposure risks throughout its life cycle-including manufacture, distribution, application, and container disposal. It meets EPA&#;s goals to reduce pesticide use and to substitute reduced risk pesticides for higher risk pesticides. Publications document commercialization of the chiral catalyst system for stereospecific production of high volume chiral products.

Conversion of Waste Plastics into Fuel: EPA estimates that the United States recycles less than 6 percent of the 30 million tons of waste plastic it produces each year. In landfills, waste plastics produce methane gas, a greenhouse gas that is 23-times more harmful than carbon dioxide (CO2). The worldwide fishing industry dumps an estimated 150,000 tons of plastic into the ocean each year, which constitutes almost 90 percent of all rubbish floating in the oceans. Natural State Research, Inc. (NSR) has developed a patent-pending, award-winning technology that converts municipal solid waste plastics (PETE-1, HDPE-2, PVC-3, LDPE-4, PP-5, and PS-6) into liquid fuels.

The typical NSR process involves heating small pieces of waste plastic to 280&#;420 °C to form a liquid slurry. After it cools, the slurry is distilled in the presence of cracking without catalyst to recover light gas and liquid hydrocarbons. Fractionation of the liquid hydrocarbons produces fuels similar to gasoline, naphtha, diesel, jet fuel, fuel oil, and home heating fuel that can be used in the majority of combustion engines. NSR&#;s technology is a new alternative to fossil fuels: it creates fuel sustainably without depleting natural resources. The raw material required to make NSR fuel, waste plastic, is abundant; until now, its disposal has posed significant environmental problems.

Unlike other technologies, the NSR thermal technology does not use any pyrolysis, catalyst, vacuum, or chemicals during its process, and the overall yield is higher than for other methods. When developed to commercial scale, the NSR technology can convert one ton of waste plastics into about 335 gallons of liquid fuel at a cost of about $0.50&#;$0.75 per gallon. NSR will license its technology to others, creating locally owned franchises employing up to 50 workers each. NSR has produced about 200 gallons of fuels to date.

Converting Pollution to Profits: Valuable Chemicals & Energy: Sulfur-containing molecules are found in many different industrial sectors and are usually desulfurized by combustion to SO2 or hydrogenation to H2S because they are toxic, corrosive, strongly malodorous, involved in the formation of particulates and are responsible for acid rain. H2S and SO2 emissions are typically converted to elemental sulfur and gypsum sludge and are disposed in landfills. Clearly, these pollution control approaches don&#;t result in valuable chemical products or energy that generate monetary incentives for industry to minimize environmentally undesirable sulfur emissions.

An alternative approach is to view the S-containing molecules as inexpensive feedstocks for the production of valuable chemical products and energy via new synthetic and selective catalytic reaction chemistry. The oxidation chemistry of S-containing molecules has previously not received much attention because the ultimate goal has been to completely oxidize to SO2 or elemental sulfur. However, the recent work at Lehigh University has discovered that S-containing molecules can indeed be selectively catalytically oxidized as well as dehydrogenated, via exothermic energy generating pathways, to highly valued chemicals such as H2, H2CO, maleic anhydride, phenol, C2-C4 olefins and alkanes as well as H2SO4. Furthermore, the application of these new synthetic methodologies can also partially displace the energy intensive and polluting synthesis of H2 (consumes enormous amounts of fuel, generates significant global warming CO2 and smaller amounts of Ox/SOx emissions), which will become even more important in the coming years. Lastly, these new selective catalytic processes are sustainable in those industries that are based on renewable resources&#;biomass.

Core Line of Cleaning Products: Most effective modern cleaners are comprised of surface active agents which are derived from petrochemical resources. While these components are effective, they tend to be environmentally harsh and dependent upon a finite and limited natural resource. In addition, many cleaners contain strong alkaline materials that are corrosive to human tissue. Children, elderly, and janitorial/custodial employees are particularly susceptible to the health hazards posed by inhalation of these cleaners. In a market production estimated at approximately 5 billion pounds per year, the products (during usage) are considered to be a major contributor to indoor air pollution. During the past few years, a new "core" line of cleaners has been developed that is less toxic to humans and the environment while maintaining the same level of performance as traditional cleaners. These four new products, derived from renewable resources, are readily biodegradable, have low corrosivity, are comprised of little or no volatile organic components, and exhibit competitive economics.

Correlating and Predicting Drug Molecule Solubility with a Nonrandom, Two-Liquid Segment Activity Coefficient Model: Quantitative knowledge of drug molecule solubility is essential for solvent selection, design, and optimization of synthesis and purification processes for active pharmaceutical ingredients (APIs). Lack of solubility information often leads to suboptimal design with respect to yield, productivity, cost, energy use, solvent consumption, and hazardous waste discharge in pharmaceutical manufacturing processes.

Although powerful, automated solubility measurement tools are available, they remain time- and labor-intensive. AspenTech researchers recently developed a novel, nonrandom, two-liquid segment activity coefficient model (NRTL-SAC) as a simple, practical molecular thermodynamic framework. NRTL-SAC characterizes drug molecular interactions in solution in terms of dimensionless hydrophobicity, hydrophilicity, polarity, and solvation. Using NRTL-SAC, chemists and engineers first measure the solubility of a drug in a few reference solvents to identify the molecular parameters of the drug. They then use the model to predict the drug&#;s solubility in pure solvents and solvent mixtures. The model delivers robust solubility predictions with accuracy within ±50 percent or better.

This level of accuracy is superior to that of all existing predictive models and is effective for solvent selection and API process design. AspenTech researchers also collaborated with major pharmaceutical companies to demonstrate the broad applicability of their model. The model has been integrated with Microsoft® Excel and process simulators in support of systematic and rational solvent selection, unit operation modeling, and design and optimization of pharmaceutical manufacturing processes. NRTL-SAC represents a quantum step forward in predicting the solubility of drugs in solvents and mixed solvents.

The NRTL-SAC technology offers a first-principles-based engineering solution, enabling chemists and engineers to design greener processes that deliver required drug purity and yield, minimize solvent use, generate less hazardous solvent waste, consume less energy, and decrease overall cost. AspenTech has been using NRTL-SAC in its products since . Its collaborators include Eli Lilly, AstraZeneca, and Bristol-Myers Squibb.

Corrosion Control with a Greener Pathway: Several years ago, a survey commissioned by the Federal government estimated the cost of corrosion in the United States at $275 billion annually. Corrosion of metals is a natural process during which metals oxidize. Selected chemicals can prevent, control, and slow down the corrosion of metals. Traditional chemicals used for corrosion control include cyclohexyl ammonium benzoate and other amine salts.

Cortec Corporation (derived from corrosion technology) began to evaluate sugar beet glucoheptonate as an anti-icing road additive in when electrochemical screening indicated it could prevent metal corrosion in salt water. Cortec hypothesized that gluconic acid derivatives could protect rebar in concrete from corrosion; after tests were successful, the company began to develop this product. Cortec now sells eleven corrosion-control products based on natural oils, six based on gluconates, one based on soy protein, and three films based on polylactic acid. Its most successful product uses gluconic acid derivatives from sugar beets as components of migratory corrosion inhibitors to protect the reinforcing steel (i.e., rebar) in concrete from corrosion by salt.

An independent study by American Engineering Testing concluded that MCI , a product derived from gluconates, delayed the onset of corrosion in steel embedded in concrete beams; when corrosion developed, MCI reduced the corrosion current and the extent of corrosion. The study involved 56 cycles of 3-percent sodium chloride (NaCl) ponding, drying the concrete beams for two weeks, and repeating the 3-percent NaCl ponding. The test measured corrosion by electrochemical measurements on the embedded rebar in the concrete blocks midway through each cycle.

Cortec has been awarded six patents covering the use of gluconates to protect rebar in concrete and has been successful in selling these products worldwide. In , sales of these products were 6 percent of Cortec&#;s total sales; this figure increased to over 7 percent in .

Corrosion-Resistance without Chromium: On-Demand Release of Environmentally Safe, Non-Chromium Corrosion Inhibitors from Electroactive Polymer Coatings: Currently, the prevalent primers and pretreatments used to inhibit corrosion of aluminum alloys for the aerospace industry contain hexavalent chromium, Cr(VI). These primers are extremely effective, but their manufacturers are under significant pressure to eliminate Cr(VI) from them. Employees exposed to Cr(VI) have increased risk of developing serious adverse health effects including lung cancer, asthma, and damage to nasal passages and skin. In addition, these standard coating systems release Cr(VI) to the environment throughout their useful life. Federal, State, and local agencies have issued regulations that limit or prohibit the use of materials containing chromium.

Crosslink has developed a commercially available, environmentally and worker-friendly coating to replace Cr(VI)-containing paint primers for protecting aluminum alloys in aerospace applications. Their novel coating is based on electroactive organic polymers (EAPs). EAPs possess two unique properties: the ability to conduct electricity through an organic polymer and the ability to bind and expel molecules or ions in response to an applied electrochemical potential. Local electrochemical reactions that occur on the surface of a metal during corrosion trigger a change in an EAP&#;s redox state. Crosslink has synthesized EAPs with corrosion inhibitors (molecules or ions) as dopants.

In Crosslink&#;s protection system, the onset of corrosion forms a local galvanic couple that triggers release of the inhibitor from the EAP. Released inhibitor molecules then diffuse to the corroding site and inhibit the anodic or cathodic reaction. In this sense, these coatings are "smart": they release the inhibitor only when corrosion occurs. A nontoxic inhibitor, 2,5-dimercapto-1,3,4-thiadiazole, forms the basis of one new chromium-free primer. Incorporation of Crosslink&#;s EAP system into paint systems such as epoxy and polyurethane could eliminate the need for chromium-based primer coatings and their associated environmental and safety risks. Crosslink has identified a business partner to commercialize its technology during .

Cost Effective Green Chemistry Approaches to Pharmaceuticals: Microwave Techniques & "Grindstone Chemistry" for Solventless Reactions and Less Pollution: The advent of new reagents, new catalysts, and new techniques of energy transfer to chemical reactants has made it possible to make traditional organic synthesis more environmentally benign. A very unusual new technique is "Grindstone Chemistry" for conducting many reactions on a large scale &#; without solvent and at room temperature &#; by just grinding together reactants (solid/solid; solid/liquid; liquid/liquid with sea sand added).

Microwave irradiation of reagents &#; with or without solvents &#; greatly enhances a wide variety of synthetic reactions in several ways: by reducing the reaction time, by ensuring high yield and less chemical waste (i.e., reduction of pollution at the source). In our laboratories microwave reactions are conducted in open systems by using moderately high boiling solvents (dimethylformamide, etc.) or no solvents if one of the reagents is a liquid. The microwave energy is controlled to keep the reaction from boiling; thus, no reflux condenser is needed. This open system is free from the risk of explosion observed sometimes in sealed systems and is user friendly.

We have improved upon several classical organic reactions described in "Organic Syntheses" &#; the established guide book for synthetic chemists. To illustrate our approach to green chemistry, we have devised an eco-friendly alternative synthesis of DAPSONE &#; a widely used anti-leprosy drug that also helps some AIDS patients, We have used microwave irradiation to accelerate enzymatic cleavage of proteins and devised rapid analysis of peptides including cyclic peptides &#; reactions of value for drug development. The use of the combination of microwaves and Grindstone Chemistry techniques will allow pharmaceutical companies to be more efficient, more eco-friendly and more competitive.

Cross-Linked Enzyme Crystals (CLECs) as Robust and Broadly Applicable Industrial Catalysts: Enzymes are proteins that function as highly efficient and selective catalysts. Enzymes are responsible for the biochemical reactions that are essential to life, and as such, they are unique in their intrinsic compatibility with living organisms. Their potential as safe and efficient industrial catalysts has been long recognized, but to date, enzymes have not exhibited the chemical and physical stability associated with more conventional, small-molecule organic and inorganic heterogeneous catalysts. Altus Biologics has developed a conceptually simple and broadly applicable solution to this fundamental problem&#;the formulation of enzymes in a cross-linked crystalline form&#;that enables enzyme use under the harsh chemical, physical, and mechanical conditions that characterize most practical industrial processes.

To date, more than 20 enzymes have been formulated as CLECs and have demonstrated their utility on a pilot scale: as industrial catalysts, in consumer products such as detergents and cosmetics, as medical and process biosensors, and in the decontamination of waste and hazardous chemicals including insecticides and nerve agents. Two applications out of this broad portfolio of uses are described&#;the CLEC-catalyzed syntheses of the dipeptide artificial sweetener aspartame and of the semi-synthetic b-lactam cephalosporin antibiotic cephalexin. In these applications, an enhancement in synthetic efficiency has been demonstrated, with dramatic source reductions in the waste streams associated with these processes.

In addition to the potential broad impact of the cross-linked enzyme crystal technology on source reduction, widespread application of CLECs might also serve to leverage America&#;s investment in the area of molecular biology beyond the preeminence already established in the biotechnology industry prototype. Novel, though otherwise impractical, enzymes derived from that technological base could, through their stabilization as CLECs, lead to a penetration and dominance of the much larger and employment-intensive commodity- and fine-chemical manufacturing industry; driven by the economic benefits derived from the implementation of more efficient, competitive, and 'greener&#; chemical manufacturing options.

Crystal Simple Green®: Invention and commercialization of new safer family of products for use in the industrial marketplace exemplified by "Crystal Simple Green," the non-toxic, biodegradable degreaser/cleaner. The use of toxic chemicals in the industrial marketplace exceeds one billion dollars in the United States. These chemical are responsible for environmental and personnel hazards. Workmen&#;s compensation claims have skyrocketed due, in part, to the use of acids, high pH solutions, and chlorinated solvents. Crystal Simple Green utilizes proprietary technology to effectively degrease/clean substrates that are heavily loaded with industrial oils, greases and hydrogenated animal fats.

Crystal Simple Green, with a mild 9.35 pH emulsifies, saponifies, and degreases substrates through a process known as micelle creation (Micro Particulate Fractionalization). This unique process breaks oils and greases into small particles, which continues to a molecular level. Crystal Simple Green is essentially non-toxic, and represents low toxicity hazard to mammals by inhalation, ingestion or topical route of entry. Furthermore, Crystal Simple Green represents no spill hazard and will not be deleterious to microorganisms utilized in the bioremediation process. In fact, Crystal Simple Green has properties that increases the effectiveness of bioremediation. These attributes, along with Crystal Simple Green&#;s cleaning efficacy further the use of safer chemical products in the industrial area.

CSSX Process Demonstration: A U.S. Department of Energy (DOE) team has successfully demonstrated a new process that will be used to decontaminate 34 million gallons of high-level radioactive waste now stored in underground tanks at the Savannah River Site (SRS). This process, called CSSX, for caustic-side solvent extraction, will separate the radioactive isotope cesium-137 from the extremely alkaline liquid in the tanks.

Although the CSSX process is a waste treatment process, our goals were the same as those used in designing any environmentally benign industrial operation. That is, the goals of CSSX are inherently green: to eliminate pollution, secondary-waste production, and risk to the environment while processing the waste to the required level.

The demonstration achieved key process goals, which showed that the volume of high-level waste can be reduced 15-fold and the cesium-137 can be removed with decontamination factors of 40,000 or higher. Furthermore, these goals were met using a very low solvent-to-feed ratio, an achievement made possible by using multistage centrifugal contactors and a new, highly selective solvent.

The team is now working to provide research and development results that will assist SRS in designing a facility for the CSSX process.

Cytec Innovation Management System: Sustainable Development of New Products: Cytec Industries Inc., led by its Innovation Group, has established a process called the Cytec Innovation Management System (CIMS). This process guides development chemists and engineers in evaluating the safety, health, and environmental (SH&E) as well as economic aspects of products under development. Cytec chemists and engineers use the CIMS web-based process management software from the earliest stages of product development through commercialization and production.

This process includes a series of stages and gates in which users assess aspects related to SH&E. CIMS requires varying degrees of data before it grants approval for subsequent stages. Cytec created the CIMS process by benchmarking best practices from other companies&#; New Product Development (NPD) processes, reviewing published NPD benchmarking studies, and surveying Cytec employees about earlier NPD processes. Cytec developed the SH&E questions after consultation with the American Institute of Chemical Engineers&#; Center for Sustainable Technology Practices.

CIMS puts in place common best-practice processes and tools that help drive commercialization by designing safe, energy-efficient, and environmentally sound products and processes. A critical component of CIMS is the Stage-Gate® process, which drives sustainable development. The Stage-Gate® process incorporates SH&E questions into the first stages of the new product development process, allowing researchers to evaluate the sustainability of a product early in the development process. Additional tools built into CIMS include Sustainable Futures models developed by the EPA and Cytec&#;s Solvent Selection Guide, which includes hazard information on 120 common solvents. Cytec incorporated EPA tools for screening at the early stages of the process to drive commercialization of greener, safer, more environmentally friendly products. Cytec has implemented the CIMS process across functional areas and business units throughout the company.

Demonstration of a Home Energy Station for Production of Electricity, Heat, and Hydrogen: Development of the hydrogen economy is driven by its potential economic, environmental, and security benefits. Displacement of fossil fuels for transportation applications will result in reduced emissions, improved air quality, and reduced energy consumption. However, emergence of the use of hydrogen as a fuel for transportation applications is hindered by the chicken-and-egg emergence of hydrogen-powered vehicles and a hydrogen delivery infrastructure. Plug Power Inc. of Latham, New York, has teamed up with Honda R&D Co., Ltd., to develop, install, and demonstrate a Home Energy Station. This fuel cell-powered system converts natural gas to electricity to power a home, thermal energy for space and water heating, and hydrogen.

The hydrogen is compressed and stored, and can be delivered to a fuel cell-powered vehicle. The Home Energy Station changes the refueling paradigm from central facilities to clean, on-site fuel generation. By using catalytic and electrochemical processes, the Home Energy Station reduces atmospheric emissions and produces energy at higher efficiencies than traditional central generating stations. The Home Energy Station produces clean, reliable energy on-site, representing a significant milestone along the path to a hydrogen economy.

DEOXO-FLUORTM Reagent: Deoxofluorination, the conversion of carbon-oxygen to carbon-fluorine bonds for pharma, agro and other chemical synthesis applications, is routinely accomplished at a small scale in the laboratory with DAST [(diethylamino) sulfur trifluoride], usually at near ambient conditions. The thermal instability of DAST has precluded its use at larger scale and at more forcing conditions. Air Products and Chemicals, Inc. undertook a program to render deoxofluorination safer at large industrial scale which led to the discover and development of the Deoxo-Fluor reagent. Extensive thermal analysis by DSC, Radex, ARC, Setaram calorimetry have clearly shown the far superior stability of the Deoxo-Fluor reagent over DAST. Ab initio quantum-mechanics calculations on the conformational structures of the reagent have provided a rationalization for this greater thermal stability.

The Deoxo-Fluor reagent is effective in the conversion of alcohols to alkyl fluorides, ketones/aldehydes to gem-difluorides, and carboxylic acids to CF3 compounds with, in some cases, superior performance as compared to DAST. Within the past 2 years, Air Products and Chemicals, Inc. has successfully brought the Deoxo-Fluor reagent product from discover to commercial production. Major pharmaceutical companies in the U.S.A., Europe and Japan are currently using the reagent for the synthesis of pharmaceutical products in their development pipeline.

Dequest® PB: Carboxymethyl Inulin, A Versatile Scale Inhibitor from the Roots of Chicory: Fouling of surfaces by mineral salt scale is a major problem in water-bearing systems. Scaling reduces heat-transfer efficiency and interferes with industrial process operations. Similarly, hardness ions hinder the efficiency of detergents and cleaning processes. Scale inhibitors are used to prevent the deposition of inorganic scales onto surfaces. Previous scale inhibitors were either biodegradable with limited applicability or poorly biodegradable with moderate toxicity but good performance. Previous inhibitors did not use renewable resources.

Carboxymethyl inulin (CMI), developed by Solutia in collaboration with Royal Cosun, provides an environmentally friendly, cost-effective, safe, and versatile alternative to traditional scale inhibitors in a wide variety of industrial applications. Moreover, CMI is a good chelator and an excellent dispersant, which makes it an attractive ingredient for household detergents. Recent research has shown that CMI can be formulated in lower amounts than can polyacrylates and polyaspartates. Unlike polyaspartate, CMI is stable in the presence of low levels of oxidizing agents like hydrogen peroxide. Thermphos has discovered synergistic effects between CMI and other chelants and has filed patents.

Phosphorous in detergents is a growing environmental concern. Many commercial detergents include CMI because it can be used in phosphorus-free formulas at much lower concentrations than other co-builders. CMI is based on inulin, an oligosaccharide harvested from the roots of chicory. It does not compete with food production. Current commercial applications include household, industrial, and institutional detergents and cleaners, secondary oil recovery, and pulp and paper processing. CMI can also replace poorly biodegradable scale inhibitors in water and process water treatment, sugar refining, and other industrial applications. It performs well on sulfate scales, especially under high total dissolved solids and high iron conditions. CMI is not a strong chelator of transition metals and, therefore, does not contribute to the unintended mobilization of heavy metals. CMI is the first inulin derivative to reach the market.

Derivatized and Polymeric Solvents for Minimizing Pollution During the Synthesis of Pharmaceuticals: A new class of solvents has been developed that has solvation properties similar to those of solvents used conventionally in chemical synthesis, separations, and cleaning operations, but for which the potential for loss by environmentally unfavorable air emissions or aqueous discharge streams is minimized. These alternative solvents are derivatives of solvents currently used in reaction and separation processes, tailored so that they are relatively nonvolatile and nonwater soluble, thereby satisfying the criteria for pollution source reduction.

The solvents can be used as neat reaction or separation media, or they can be diluted in an inert environment such as in higher alkanes. Polymeric or oligomeric solvents have been synthesized using macromonomers incorporating the desired solvent functionality. These polymeric solvents are easily recovered using mechanical separations such as ultrafiltration rather than energy-intensive distillation processes. This new concept for the design and synthesis of solvents offers the potential for significant source reductions in air and water pollution and can be considered to be widely applicable to fine chemical and pharmaceutical synthesis, separations, and cleaning operations. It is expected to reduce the complexity of downstream processing options considerably and lead to energy efficient reaction/separation sequences.

Design of CO2-Soluble Ligands for Affinity Extraction Using CO2: Carbon dioxide has elicited significant interest among the academic and industrial community over the previous decade in that it exhibits properties which render it a relatively "green" solvent. Carbon dioxide is an inexpensive, non-toxic solvent whose use in chemical processes is not limited by either FDA or EPA regulations. Use of CO2 in extractions from water (or in biphasic reaction systems) is particularly advantageous in that, unlike the analogous situation using conventional organic solvents, one needn&#;t worry about contamination of the aqueous phase when using CO2. Unfortunately, because CO2 is a low dielectric fluid, extraction of polar materials from aqueous solution using CO2 has been heretofore technically infeasible. The work of Professor Eric J. Beckman at the University of Pittsburg has shown that design and use of highly CO2-soluble ligands allows one to employ carbon dioxide in extractions of polar materials from water which were previously thought to be untenable.

Using fluoroether-functional affinity ligands, for example, Professor Beckman has shown that one can extract proteins from aqueous solution into CO2 with retention of activity following recovery by depressurization. Analogous chelating agents have been used to extract metals into CO2 as well. While initial work has targeted primarily extractions, the described CO2 soluble ligands can also be used to solubilize catalysts in CO2 (enzymes and metals are examples) for use in carrying out reactions either in CO2 or in CO2 water biphasic mixtures.

Design of Rubberized Concrete from Recycled Rubber Tires: The United States produces about 279 million scrap tires per year. In addition, about 3 billion used tires are currently stored in waste piles throughout the country. Solid waste management experts recognize the need to recycle, reuse, or reduce the waste rubber tires, since this would lead to a direct diminution of waste tires in landfills. A number of processes have been suggested for reusing the waste rubber. Using tires as fuel and as asphalt material has provided only limited success.

The work of Dr. Dharmaraj Raghavan at Howard University has led to the development of a technology that mixes rubber particles from scrap tires into portland cement resulting in a lighter material with improved performance of mortar and probably concrete. The worldwide production of cement exceeds 1 billion tons annually, with the possibility of it nearly doubling in the next 14 years. Cement based materials are inexpensive, easy to produce, and possess valuable engineering properties such as high durability and compressive strength. One of the major shortcomings of cement based material is the vulnerability of concrete to catastrophic failure and to plastic shrinkage cracking. An encouraging finding was that plastic shrinkage cracking can be reduced significantly and the vulnerability of concrete to catastrophic failure can be greatly diminished by the addition of sufficient fibrous rubber.

Chemical tests of the rubber retrieved from rubberized concrete showed no evidence of rubber undergoing any degradation and consequently no threat of released chemicals from the leached rubber into the environment. Possible uses of the rubberized concrete would be in subbases for highway pavements, highway medians, sound barriers, and other transportation structures. Currently the United States spends $250 billion annually on infrastructure projects. Even if rubberized concrete replaced only a small fraction of the conventional infrastructural material, the ramifications to the civil and composite industries will be substantial. The technology to reuse rubber tires into cement system yields value-added infrastructural material, while eliminating the imminent threat of health hazard and explosion potential because of the flammable nature of rubber tires.

Designing an Environmentally Friendly Copper Corrosion Inhibitor for Cooling Systems: Copper alloys are widely used in industrial cooling systems because of their good heat transfer qualities. However, unless they are protected by an inhibitor, copper alloys will corrode in cooling systems. This corrosion produces extremely toxic copper compounds that are then released into the environment. Azole materials are the best available copper corrosion inhibitors and, in general, they protect copper very well. Tolyltriazole (TTA) is by far the most frequently used azole and is considered to be the industry standard. However, azole materials have a serious drawback in that they are not compatible with oxidizing halogens, such as chlorine and bromine. Oxidizing halogens are the most common materials used to control microbiological (MB) growth in cooling water systems.

TTA reacts with chlorine, producing a chlorinated species that is not protective to copper. When corrosion protection is lost, TTA feed rates are usually increased in an attempt to overcome the reaction with chlorine and maintain a high enough residual to protect the copper surface. Very high TTA dosages are frequently applied to improve performance, often with limited success. BetzDearborn has developed a new Halogen-Resistant Azole (HRA) that does not react with chlorine and protects copper when chlorine is present. The substitution of this new material for TTA provides substantial environmental benefits. These were demonstrated in a field test at a nuclear power plant that was utilizing chlorine for MB control. HRA was compared to TTA with respect to copper corrosion rates and discharge toxicities. Upon examination of the discharge, it was clear that copper-containing compounds, formed as a result of copper corrosion, were the most significant causes of toxicity to aquatic species. The use of HRA resulted in a five-fold decrease in the amount of copper released to the environment, compared to TTA.

Since HRA does not react with oxidizing biocides, considerably less chlorine or bromine is required for prevention of MB activity. A reduction in chlorine usage of 10 to 20% was observed at the above nuclear power plant, and reductions of 35 to 40% have been observed at other industrial sites. Lower chlorine usage means lower amounts of chlorine- or bromine-containing compounds ultimately being released in discharge waters. In addition, substantially lower concentrations of HRA are required for copper alloy protection compared to TTA.

At the nuclear power plant trial, the five-fold reduction in the copper discharged was obtained with 2.0 ppm HRA compared to 3.0 ppm TTA. Furthermore, a mass balance showed that only 9% of the TTA was recovered (compared to 90% of the HRA). The TTA loss was due to the reaction with chlorine and the formation of a chlorinated azole. Thus, the use of HRA resulted in a net reduction in the amounts and types of azole and halogenated azole compounds that were released into the environment. Finally, direct measurement of LC50 acute toxicities for fathead minnows, done on site in the plant effluent at the nuclear facility, showed a reduction in toxicity when TTA was replaced by HRA.

Designing Safer Chemicals: Spitfire Ink: As the information age enters a significant period, a new paradigm is being introduced to the printing industry. With the advancement of computer technology, the demand for peripheral printing devices has accelerated. For the past 10 years, this growth industry has been truly in its infancy. Various chemical systems have been employed with a multitude of electronic and/or mechanical printing devices, primarily addressing office applications. The computer-based printing devices, which consume large volumes of chemicals (inks, resins, colorants, solvents, etc.) are rapidly progressing to the extent that traditional printing technologies are being challenged. One of these chemical systems is phase change ink.

The many attributes of phase change ink make it a viable contender for a leading position in the printing industry to replace less environmentally friendly alternatives. Phase change ink, also known as hot melt or solid ink, addresses many of the limitations of the ink and printing processes associated with the well-defined, centuries old printing methods, (e.g., offset, flexography, gravure, letterpress). To demonstrate the enormity of the opportunity, chemical development of phase change inks has favorably addressed source reduction, pollution prevention, emission standards, ground-water contamination, airborne particulates, waste abatement, worker and consumer exposure, hazardous chemical reduction and nonreusable consumables. The traditional printing techniques that often have significant worker and environmental liabilities can now be replaced with modern technology sensitive to, and having an understanding of, complex "green chemistry" issues.

Tektronix is commercializing a four-color set of process shade, phase change inks (Spitfire Ink) for use in color printers also manufactured by Tektronix. The chemical design of Spitfire Inks started with consumer and manufacturing operator safety, environmental concerns and the expected application performance. A retro-synthetic analysis accounting for these primary "must haves" translated to the synthesis of new resins that were water insoluble, required no volatile organic solvents (VOCs) to manufacture or use, allowed for safe manufacturing, complied in "spirit and intent" with environmental regulations and provided a flexible technology to a growing and expanding industry. These goals were satisfied by foresighted design aimed at safer chemicals ultimately embodied in Tektronix&#; Spitfire Ink.

Developing Direct Catalytic Addition of Alkynes to Aldehydes and Imines in Water and under Solventless Conditions: Optically active propargyl amines and alcohols are important synthetic intermediates for the synthesis of various nitrogen- and oxygen-containing compounds and are components of bioactive compounds or pharmaceutical agents. The resulting alkynyl additional derivatives can undergo further transformations and are versatile synthetic tools. However, these compounds are often prepared in at least three steps:

(1) synthesis of a highly reactive organo-metallic reagent such as the BuLi from organic halide and a highly reactive metal such as lithium (although such reagents have been commercialized);

(2) converting of alkynes to alkynilides;

(3) reaction of alkynilides with aldehydes or imines.

All three steps generate stoichiometric amounts of waste, as well as require inert atmosphere and anhydrous organic solvents. Within the last several years, we have developed various catalytic direct addition of alkynes to aldehyde and imines in water and under solventless conditions. We have also developed the first direct catalytic enantioselective three-component-addition of alkdehyde, alkyne, and amine in water and under solventless conditions. The results have been published in J. Am. Chem. Soc. (, ) and Proc. Nat. Acad. Sci. ( in press) etc. and were cited in C& EN (, ).

Developing Highly Efficient C-H Activation of Hydrocarbons: The preparation of high-valued organic chemicals often involves lengthy, multi-step synthetic sequences. These typically require large amounts of various chemical reagents, such as oxidizing and reducing agents, drying agents, and organic solvents for the performance of the reactions. Large amounts of organic solvent are also often required for the separation of the desired products from one another, especially when chromatography is employed. The most effective way to solve this problem is to drastically reduce the the number of chemical steps required in these synthetic sequences.

Bergman has demonstrated that the employment of C-H activation reactions within synthetic sequences provides important progress toward this goal. Within the last two decades, the Bergman group has pioneered the direct activation of C-H bonds in organic molecules that are found in locations remote from other functional groups. Due to this pioneering work these C-H activation reactions are now being used successfully in the synthesis of various chemicals and pharmaceutical products. Ultimately this should have a profound impact on various fields and sectors of chemical manufacturing and production. Bergman&#;s studies of the mechanism of C-H activation have also provided a substantial amount of fundamental information about this important process, such as the factors that promote highly activation of different types of C-H bonds in hydrocarbons.

Developing Lignocellulosic Biorefineries: Lignin typically represents 20&#;30 percent of plant biomass. Catalytic oxidative cracking of lignin is a crucial component of the efficient conversion of biomass resources to biofuels, biochemicals, and biomaterials. At present, however, the only use of lignin is as a low-value heating fuel.

Historically, oxidation reactions have required stoichiometric amounts of oxidizing reagents that have considerable drawbacks such as high cost, waste byproducts, and serious environmental disposal issues. The traditional oxidants include KMnO4, MnO2, CrO3, and Br2. In comparison, molecular oxygen is a superior oxidant that is abundant, costs less, and has a better safety and environmental profile. Researchers have directed concerted effort at developing systems that use various transition metals to catalyze aerobic alcohol oxidation, but many of these catalytic systems also require aromatic or halogenated hydrocarbon solvents that are volatile organic compounds (VOCs).

Professor Ragauskas is focusing on developing catalytic systems to replace previous VOC solvents with ionic liquids. The unique properties of ionic liquids include low volatility, high polarity, selective dissolving capacity, and reaction stability over a wide temperature range. These properties lead many to recognize ionic liquids as attractive, alternative, green reaction media. Professor Ragauskas has developed ionic liquid systems that are capable of solubilizing lignin. He and his group have discovered novel aerobic catalytic oxidative systems that can functionalize or fragment lignin. They have developed an oxidative chemistry based on ionic liquids that exhibits excellent selective catalytic properties, allows simple recovery of product, recycles its catalyst, uses O2 as an ultimate oxidant, and does not generate hazardous heavy metal wastes. Professor Ragauskas&#;s oxidative system makes a unique contribution to green chemistry, especially in applications relevant to converting lignin to biodiesel and biogasoline.

In , Professor Ragauskas published his recent work in the Journal of Organic Chemistry and in Tetrahedron Letters.

Development and Commercial Application of SAMMS®: A Novel Compound that Adsorbs and Removes Mercury and Other Toxic Heavy Metals: Mercury contamination poses a serious threat to the environment and human health, but many common adsorbents are themselves problematic. Self-assembled monolayers on mesoporous supports (SAMMS®) successfully adsorb and remove toxic metals (e.g., mercury, cadmium, lead) and replace less-effective adsorbents (e.g., activated carbon, ion exchange resins). SAMMS® is a mesoporous ceramic substrate with a single layer of functional sorbent molecules bonded to the surface. The functional molecules have high affinity for specific ions. SAMMS® has superior adsorption capacity for targeted heavy metals, is cost-effective, and significantly reduces the volume of hazardous waste.

The original SAMMS® synthesis required toluene and other flammable organic solvents. The resulting waste stream contained water, methanol, toluene, and traces of mercaptan. It required disposal as hazardous waste. Steward Advanced Materials dramatically improved the SAMMS® synthesis with nonflammable, nontoxic supercritical carbon dioxide (SC CO2). With this patented, commercially viable, green chemical process, SAMMS® manufacturing is faster and more efficient; it also yields a higher-quality product. The only byproducts are carbon dioxide (CO2) and the alcohol resulting from the hydrolysis of the alkoxysilane. Th e CO2 and alcohol are readily separated, allowing the CO2 to be captured and recycled. The pure alcohol can be recycled as a feedstock, rather than becoming waste as in the original synthesis.

The SAMMS® materials emerge from the reactor clean, dry, and ready for use. Th e benefits of the green manufacturing process for SAMMS® materials coupled with the superior adsorption characteristics of SAMMS® materials currently deployed in the chemical industry result in substantially reduced releases of toxic metals to the environment. Commercial uses of thiol-SAMMS® include removal of: (1) multiple toxic heavy metals from contaminated mining impoundments, (2) heavy metal catalysts from pharmaceutical reaction mixtures, and (3) mercury from contaminated ground water and industrial process water with a discharge limit of 1.3 parts per trillion.

Development and Commercialization of High-Value Chemical Intermediates From Starch and Lactose.: Synthon has developed a method for the utilization of high-volume carbohydrate feedstock for the production of fine chemicals. One of the major tasks facing the chemical industry today is the identification and development of high-volume, renewable, commercially viable raw materials that can assume a large part (if not all) of the central role that oil-based materials play in that industry. Starch is one of the most abundant materials obtainable in pure form from biomass. As a raw material for the practice of chemistry from environmentally benign and renewable resources, it holds much promise and seemingly as many challenges.

Three of the most important aspects of starch structure and chemistry that are in step with requirements for a green chemistry feedstock are its solubility in water, the richness of functional groups, and its optical purity. The same is true of lactose, a material that is underutilized and available in thousands of metric tons per year from cheese making. These three promising features represent the three most difficult technical challenges in attempts to use starch and lactose as raw materials. They are practically insoluble in other environmentally friendly solvents such as alcohols and esters thus limiting the range of relevant chemistries. The high density of functional groups (polyhydroxylation) has made it (until now) nearly impossible to do anything useful with these on a grand scale in a selective fashion. The optical purity is embodied in functionalities that make conserving it a challenge.

Over the past three years, Synthon Corporation has been working to overcome these technical barriers by developing, demonstrating, and commercializing a new chemistry that will fundamentally revise the position of these two important and critical raw materials on the list of renewable resources for manufacture of chemical commodities. In the process, these materials are oxidized in dilute aqueous sodium hydroxide under controlled conditions with peroxide anion to form (S)-3,4-dihydroxybutyric acid and 2-hydroxyacetic acid (glycolic acid) with very high conversion. (S)-3,4-dihydroxybutyric acid can be converted to the lactone by acidification and concentration.

Glycolic acid and the lactone can be utilized in the production of a variety of fine chemicals for particular use in the pharmaceutical, agrichemical, and polymer industries. Glycolic acid, for example, is used in the manufacture of specialty polyesters and in the preparation of paints. It is normally made by the environmentally unfriendly method of chlorinating acetic acid and hydrolyzing the chloro derivative with sodium hydroxide. The Synthon product brochure now lists over 30 such products available from gram to ton quantities. The process has allowed Synthon to take a substantial lead in the area of high-valued chiral intermediates through the green chemistry approach where the pool of natural raw resources is tapped.

Development and Commercialization of Oleic Estolide Esters: Each year, 2.4 billion gallons of lubricants are used in the United States, according to industry and EPA estimates. Lubricants comprised of sustainable carbon that perform well in demanding applications are in high demand. Naturally occurring vegetable oils (triglycerides) provide excellent lubricity and have high viscosity indexes; they are also biodegradable, nontoxic, and economically attractive. Their oxidative and hydrolytic instability and their poor performance at low temperatures, however, exclude their use in passenger-car motor oils (PCMOs) and low-temperature environments.

LubriGreen has overcome the inherent disadvantages of vegetable oils and preserved their favorable properties by derivatizing fatty acids from triglycerides into estolides, which are oligomers of fatty acids. Patented oleic estolide esters are central to LubriGreen&#;s technology. Their synthesis proceeds by an acid-catalyzed SN1 addition of the carboxyl of one fatty acid to the site of unsaturation on another to form an estolide. (The catalyst is a recoverable, reusable organic superacid.) The free acid estolides are then esterified with a branched alcohol. The novel structure of oleic estolides gives them excellent lubricity, high viscosity indexes, and good cold-temperature properties. Like triglycerides, oleic estolides are beneficial in environmentally sensitive settings because they are biodegradable and nontoxic. Because the estolides are fully saturated and their secondary esters create a steric barrier to hydrolysis, they have good oxidative and hydrolytic stability.

Estolides are viable for the most severe lubricant and industrial applications, including PCMOs, hydraulic fluids, greases, gear oils, metal working fluids, and dielectric fluids. Estolides have the potential to displace a significant portion of the lubricant market, reducing emissions and the release of hazardous chemicals into the environment. Test results show that oleic estolide esters may also have advantages in performance and fuel efficiency over petroleum-based PCMOs. LubriGreen is currently working with the world&#;s largest formulators, lubricant distributors, and others to commercialize its products during .

Development and Implementation of Low Vapor Pressure Cleaning Solvent Blends: Lockheed Martin Tactical Aircraft Systems (LMTAS) (formerly General Dynamics Fort Worth Division) has developed low vapor pressure organic solvents. LMTAS patented these solvent blends and the technology is being used by the aerospace industry, the military, and various industries. Additionally LMTAS substituted one of the new solvent blends (DS-104) for a CFC-113 based general purpose cleaning solvent used in the surface wiping of aircraft parts, components, and assemblies in all aspects of aircraft manufacturing. The substitution resulted in major reductions in solvent use and air emissions, the elimination of ozone depleting compounds from cleaning during aircraft assembly, cost reductions, and improved chemical handling and usage practices.

From to , LMTAS produced mainly F-16 fighter aircraft at a rate of 220 to 350 aircraft per year. Throughout the 6 years, LMTAS used a general purpose wipe solvent containing 85 percent CFC-113 by weight throughout the manufacturing process. The use of the CFC-113 solvent blend resulted in the emission of approximately 255 tons per year of CFC-113 and 45 tons per year of volatile organic compounds (VOC) The implementation of DS-104 at LMTAS has reduced wipe solvent VOC emissions to 7 tons per year in , 3 tons per year in , and 2 tons per year in , with no CFC emissions. After the LMTAS implementation, other companies and military operations throughout the United States have implemented this technology.

Additionally, this technology has been implemented in several countries, such as Australia, Canada, Greece, Israel, Mexico, the Netherlands, South Korea, Taiwan, and Turkey. Several other European countries will implement this technology in . These cleaners were developed primarily for aerospace; however, they have found cleaning applications in many industries such as: automotive, bubble gum removal in movie theaters and universities, various ink removal industries, postal operations, electronics, building maintenance, steel industry, and nondestructive testing methods. EPA has recognized this technology in the Aerospace National Emission Standard Hazardous Air Pollutants and the proposed Aerospace Control Technology Guideline.

Development of a Biodiversity Search and Enzyme Optimization Technology: Biocatalysis is widely regarded as a promising new approach to source reduction of pollution associated with chemical manufacturing. It has not been widely adopted to date, however, due to the limited availability of process-compatible biological catalysis. Recombinant Biocatalysis, Inc. (RBI), has developed a whole new tool kit of biological catalysis for chemists.

Catalysts are central to modern chemical manufacturing as well as to life. A good catalyst accelerates the rate of a desired reaction compared to unwanted, waste generating, side reactions. Enzymes are wonderfully selective and specific catalysts. Enzymes, however, evolved to work in living systems, and enzymes that work well in a chemical process plant have not been broadly available to chemists and chemical engineers. RBI has developed a new technology specifically to meet that unmet need. By turning state-of-the-art biotechnology to the problem of making useful enzymes for chemists, RBI has enabled a step change in the availability of useful protein-based catalysts for the chemical process industry.

RBI has developed and applied a powerful, new biodiversity search technology to scan natural sources for new enzymes. Once the best enzyme that nature has to offer for a particular application is identified, RBI applies additional high throughput technology to optimize the enzyme to make it more useful in a chemical plant. This new technology already has produced more than 150 new, robust biological catalysts for the chemical process industry and will generate more than 3,000 by .

Development of a Nickel Brightener Solution: Historically, electroplaters of duplex nickel had to use formaldehyde and coumarin-bearing nickel plating solutions to obtain a nonsulfur nickel deposit, which is essential to the duplex nickel process, for maximum corrosion protection of external automotive trim and bumpers. The Watts" bath, introduced in , made it possible to increase the speed of nickel deposit by a factor of ten by increasing the electrical current density.

This development lead [sic] to the bright nickel plating baths known today, which use organic and inorganic additives. Organic aromatic sulfonic acid was later introduced to the Watts" bath to achieve the first practical bright nickel plating solution. In , formaldehyde was added to the solution followed in rapid succession by other additives. Coumarin, along with formaldehyde, became the important ingredients in a variety of nickel plating baths referred to as 'semibright". Today, semibright nickel plating occupies an important position in plating. Benchmark Products has developed a nickel brightener solution that, while improving the performance of electroplating, also significantly reduces the environmental impact by eliminating two toxic ingredients, formaldehyde and coumarin, and substituting nonhazardous ingredients.

Development of a Practical Model and Process to Systematically Reduce the Environmental Impact of Chemicals Utilized by the Textile and Related Industries: It was discovered in the early s that discharges from textile dyeing and finishing operations were adversely impacting publicly owned waste treatment facilities. The results of early toxicity reduction evaluations pinpointed toxic and poorly degraded textile chemicals and surfactants as culprits. It was decided that elimination of toxic agents prior to formulation was an important long-term objective to provide for a sustainable textile industry in the United States. To achieve products "Designed for the Environment," a means to inexpensively screen chemicals and raw materials and communicate results internally and externally to consumers and regulators was needed.

It was discovered by Burlington Chemical that the results from three OECD tests, OECD 301D, 202, and 209, could be related in an expert computer system (AQUATOX®) to design textile chemicals with greatly reduced environmental impacts. This discovery led to the development of a waste/toxicity reduction program, Burco® Care, based on this information. Burco® Care has resulted in the production of low-impact wet processing chemicals.

It spawned a system of comparing textile chemicals for environmental impact that can be utilized in purchasing decisions by textile manufacturers and has been found suitable by U.S. textile market leaders. Burco® Care is a giant leap away from simple regulator compliance to the creation of a systems-based, thinking approach to building value by reduction of risk and improvement of the environment.

Development of a Safer and More Effective Biodegradable Antimicrobial Cleaning Product: Currently most antimicrobial cleaners are harmful to inhale or for skin contact as they use chlorine, phenol, alcohol or Quaternary amine based ingredients. TPP1is a special blend of enzymes, bacteria, and surfactants which work together at a high pH. It is very effective at killing harmful bacteria and fungi. It is operator safe and can maintain surfaces free of antimicrobials for extended lengths of time. Funding is needed at this point to carry out further Environmental Protection Agency required testing in order to register the product for use. The TPP1 product already is known to kill certain microorganisms as noted. This product may also have applications in defending against a biological weapon attack. Its use in this area would be an added benefit.

Development of an Effective, Coordinated Family of Safe, Green Cleaning and Maintenance Products: Traditional cleaning products are often comprised of harsh chemical components selected to aggressively remove deposits from hard surfaces. In many cases these effective products need to be handled very carefully because otherwise they can be very harmful to human health as well as damaging to ecological systems. Rochester Midland invoked a different set of criteria for the development of its ENVIROCARE family of safe, green cleaning and maintenance products. The first priority was that all of the products would be environmentally preferable.

The pragmatic definition of "environmentally preferable" is products and related services that have a significantly lower detrimental effect on human health and the environment when compared with competing products intended for the same end-use application. At the same time the products had to perform well in their intended applications and this presented several strong technical challenges since many of the more effective conventional cleaning products contain strong acid or alkaline components not tolerable in the ENVIROCARE products.

An additional important criterion that was invoked was that whenever possible the main components used in the environmentally preferable products would be derivable from renewable resources and with a lesser reliance on petrochemical derivatives.

Development of Environmentally Benign Nonfouling Materials and Coatings for Marine Applications: Biofouling on ship hulls and other marine surfaces is a global environmental and economic problem. The majority of current marine coating products are antifouling coatings (i.e., coatings that release biocides to kill marine microorganisms). Because biocides are harmful to the marine environment, their applications are extremely limited. Nontoxic, fouling-release coatings based on silicone compounds are also available, but have not gained popularity and are only effective on vessels moving at high speeds (over 14 knots). Furthermore, these coatings require expensive material, application, and maintenance.

Professor Jiang has developed unique nonfouling coatings (i.e., coatings to which marine microorganisms cannot attach). Unlike antifouling coatings, his nonfouling coatings are nontoxic; they neither contain nor release biocides. Unlike fouling-release coatings, his coatings are highly resistant to attachment by marine microorganisms, even on stationary surfaces.

Professor Jiang&#;s discovery of superlow-fouling zwitterionic materials based on sulfobetaine (SB) and carboxybetaine (CB) enabled his development of nonfouling marine coatings. SB and CB are highly effective, very stable, nontoxic, and low-cost. His "hydrophobic" zwitterionic precursors enabled Professor Jiang to develop self-polishing, durable coatings for long-term applications. The "hydrophobic" zwitterionic precursors have strong mechanical strength as coatings; in seawater, they hydrolyze to "hydrophilic" nonfouling zwitterionic groups at the outer-most layer of the coatings. Over the last three years, Professor Jiang and his group have developed three generations of SB- and CB-based nonfouling marine coatings. Both laboratory tests and field tests in Florida have been successful.

Among many technologies under development for marine coatings, Professor Jiang&#;s nonfouling technology clearly stands out as the most promising. Its environmental and economic impacts are enormous. These SB- and CB-based materials are very promising for biomedical applications as well; Stericoat, an MIT spin-off business, is using the technology to prohibit microbial growth from attaching to medical devices. Professor Jiang has filed several patents for his technology.

Development of Extraordinarily Active Biocatalysts for Highly Selective and Efficient Synthesis of Chemicals and Pharmaceuticals: Enzymes occupy a unique position in synthetic chemistry because of their exquisite selectivities and high catalytic rates under ambient reaction conditions. Nevertheless, to be used more routinely, enzymes must function in environments that are appropriate for synthesis; key among these is nonaqueous media. Unfortunately, enzymes are poorly active in organic solvents, and this has limited their synthetic and commercial viability, particularly in large-scale processing. Furthermore, the low activity of enzymes in organic media necessitates large reactor volumes and large quantities of solvent in current commercial applications of nonaqueous biocatalysis.

By elucidating the mechanisms that underlie the low activity of native enzymes in dehydrated environments, we have developed methods to dramatically activate a wide variety of commercially relevant enzymes in organic solvents. In particular, by engineering the microenvironment of the biocatalyst through lyophilization in the presence of simple salts, we have opened the door for the application of enzymes in many new processes. New enzymatic processes will offer all the benefits of biocatalysis including high activity and specificity, reduced byproduct formation, and environmentally-friendly processing, and thus will provide a green alternative to less efficient synthetic schemes. This technical achievement is particularly relevant for green processing in the chemical, food, and pharmaceutical industries.

Development of Green and Practical Processes Utilizing Dialkyl Carbonates as Alkylating Reagents: In the last five years, Novartis&#;s green chemistry project has developed an environmentally friendly methylation process that employs 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) or 1,4-diazabicyclo[2.2.2]octane (DABCO) as novel catalysts to promote methylation reactions of phenols, indoles, benzimidazoles, and carboxylic acids with dimethyl carbonate under mild conditions in nearly quantitative yields. Similarly, Novartis has developed a novel and green process using dibenzyl carbonate with catalytic amounts of DABCO or DBU to benzylate nitrogen, oxygen, and sulfur atoms. Either microwave irradiation or an ionic liquid provide additional rate enhancement. By combining DBU or DABCO, microwave irradiation, and an ionic liquid, Novartis can perform alkylation reactions that previously took up to several days efficiently in high yields within minutes. Novartis&#;s technology avoids toxic or carcinogenic reagents such as methyl iodide, dimethyl sulfate, benzyl chloride, and benzyl bromide.

It also eliminates the use of a stoichiometric amount of base if applicable substrates contain no acidic protons. Their novel technology has the additional benefit of rapid reaction times, ease of operation, and use of readily available catalysts and ionic liquids. These features should make this newly developed chemistry of great benefit to humans and the environment. The United States Patent and Trademark Office has granted four patents to Novartis for these novel inventions. In addition, leading peer-reviewed journals have accepted six publications. By the end of , these papers had been cited thirty times by other scientists, confirming the utility and value of these inventions.

Development of High Performance, Environmentally Benign Hard Disk Drive Polishing Fluids and Corrosion Inhibitors: Magnetic hard drives are an essential component of computer hardware and handheld consumer electronic devices today. At the heart of these drives lies a giant magnetorestrictive (GMR) read/write head situated closely above a rapidly rotating magnetic hard disk. The GMR head surfaces must be highly polished to ensure their reliable operation within hard drives. Conventional lapping fluids used to polish these heads are composed of fine diamond abrasive powder dispersed within toxic nonaqueous solvents such as ethylene glycol. These solvent-based lapping fluids pose significant handling and disposal concerns for hard disk manufacturers. Each year, commercial polishing operations produce over 100,000 gallons of ethylene glycol polishing waste, which is not recyclable. Aqueous polishing fluids are critical to the industry, but water can corrode the sensitive electronic circuitry.

Ventana Research has developed a new class of benign synthetic copolymers whose aqueous solutions have high corrosion inhibition properties and are highly effective at lapping GMR read/write heads. These copolymers have an aspartate&#;aspartamide backbone and pendant combs containing a phenolic oligomer phytochemical functionality (i.e., gallate esters). Besides being nontoxic and environmentally friendly, these copolymers are capable of polishing GMR read/write heads more rapidly and efficiently with less waste than conventional lapping fluids. This affords manufacturers considerable savings by increasing production rates and reducing waste disposal costs.

Since , Pace Technologies, a major worldwide distributor of polishing consumables, has been distributing Ventana&#;s lapping fluid to manufacturers of hard drives as well as manufacturers of other products that require precision polishing such as optical lenses and flat-panel displays. In , Ventana received a Phase II Small Business Innovation Research (SBIR) grant from the National Science Foundation to continue developing its polishing fluid. Ventana has also developed a series of new corrosion inhibitors and paint primers from its phytochemical precursors and spun them off as a separate technology.

Development of Nike Brand Footwear Outsole Rubber as Environmentally Preferred Material: One of Nike&#;s long-term corporate environmental goals is to eliminate from its products all substances known or suspected to be harmful to human health or the environment. Nike is pursuing the vision of Considered Design, where its goals are to make innovative, performance- quality products that demand less of our natural resources and to incorporate sustainability as a design component from the beginning.

With these ultimate goals, Nike Footwear has demonstrated its industry leadership by successfully eliminating many toxic substances from its rubber outsoles. Nike Footwear redesigned two of its rubber formulations using the Cradle-to-CradleTM Design Protocol to assess chemicals against 19 human health and environmental criteria. Using this protocol, Nike identified rubber ingredients to be replaced and preferred alternatives to meet its performance requirements. Using more benign accelerators, vegetable oils, and modified processing, Nike created new environmentally preferred rubber for outsoles. The new formulations contain 96 percent fewer toxic substances by weight than the original formulations, provide equal performance, look the same, and cost no more than traditional rubber. To Nike&#;s knowledge, these are the most advanced and sustainable rubber formulations within the footwear industry; they will help initiate collaboration with manufacturers in other industries in the design and use of more sustainable materials. Nike is currently pursuing the establishment of a consortium of companies to pool resources to jointly research, develop, and use preferred chemicals, helping both to improve cost factors and to increase the sustainability of materials that can be used collectively. The goal is to increase the list of chemicals that are tested and categorized as well as to open the protocol to scientific peer review.

In , Nike produced about 170 million pairs of shoes worldwide that contained some of its new rubber formulations, representing approximately 25,000 metric tons of environmentally preferred rubber.

Development of Novel Liquid Crystal Polymers: A new class of liquid crystal polymers which have a backbone chain of either polyiminoborane (-BH-NH-BH-NH- or [BNH2]x) or polyaminoborane (-BH2-NH2-BH2-NH2- or [BNH4]x) or polyborozine ([B3N3H6]x) have been invented and some of their applications demonstrated over the past three years. These polymers almost align, when present at an interface, and their angle of alignment mainly depends on the side chains, which are polymethylsiloxane polymers. Depending on this angle of alignment (?), quantified by an order parameter (S), where S is defined as 1/3 (3cos2? -1), the interfacial properties of the liquid crystal polymer can be manipulated.

A PCT application [1] defining this new composition of matter was filed August 12, , and all claims were approved without dispute. U.S. EPA funded TechSolve, Cincinnati, OH, to conduct toxicological testing, and determination of characteristics for use as "green" metal working fluids. Results of these studies have been published as an interactive CD (EPA/600/C-03/063), which have concluded that these polymers are environmentally benign and exhibit superior metal working fluid characteristics. LCP Tech, a small business company, was created to commercialize these polymers as metal working fluids, and pursue other applications, such as fire retardants, fuel cells, and intelligent membranes.

Development of Two Unique Processes for Manufacturing High-Purity Cyclopentane from Dicyclopentadiene: The team working in Baytown Texas developed two unique processes for manufacturing high-purity cyclopentane from dicyclopentadiene. Cyclopentane replaces ozone-depleting substances (ODS"s) such as CFC-11 or HCFC-141b foaming agents used in the manufacture of rigid polyurethane or polyisocyanurate insulation. Cyclopentane has the necessary physical properties including low vapor thermal conductivity and vapor pressure to make it a viable replacement for ODS"s but was not commercially available in sufficient quantity due to lack of an economic manufacturing process. This team"s invention (US Patent ) is employed in a manufacturing facility started up in December located at Sarnia Ontario. That facility was built primarily to support the conversion of US insulation manufacturers from the use of ODS"s to the green cyclopentane substitute. US consumption of ODS"s in polyurethane and polyisocyanurate insulation amounts to about 100 Mlb/yr, all of which may be replaced by cylopentane.

Development of Water-Based Materials for Post-it® Super Sticky Notes: In the late s, 3M developed a prototype of a new, enhanced Post-it® Notes product for use on vertical and hard-to-stick surfaces. This prototype used solvent-based adhesive formulations. At the same time, 3M launched an initiative to reduce volatile organic compound (VOC) emissions by 90 percent by the year . Rather than install pollution control equipment to control the VOC emissions from the proposed manufacturing process for the new Post-it® Notes, 3M delayed introducing the product until it could develop a new, water-based adhesive formulation. 3M finally introduced Post-it® Super Sticky Notes in .

The new water-based microsphere materials that 3M uses in its Post-it® Super Sticky Notes yield the desired performance, generate fewer air emissions, have a reduced environmental risk profile, and are less expensive to manufacture than the original, proposed, solvent-based formulations. The formulations are trade secrets, but they are based on acrylate polymers. They do not contain any fluorochemicals, alkylphenol ethoxylates, poly(vinyl chloride), phthalates, or heavy metals intentionally added or present as impurities above de minimus levels. The new formulations reduce annual VOC emissions by 33,400 pounds (with pollution controls) or 2,170,000 pounds (before pollution controls) and Toxic Release Inventory (TRI) emissions by 20,500 pounds (controlled) or 1,024,000 pounds (before control) compared with the projected emissions of the proposed, solventbased process.

The water-based system eliminates the need for a thermal oxidizer to control VOC emissions, reducing 3M&#;s emissions of CO2 from fuel combustion. It also increases worker safety and reduces the possibility of fire, chemical release, or explosion. The waterbased system also generates significant cost savings. 3M&#;s Post-it® Super Sticky Notes are an excellent example of the benefits of green chemistry and the importance of integrating 3M&#;s core values into decision-making. Following its success with Post-it® Super Sticky Notes, 3M added water-based formulations to Post-it® Sticky Picture Paper for printing digital pictures and to other specialty applications in .

Device and Method for Analyzing Oil and Grease in Wastewaters without Solvent: The Clean Water Act lists oil and grease together as one of five conventional pollutants. All National Pollution Discharge Elimination Systems (NPDES) permits, all pretreatment permits, and all Industrial Effluent Guidelines require measurements of oil and grease. Millions of analyses for oil and grease are done annually in the United States. Following the Montreal Protocol in , EPA replaced a Freon extraction method for oil and grease testing with an n-hexane extraction method (EPA ; EPA a). This created several problems: (1) n-hexane is a hazardous, flammable liquid; (2) n-hexane is a known neurotoxin; and (3) testing generates millions of liters per year of n-hexane waste that require disposal. Thus, the current methodology is inconsistent with the intent of the Clean Air Act and Clean Water Act, both of which identify n-hexane as a hazardous pollutant.

TM-based polymeric membrane to capture and concentrate oil and grease from water, a metal-membrane support, and a polypropylene housing designed for pressurized water samples.

Orono Spectral Solutions (OSS) developed a solid-phase, infrared-amenable extractor technology that both eliminates solvents from oil and grease analysis and provides more economical, accurate analyses. OSS&#;s extractor unit is small, robust, and disposable (or partially recyclable), and it contains no toxic substances. The extractor unit includes a Teflon-based polymeric membrane to capture and concentrate oil and grease from water, a metal-membrane support, and a polypropylene housing designed for pressurized water samples.

The membrane does not absorb IR light in the spectral regions of interest; after drying, the device can be put into an IR spectrophotometer to determine the amount of oil and grease. This patent-pending technology has successfully completed ASTM (American Society for Testing and Materials International) multi-laboratory validation and received ASTM method number D. EPA is currently considering replacing method with this one. This replacement would save one million liters of hexane annually and produce estimated benefits to the U.S. economy of $50&#;$60 million. OSS is actively commercializing this technology worldwide.

Diesel DeOx Catalyst: By , EPA will implement more stringent standards restricting emissions from heavy-duty diesel vehicles. These standards are creating a market for products that reduce diesel emissions.

Argonne National Laboratory has developed a technology to remove nitrogen oxides (Ox) from diesel exhaust gases. The Argonne Diesel DeOx Catalyst works by selective catalytic reduction of Ox to N2 using diesel fuel hydrocarbons as the reducing agent. The catalyst formulation is based on copper zeolite formulations (Cu-ZSM-5) that can reduce Ox, but are unstable. Argonne added a cerium oxide coating over the Cu-ZSM-5 formulation, which improved both the catalyst&#;s long-term stability and its activity at lower temperatures. This catalyst is effective and economical when used with the ultra-low sulfur diesel fuel that is now required for on-highway use. In contrast to other systems, Argonne&#;s system performs better in the presence of water vapor, making it ideal for automotive and truck exhaust systems, which always contain water. The DeOx system can be installed on both existing and new vehicles.

Argonne&#;s Diesel DeOx Catalyst is a totally passive, easy-to-use system that converts 95&#;100 percent of Ox to atmospheric nitrogen (N2) and meets EPA&#;s standards. It is expected to have lower manufacturing and installation costs than competing technologies. The materials used to produce the system are relatively inexpensive and nontoxic. The catalyst is expected to have a long lifetime.

Integrated Fuels Technology (IFT) is collaborating with Argonne to develop this technology. By combining its own fuel-saving technologies with Argonne&#;s DeOx formulation, IFT expects to advance its integrated approach to emissions control and achieve substantial Ox reduction without adversely affecting other performance-enhancing or emission-reducing technologies. Currently, IFT is refining the design and manufacturing methods for the product. Promising future markets include passenger vehicles and stationary sources including industrial diesel engines, coal-fired power plants, and methane-fueled "peaker" power plants.

Direct Biocatalytic Synthesis of Functionalized Catechols: A Short Route to Combretastatin A-1: The projects described within this document are nominated for an academic award under Focus Area I, the use of alternative synthetic pathways for green chemistry. The prevention of pollution at its source is addressed by replacement of currently used methods of oxidation (all based on metal reagents) with enzymatic techniques (all performed in water). In previous projects we have already proven the value of the enzymatic oxidation in the attainment of important pharmaceuticals from metabolites of aromatic compounds. Halogenated aromatic compounds, viewed in many cases as harmful to the environment, are enzymatically converted to useful synthons and effectively removed from the hazardous waste pool with the added economic benefits of strategic conversion that would not be available through incineration of such compounds.

It must be emphasized here that the enzymatic conversion of the toxic aromatic materials takes place in the very first step of the synthetic pathway and that all subsequent synthetic intermediates are harmless. The residual mass from the enzymatic processes is judged suitable for disposal to municipal sewers, thus further reducing the amount of actual waste. The key philosophy of our projects rests on the managed processing of aromatic waste to value added substances. A new definition of efficiency, "Effective Mass Yield," is provided as the percentage of the weight of desired product in the weight of all non benign mass requiring treatment or disposal that is used in the manufacturing process.

Discovery and Development of a Green Process for Radafaxine: GlaxoSmithKline has identified and fully evaluated two viable commercial routes of manufacture for Radafaxine, a compound that has shown antidepressant activity in animal models of depression. Radafaxine is an (S,S)-enantiomer. The corresponding (R,R)-enantiomer is associated with undesirable effects. The key challenge was to separate the two enantiomers efficiently and minimize the environmental impacts associated with the undesired enantiomer. Route B3, an initial improvement on the traditional synthesis, uses an original and innovative dynamic kinetic resolution to synthesize the desired single enantiomer.

This simple process has several advantages and produces the desired enantiomer without expensive and environmentally unacceptable chiral catalysts or templates. It also replaces the environmentally undesirable solvents dichloromethane and acetonitrile. The second process, multicolumn chromatography (MCC), improves on route B3, retaining all of its advantages. The MCC process also re-epimerizes and recycles the undesired enantiomer, delivering an overall process with significant environmental benefits.

Detailed analysis demonstrates that the MCC-based process meets all commercial and quality criteria; in addition, it reduces the use of valuable resources and greatly decreases the process liquid waste streams. The traditional synthesis required 260 kg of input material and 194 kg of solvent per kg of product. The mass intensity of the MCC process is approximately 20 kg of input material per kg of product, an incredibly low number for a pharmaceutical product. The MCC process uses only 19 kg of solvent per kg of product, with potential for further recovery. GlaxoSmithKline performed a pilot study on medium-to-large scale in-house MCC equipment during . At peak production, GlaxoSmithKline calculates that the MCC process could reduce the overall waste load by 5,000 metric tons per year.

DispersitTM: A Waterbased Oil Dispersant for Oil Spills in Salt and Fresh Water: Oil spills in marine environments pose a significant ecological and economic threat. Mechanical recovery methods are ineffective. Petroleum based dispersants, while effective, present their own environmental problems, in addition to, health threats to the user. Other waterbased dispersants, are either ineffective or highly toxic. Dispersit is a breakthrough formula combining effectiveness with safety. It is an effective and non-toxic oil spill dispersant combining a predominately oil-soluble surfactant with a predominately water-soluble surfactant and a co-solvent for coupling a mixture of the predominately oil-soluble surfactant and the oil spill, with the predominately water-soluble surfactant. Water is included in the combination to help advance the interaction between the predominately oil-soluble surfactant and the predominately water-soluble surfactant, as well as, the co-solvent. The water component also helps reduce the viscosity of the dispersant to allow it to be pumped under pressure. The resulting product performs to a superior degree in both fresh and salt water. It does not pose a threat to human health.

DOE Methods for Evaluating Environmental and Waste Management Samples: "DOE Methods for Evaluating Environmental and Waste Management Samples" ("DOE Methods") is a document that provides new technology and consolidated methods to analytical chemistry laboratories around the country. These laboratories are working on one of the world"s most challenging environmental issues: Cold War legacy waste. Sampling and analytical technologies that minimize waste production are given priority over traditional methods. It has been demonstrated, for example, that some of the technologies produce 60 to 70 percent less hazardous and radioactive waste than other available technologies.

The guidance information in "DOE Methods" also helps minimize the number of analyses and saves time and money. Guidelines are provided on how to (1) efficiently develop a sampling and analysis program, (2) effectively and efficiently sample waste, (3) handle radioactive samples safely, and (4) select appropriate analytical methods. Cross references allow the users to select from currently available standard methodologies. "DOE Methods" has been available for both DOE and commercial use since . It is updated every 6 months, thereby accelerating the release of new technology to speed EM [sic] operations.

The significance of the document is in its unique application to the analysis of radioactive components and highly radioactive mixed waste. The document currently contains about 65 sampling and analytical methods, many of which are focused on the mixed-waste issue. The highly challenging world of environmental problems cannot be solved without effective sampling and analytical methods. "DOE Methods" takes a major step in the resolution of this problem.

Doped Semiconductor Nanocrystals as Heavy-Metal-Free Quantum Dots: Nearly all the colloidal fluorescent quantum dots being produced today with quality high enough for real-world applications contain toxic heavy metals such as cadmium, mercury, and lead. Although these quantum dots have better size-dependent electrical and optical properties than do bulk semiconductors, they are not used widely, due in part to the toxicity of their heavy metals.

Other researchers have studied doped nanocrystals as alternatives to heavy-metal-based quantum dots since the s, but they have not discovered reaction schemes that achieve pure dopant emission at high fluorescence quantum yield. Often, a large portion of the nanocrystals were undoped, resulting in emission peaks from both the undoped and doped nanocrystals.

Professor Peng and NN-Labs have developed a breakthrough synthesis for doped quantum dots (D-dotTM) that are free of heavy metals. Professor Peng developed quantum dots that replace the toxic dimethyl metal precursors with metal oxides. This technology produces doped semiconductor nanocrystals with pure dopant emission (over 99 percent) at fluorescence quantum yields greater than 80 percent. These doped quantum dots do not suffer the reabsorption self-quenching inherent in intrinsically emitting quantum dots, due to the large Stokes shift between the host absorption and dopant emission. In addition, these new high-quality, doped quantum dots have far greater thermal and photo stabilities than do conventional quantum dots. The superior quality of these new, heavy-metal-free, doped quantum dots will enable quantum dot applications to reach the commercial level without introducing toxins into the environment. These quantum dots are a suitable alternative in many applications from solid-state lighting to biomedical labeling.

Professor Peng has filed a patent for this technology. During , NN-Labs launched its first two doped nanocrystal product lines, Yellow and Orange D-dotsTM. It is developing a full spectrum of D-dotTM emitters.

DryExx Conveyor Lubricant Program: In commercial food and beverage container filling operations, conveying systems typically move at very high speeds. Copious amounts of dilute, aqueous lubricant solutions are applied to the conveyors or containers with spraying or pumping equipment. Traditionally, these solutions lubricate the conveyor chain, run off the conveyor, and eventually enter the facility&#;s effluent stream. Concentrated lubricant solutions often consist of fatty acid or fatty amine surfactants. Traditional lubricant solutions and their associated technology have several disadvantages.

First, dilute aqueous lubricants typically require large amounts of water on the conveyor line. The area near the conveyor line becomes very wet and the excess water must then be disposed of or recycled.

Second, some aqueous lubricants can promote microbial growth.

Third, diluting the concentrated lubricant before use can produce variable concentrations of dilute solution and thus, variable performance. Finally, variations in water quality can alter the performance of the dilute lubrication solution. For example, alkaline water can lead to environmental stress cracks in poly(ethylene terephthalate) (PET) bottles. The DryExx Conveyor Lubricant Program lubricates conveyor chains without added water. The DryExx Program consists of the DryExx chemical formulation and a dispensing concept.

The DryExx formulation contains a mixture of water-miscible silicone material and a water-miscible lubricant. It contains no hazardous ingredients in quantities requiring reporting. The product is targeted for food and beverage bottlers who package products in PET containers using conveyors with plastic or polyacetyl chains. Currently, Ecolab estimates this program is saving U.S. bottling facilities 240 million gallons of water annually and is preventing an additional 1 million gallons of conventional lubricant concentrate from entering the effluent stream.

DryWashTM Carbon Dioxide Dry Cleaning Technology: DryWashTM is a patented, Hughes-specific liquid carbon dioxide garment dry cleaning technology and is a safe, ecologically acceptable, and cost effective alternative dry cleaning process. Currently, the dry cleaning industry uses perchloroethylene (PCE) (85 percent of establishments), petroleum-based or stoddard solvents (12 percent of establishments), CFC-113 (less than 2 percent of establishments), and 1,1,1 trichloroethane. All conventional dry cleaning solvents present health risks, safety risks, or are environmentally detrimental.

PCE is a suspected carcinogen, petroleum-based solvents are flammable and smog producing, and CFC-113 is an ozone depletor and targeted to be phased out by the end of . Health risks due to exposure to cleaning solvents and the high costs of implementing and complying with safety and environmental restrictions and regulations, have made dry cleaning a much more difficult business in which to achieve profitability. Solvents are suspected of contaminating ground water, air, and food products (i.e., in nearby markets). For these reasons, there is an ongoing search for alternative, safe, and environmentally friendly cleaning technologies, substitute solvents, and methods to control exposure to dry cleaning chemicals.

DryWashTM reuses carbon dioxide, a naturally occurring byproduct of combustion that is a readily available, inexpensive, and unlimited natural resource. It is also chemically stable, noncorrosive, nonflammable, nonozone depleting, and nonsmog producing. Performance has been demonstrated to major dry cleaning equipment manufacturers worldwide and to the EPA. Actual garments, along with International Fabricare Institute (IFI) standardized cleaning test fabrics, were used for the demonstrations. The performance of the DryWashTM cleaning process was quantified favorably against commercial perchloroethylene cleaning by Los Alamos National Laboratory, using IFI standards.

DUAL-ICE®: A Non-Toxic, Non-Caustic Instant Cold Compress: Instant cold compresses have been employed by both industry and the general public for decades. Instant cold compresses employed for trauma or heat stress are mainly a combination of water and ammonium nitrate encased in a thin polyplastic bag. Ammonium nitrate is classified as a hazardous substance by the EPA and is recognized as potentially explosive and detrimental to the environment. In addition, the generically low-stress packaging applied by most commercial manufacturers of items employing this chemical places the consumer at unnecessary risk. In response to a need by the U.S. Marine Corps, which was prohibited from deploying current instant cold compresses for numerous factors, H and H Associates developed DUAL-ICE®, an environmentally safe alternative to ammonium nitrate cold packs.

Following proof-of-principal testing, H and H engineers deduced that a combination of ammonium chloride, urea, and water would act to provide the necessary endothermic reaction. The product is fully non-toxic, non-caustic, non-hazardous, and heavily packaged for rough handling. DUAL-ICE® demonstrates a high cooling potential, maintains a shelf life of at least one year, and is air- and ground-shippable. Furthermore, the postendothermic reaction chemical byproduct is such that, after the initial use as an instant cold compress, DUAL-ICE® is fully reusable as a refreezable cold pack that remains flexible and conforms to an injured appendage or area.

DuPont Petretec(SM) Polyester Regeneration Technology - Making Polyester Evergreen: Thirty-five billion pounds of polyethylene terephthalate polyester (PET) are produced globally each year. PET goes into thousands of end uses and it is also the "greenest" of the polymers. Due to this polymer"s inherent thermal stability, PET-type thermoplastics lend themselves to direct recycling and serve as a raw material for the production of numerous products. The success of PET bottle recycling, for example, annually diverts more than 600 million pounds of PET bottles per year from landfills. This recycling technology, however, requires high-purity waste and the recycled material generally may only be used for carpeting or pillow fibers. There are a large number of uses for virgin PET where the material has been dyed, coated, or mixed with a co-polymer and therefore is not suitable for direct recycling.

This material is landfilled. The patented DuPont Petretec(SM) polyester regeneration technology provides an environmental and economical alternative to landfills and offers many advantages over recycling. Petretec(SM), DuPont"s proprietary form of methanolysis, makes polyester evergreen. The process provides a safer and more economical way to reuse materials, especially those with much higher contaminant levels than other recycling methods. It takes PET fibers, films, and resins currently going to landfills, unzips the PET molecule, and breaks it down into its raw materials, dimethyl terephthalate (DMT) and ethylene glycol (EG). The Petretec(SM) process allows these raw materials to retain their original properties so they can be reused over and over again in any first-quality application. The process accepts polyester with a broader variety of contaminants and at higher levels than any other process.

Petretec(SM) reduces dependence on oil-derived feedstocks and diverts polyester from the solid-waste stream into useful new products. In the Petretec(SM) technology, scrap PET reacts with methanol vapor at elevated temperature greater 260 °C) to produce a vapor stream of DMT, EG, and excess methanol. A glycol azeotroping agent, methyl p-toluate (MPT) is added and the components are separated. Purification is accomplished by extensive fractional vacuum distillation. The products are then shipped back to PET fiber, film, and resin producers. Each kilogram of PET made from the Petretec(SM) process using RDMT and glycol, reduces the demand for about one-half kilogram of the traditional hydrocarbon raw materials. DuPont invested $12 million to convert part of its Cape Fear facility, near Wilmington, North Carolina, to a methanolysis plant. the new plant can handle more than 100 million pounds of scrap PET and capacity is easily expandable. By actually unzipping the molecules, we can begin the cycle of using these materials in an endless series of new applications.

Durable AMPS® Antimist Polymers for Aqueous Metalworking Fluids: The generation and accumulation of metalworking fluid (MWF) mists in the plant environment during metalworking production gives rise to worker health and safety concerns. It is estimated that about 1.2 million workers are potentially exposed to MWFs annually. In response to increasing worker health concerns from MWF mists, the United Auto Workers Union has petitioned the Occupational Safety and Health Administration to lower the permissible exposure limit (PEL) of oil mist mg/m3. The current mist control methods being used for exposure control have drawbacks. For instance, engineering mist controls based on machine enclosures and mist collection are exorbitantly expensive to install and maintain. A second type of chemical mist control method, based on high molecular weight polymers as antimist (AM) additives for aqueous MWFs, has found limited acceptability because AM polymers lose their performance due to shear degradation, requiring frequent additions to maintain performance.

The development of durable AMPS® polymers at Lubrizol solves this problem. These polymers suppress mist formation at the source by stabilizing MWF against breaking up into small droplets that get suspended in the plant environment as mist. The reduction in mist minimizes worker exposure to MWF chemicals and other pollutants present in the mist, creating a safer worker environment. Because they are shear stable, the AMPS® polymers provide long-lasting mist reduction. The application and performance of the AMPS® polymers were evaluated during field trials at small machine shops and large Ford manufacturing plants. In a small machine shop field test, a one-time addition of 1,000 ppm AMPS® polymer resulted in a stable 60% mist reduction. During large-scale plant trials at Ford Motor Company, a one-time addition of 1,000 ppm AMPS® polymer resulted in stable 40 to 60% mist reduction over two months in the plant environment. The worker response to reduced mist levels during these trials was extremely positive.

It was felt that after the polymer addition, there was a distinct improvement in plant air quality, general improvement in working conditions, and less slippery floors from oil mist deposits. AMPS® polymers provide a low-cost method of suppressing mist generation and controlling exposure because they provide long-lasting mist suppression at low (ppm) concentrations. These polymers are less labor-intensive to implement in the field because they disperse easily in the MWF and do not require frequent addition. They are manufactured as aqueous solutions and do not contain any volatile organic compounds. Extensive sensory, inhalation, and dermal toxicity tests have shown that AMPS® polymers exhibit a profile of minimal toxicity under conditions of use. Waste water treatment evaluations have shown that they do not affect the waste treatability of aqueous MWFs.

Duraflame® All-Natural Manufactured Firelog: Duraflame, Inc. is America&#;s leading marketer of manufactured firelogs. Headquartered in Stockton, CA, Duraflame is a privately held company that has been in business for more than 30 years. What started out as an effort to recycle the sawdust produced by wood milling operations has grown into a way of doing business for Duraflame. The company&#;s Research and Development Department regularly experiments with resources to determine unique approaches to product development and is continually striving to create convenient, environmentally responsible products to meet consumer needs.

Faced with a shrinking supply of petroleum wax and a rise in restrictions on wood-burning fireplaces by air quality districts (particularly in the Western states), the company has focused on developing manufactured firelogs using materials that are both cleaner burning and recycled or renewable. In , Duraflame introduced a new all-natural firelog made from recycled biomass products such as wood sawdust, ground nut shells, recycled cardboard, and plant waxes (to replace petroleum wax) as a combustible binder.

Standard petroleum wax&#;sawdust firelogs produce approximately only one third of key air pollutants associated with residential wood combustion compared to an equivalent natural wood fire. In contrast, Duraflame&#;s new all-natural firelogs produce approximately one quarter of the emissions of an equivalent natural wood fire. The Duraflame® All-Natural Firelog is now available in supermarkets across the United States and Canada.

Earth Conscious Chemistry: Eliminating 1,4 Dioxane in Cleaning Products: 1,4-Dioxane is an unwanted contaminant in many common personal care products sold in the United States. It occurs as a byproduct of common ethoxylated surfactants (e.g., sodium lauryl ether sulfate). 1,4-Dioxane is a cyclic ether that is highly miscible in water and migrates rapidly in soil. EPA has listed the compound as a probable human carcinogen based on the results of animal studies. 1,4-Dioxane is also listed with a group of pollutants in state and federal guidance for air pollution control. Earth Friendly Products has worked diligently to remove 1,4-dioxane from all of its products. Testing for 1,4-dioxane by gas chromatography/mass spectrometry conducted by the Organic Consumers Association (OCA) included new results from 20 laundry detergents: 13 conventional, mainstream brands and 7 brands self-identified as "natural."

The conventional brands had significantly higher levels of 1,4-dioxane. The highest were Tide® with 55 ppm, Ivory Snow® with 31 ppm, and Tide® Free with 29 ppm. OCA has confirmed in their latest report for that ECOS® Laundry detergent by Earth Friendly Products was free of 1,4-dioxane. Since June , Earth Friendly Products has successfully scaled up its formulas to produce natural products that do not contain any harmful chemicals, including 1,4-dioxane. The company uses a blend of coconut oil with anionic fatty acid chains that make excellent surfactants due to their dual hydrophilic and lipophilic properties. There is no sodium chloride salt added or used in any step of manufacturing or production of the company&#;s laundry products. Each product is made with sustainable, plant-based ingredients that are studied to ensure minimal environmental impact before and after production. This ensures that all of the company&#;s products are not only biodegradable, but also free of phosphate, caustic, formaldehyde, petrochemicals, chlorine, synthetic perfume, and ammonia.

EarthShell Packaging: Designed with the Environment in Mind: EarthShell composite material is made from common raw materials and has unique environmental attributes, comparable performance characteristics and is competitively priced with conventional paper and plastic packaging. EarthShell Packaging was developed over many years using a Life Cycle Inventory and in consultation with leading environmental experts to reduce the environmental burdens of rigid food service packaging through the careful selection of raw materials, processes and suppliers. EarthShell Packaging substantially reduces risk to wildlife compared to polystyrene foam packaging because it biodegrades when exposed to moisture in nature, physically disintegrates in water when crushed or broken and can be composted in a commercial facility (where available) or in your backyard.

The EarthShell Packaging composite material is made by combining starch, limestone, fiber and water to form a batter. The batter is placed into heated molds and baked for about a minute. The water turns to steam and forms and sets the product. The products are then coated with biodegradable coatings, printed and boxed. The use of advanced particle-packing technology allows the addition of large amounts of limestone (CaCO3) reducing the overall cost while maintaining the strength and other properties. Over 130 patents speak to the unique nature of the EarthShell technology.

EarthTec®: Green Water Treatment: EarthTec® is an EPA-registered algaecide and bactericide (EPA Number -1) that is certified by the National Sanitation Foundation (NSF) Standard 60 as a drinking water additive. It uses no chlorine and contains less copper than competing products. The proprietary copper formulation made by EarthTec® is 99.9-percent-suspended cupric ions (Cu(II)); its proprietary base product, ET-, keeps the copper biologically active and suspended. The copper remains fully dissolved indefinitely, thereby insuring long-term organic control as well as less environmental release. EarthTec® is not an organic compound.

Earth Science Laboratories has done extensive empirical research to develop and design the proprietary chemical technology that makes EarthTec® environmentally superior to chlorine. These studies conclude that EarthTec® lowers trihalomethane production, reduces disinfection byproducts and their precursors (natural organic matter), and reduces geosmin, eliminating the taste and odor in drinking water. EarthTec® also lowers haloacetic acid levels and reduces total organic carbon, both particulate and dissolved. Unlike chlorine, EarthTec® creates no carcinogenic disinfection byproducts. EarthTec® reduces the use of copper and other chemicals, eliminating hazardous chemical substances from the environment relative to the competing, chlorine-based technology. One can use 88.5-percent less EarthTec® than other copper sulfate products.

Compared to other copper sulfate products and chlorine, EarthTec® is less toxic than those current products, is safer for the atmosphere, is nonflammable, and reduces toxicity to humans, animals, and plants, producing human health and environmental benefits. EarthTec® is also more cost-effective than other copper sulfate products and chlorine.

The motto of Earth Science Laboratories is "clean water for the planet" and their mission, in part, is to produce environmentally responsible water treatment products in an ecologically accountable manner. Earth Science Laboratories manufactures EarthTec® and sells it worldwide. Professors Schweitzer and Reed performed empirical research comparing the product to chlorine.

ech2oTM - Electrically Charged Water: Traditional floor cleaning methods use an automatic scrubber filled with a large volume of cleaning solution consisting of water and a chemical detergent. Tennant Company&#;s ech2oTM technology eliminates the need for adding a chemical detergent to the automatic floor scrubber. The ech2oTM technology electrically activates tap water, causing it to perform like an all-purpose detergent. By removing the need for chemicals in the automatic scrubber, this technology eliminates the negative environmental and health impacts associated with producing, packaging, transporting, using, and disposing of traditional chemical detergents. Compared to traditional cleaning methods, the ech2oTM technology reduces water use by 70 percent and eliminates the need for chemicals.

The electrically charged ech2oTM solution is created in a special unit that is installed in Tennant&#;s automatic floor cleaning machines. The ech2oTM solution attacks the dirt and suspends it off the floor&#;s surface, enabling the scrubber&#;s pads or brushes to easily remove the soil. Approximately 45 seconds after the ech2oTMcleaning solution is created, it returns to plain water. What is left in the automatic scrubber&#;s recovery tank is plain water and the soil removed from the floor. In this process, 100 percent of the water used reverts to neutral tap water and can be handled and disposed of safely.

Tennant is the first in its industry to harness the cleaning power of water for cleaning hard floor surfaces and to use electrically charged water on a mobile platform. Tennant plans to make its patent-pending processing units available on several models of its cleaning machine platforms. Tennant launched its product during ; it has a number of patents pending.

EcoFuel - A Safe and Effective Canned Heat Alternative: DynynStyl developed a new canned heat product, EcoFuel, that offers major safety and environmental benefits. EcoFuel is designed to greatly reduce the safety hazards associated with SternoTM type fuels. DynynStyl worked with a new concept of delivery that eliminates danger both in use and disposal. EcoFuel is non-flammable, non-explosive and spill resistant. The odorless and consistent combustion controlled with a dual aperture lid produces a regulated burn time and temperature as a 5 hour Cooker or 10 hour Warmer. The rapid light igniter permits easy lighting and relighting until the fuel is completely consumed. All components are 100% biodegradable except the inert fiber.

EcoFuel has effectively proven a major reduction of risk due to fires, explosion, flash back, and spontaneous combustion in military and institutional markets. The elimination of personal injury and damages associated with low flash point fuels has received approvals and endorsements from fire and safety professionals. EcoFuel&#;s high flash point does not require special storage, handling or transportation.

The reusability and ability for complete consumption of EcoFuel provides a solution to the vast volume of unburned fuels left by conventional canned heat products. Also reduced are the secondary waste stream of packaging materials and the energy for manufacturing and transportation. One can of EcoFuel replaces five cans of SternoTM.

Ecological Paint Antimicrobial Clear Coat: Ecological Paint Antimicrobial Clear Coat is a self-curing water-based paint formulated to address public health concerns linked to the transference of bacteria and mold on public and private surfaces that people are likely to touch. Innovative Formulation has developed an antimicrobial, mold and bacteria retardant paint that is totally nontoxic and contains no volatile organic compounds (VOCs). Their Clear Coat is the first nontoxic antimicrobial paint product; other advertised non-VOC paints use solvents such as methyl ethyl ketone, acetone, and other ketones.

Clear Coat uses a sophisticated silver nanoparticle cage technology. For hundreds of years, silver has been acknowledged as effective in stopping the growth and spread of bacteria. Innovative Formulation has designed a dispersal system that releases silver ions in a uniform, non-clumping manner, providing comprehensive antimicrobial coverage of all treated surfaces. The nano emulsion polymer carrying system in Clear Coat is a single-component, fully crosslinked acrylate. Clear Coat uses pharmaceutical-grade pigments.

Toxic chemicals are a health hazard. The paint produced in the United States during contained almost 5 million kilograms of VOCs. The origin of many respiratory conditions in the U.S. population is unknown, but it is, in the company&#;s opinion, related to toxic chemicals in the atmosphere. Airborne toxic chemicals may also be related to the high incidence of liver and pancreatic cancers in the United States.

Innovative Formulation has created a completely safe antimicrobial paint that is virtually free of hazardous chemicals. No other paint company in the United States can legitimately and accurately make such representations. Innovative Formulation has been producing its Clear Coat since December at a plant in Tucson, AZ. A major fast food chain is currently using Clear Coat and a major hotel chain is testing the product.

Ecomate® Environmentally Benign Blowing Agent for Polyurethane Foams: Traditionally, chlorofluorocarbons (CFCs) were the preferred blowing agents for polyurethane foams. Foams blown with CFCs had good insulating and structural properties for use in refrigerators, building construction, and spray foam. CFCs were removed from polyurethane foam in the s, however, due to their potential to destroy the ozone layer. Hydrochlorofluorocarbons (HCFCs) have a lower Ozone Depletion Potential (ODP) and are currently replacing CFCs, but were scheduled for phase out by in the United States. Ecomate® (methyl formate) is a zero-ODP, zero Global Warming Potential (GWP) blowing agent designed to replace CFCs, HCFCs, and hydrofluorocarbons (HFCs). Ecomate® is also VOC-exempt, meaning it does not contribute to smog.

With little or no modification of existing manufacturing processes, ecomate® foaming systems provide foam with insulating and structural characteristics equivalent to those of conventional polyurethane foams. Foam Supplies, Inc. developed ecomate® as a green replacement for both HCFCs and the high-GWP hydrofluorocarbons (HFCs), which have GWPs of 725 to 1,810. Each pound of ecomate® replaces about two pounds of alternative blowing agents. Using ecomate® as a blowing agent in polyurethane foams has eliminated almost one million metric tons per year (mt-CO2e) of high-GWP compounds such as HFC-134a and HFC-245fa. Using one million pounds of ecomate® would eliminate the equivalent of 1.4 billion&#;3.4 billion pounds of CO2 emissions or 0.6 million&#;1.5 million mt-CO2e. Ecomate® blowing agent costs substantially less than HFCs, and there are usually no significant capital expenses associated with implementing the ecomate® technology.

Ecomate® foaming systems allow manufacturers to help the environment without increasing their costs. Ecomate® has been demonstrated in pour-in-place, boardstock, and spray insulation systems as well as in boat flotation foam. Ecomate® currently has a variety of applications in several countries; its availability has allowed EPA to accelerate the phase out of HCFCs in the United States.

ECONEA® 028: Designing and Developing a Metal-Free, Environmentally Safe, and Effective Antifoulant for Use Against Hard Fouling Marine Organisms: ECONEA® 028 is the trade name for a new, non-metal compound developed and tested by Janssen to replace copper compounds now used to control hard fouling organisms on underwater surfaces. Paint containing 3-6% ECONEA® 028 provided excellent hard fouling control on numerous test panels on commercial and military vessels. Once released at the surface of the paint into the environment, ECONEA® 028 is transformed rapidly into less toxic degradation products that pose minimal risk to aquatic life at predicted environmental concentrations.

ECONEA® 028 degrades rapidly in seawater by hydrolysis, and in sediment by anaerobic and aerobic metabolism (half-lives of 3 hours, < 1 hour, and < 1 day, respectively). Environmental modeling indicates that ECONEA® 028 can remedy an existing environmental problem in San Diego Bay (SDB), where copper levels exceed clean water standards. Elimination of copper from U.S.Navy antifouling paints, by combining ECONEA® 028 for hard fouling with an existing antifoulant for soft fouling, potentially can reduce copper loading in SDB by over 7,000 Kg per year from hull leachate. The combined copper burden in aquatic ecosystems of four military ports can be reduced by over 25,000 Kg annually using this technology, with potentially over 98,000 kg copper annually by conversion of the entire military fleet.

Effluent-Free and Selective Delignification Using Only Oxygen and Water: A fundamentally new chemistry provides controlled electron-transfer pathways for remarkably selective O2 oxidation of the lignin in wood fiber or pulp to its natural biosynthetic precursors, CO2 and H2O. The CO2 can, in turn, be reacted with CaO to produce the clay filler normally added to cellulose in papermaking. The high selectively of this chemistry makes it possible, for the first time, to replace chlorine dioxide, ozone, peroxides, and all such environmentally less attractive, or more energy-intensive or costly oxidants, by O2. Moreover, the conversion of lignin to its natural precursors (lignin mineralization), makes it possible, for the first time, to completely eliminate the liquid waste (chemically modified lignin fragments) emitted by all existing or proposed delignification processes.

These outcomes are achieved in two steps by a new multi-functional oxidant and catalyst system. This system is a thermally equilibrating, and thus inherently stable, aqueous ensemble of polyoxometalate (POM) salts. The ensemble is designed to include key species necessary for anaerobic (and hence, highly-selective) oxidative depolymerization and solubilization of lignin (step 1), for catalytic O2-mineralization of lignin (step 2), and for maintaining the pH near neutral at all times. In related work, 100% oxygen-atom-efficient catalysts for chemoselective O2-oxidations have been developed.

EHCTM for a Greener Groundwater Treatment Technology: The patented EHCTM technology is a remediation product used for the in situ treatment of groundwater and saturated soil contaminated with persistent organic compounds. EHCTM is an injectable material composed of microscale zero-valent iron (ZVI) and foodgrade organic carbon (solid or liquid) that ferments slowly to release fatty acids and nutrients in situ. The product supports rapid and complete destruction of chlorinated solvents, explosives, pesticides, and many other persistent compounds that may be present as contaminants in soil, sediment, and groundwater.

EHCTM works through a number of mechanisms: (1) direct abiotic reduction due to contact with the zero-valent iron; (2) enhanced thermodynamic conditions due to lowered redox potential; (3) indirect chemical reduction by reduced metals; and (4) biostimulation of dehalogenating bacteria down-gradient from injection locations.

Because it is, in part, a plant-based material, EHCTM can provide safe, renewable, costefficient, and effective remediation for many sites. Compared to some in situ chemical oxidation (ISCO) technologies, EHCTM is nonhazardous and much less disruptive of natural ecosystems. Compared to conventional organic substrates, ZVI and the complex carbon source in EHCTM minimize the production of potential fermentation end-products, such as methane. ZVI provides a substantial pH-buffering capacity, whereas conventional organic substrates can lead to aquifer acidification that adversely influences the natural attenuation mechanisms. EHCTM supports the complete dechlorination of trichloroethylene, tetrachloroethylene, and carbon tetrachloride without the accumulation of metabolites; this is a key factor differentiating EHCTM from competitive groundwater treatment technologies such as molasses, lactates, and vegetable oils. An EHCTM injection is typically required only once and is complete in one to two weeks with an active lifespan of three to five years in groundwater, minimizing its carbon footprint.

Since the first field-scale project in , EHCTM has been used to treat approximately 100 locations around the globe.

ElectroBrom Biocide System: The ElectroBrom Biocide System uses a novel, low cost electrolytic cell, based upon impregnated electrolytic graphite, to economically produce a biocidal hypobromite solution on demand and on-site, from a nonhazardous aqueous precursor solution equimolar in bromide and chloride anions. Electrolysis of an equimolar bromide-chloride solution provides for maximum production of the desired hypobromite ion, which has a substantially higher biocidal efficiency in the alkaline cooling waters commonly encountered today than chlorine based biocides. Due to the reasonable cost of the technology, it can be used to cost effectively provide the continuous halogenation recommended by OSHA and CTI for control of Legionnaires" Disease. This technology can eliminate the transport, handling, and discharge of up to 40 million lbs/yr of toxic, hazardous chemicals used for biological control in an estimated 300,000 cooling towers located throughout our towns and neighborhoods.

Electrodialysis and Chromatographic Separation Technology for Chlorine-Free Production of Potassium Hydroxide and Hydrochloric Acid: The United States consumes approximately 2 billion pounds of potassium hydroxide (KOH) per year. The traditional chloralkali process for KOH uses electrolysis of potassium chloride in water and produces chlorine gas (Cl2), hydrogen gas (H2), and KOH. Cl2 is a hazardous air pollutant (HAP) that faces declining demand due to the phase-out of chlorinated chemicals. NSR has commercialized the first environmentally friendly, cost-effective alternative to the chloralkali process in decades. NSR&#;s new process manufactures 45&#;50 percent KOH and 7 percent hydrochloric acid (HCl). The process uses NSR&#;s novel electrodialysis IonSelTM stacks, which include bipolar membranes of specialty polystyrenes modified with ion exchange groups.

The novel design of IonSelTM stacks allows the cells to operate at high efficiency, consume 40 percent less energy, and generate high-purity products. The process rearranges ions in solution and is particularly suited to recycling salts generated in other applications including those from the pulp and paper industries and from the environmental control systems in coal-fired power plants. NSR&#;s process yields high-purity, food-grade products without mercury (a health hazard to children) or oxidizing species like chlorate and hypochlorite. The lower energy consumption per unit of KOH made by NSR&#;s process allows smaller plants to produce equivalent amounts of HCl and KOH profitably. Smaller plants cost less, can be built close to end-users, and reduce transportation hazards. NSR supplies food grade 7 percent HCl to Archer Daniels Midland by pipeline.

This efficient transfer eliminates the unnecessary transport and accidental release of fuming 35 percent HCl. NSR&#;s single plant eliminated the production of 2 million pounds of Cl2 during ; at full capacity, it would eliminate the production of 10 million pounds of Cl2 per year. NSR&#;s technology could potentially eliminate the production of billions of pounds of unnecessary Cl2 each year.

Electrometallurgical Treatment of Nuclear Waste: Researchers at Argonne National Laboratory have developed an electrometallurgical treatment that can effectively separate toxic, hazardous, or radioactive metals from a wide variety of nuclear wastes. The key step in the process involves the fast, compact electrorefining of large quantities of waste material in an electrochemical cell. Argonne researchers have demonstrated this step by the extraction of more than 200 kg of uranium from spent fuel in one month. The uranium product can be stored, recycled, or converted to an oxide for disposal as a low-level waste.

The metal residue, fission products, and transuranic elements from the spent fuel can be immobilized in highly stable waste forms for disposal in a geologic repository. Compared with conventional processing, electrometallurgical technology holds promise for significantly reduced costs, greatly decreased volumes of high-level radioactive waste, and negligible volumes of secondary or low-level wastes. This technology could facilitate the environmentally sound processing of most of the more than metric tons of spent fuel accumulated within the Department of Energy complex. This technology also has potential spin-off applications for industry, such as the treatment of enrichment tailings from nuclear plants and the disposal of nontoxic wastes (e.g., barium-contaminated slats) from industrial processes.

Electronic and Photonic Polymers from Biocatalysis: As technologies continue to become more sophisticated in this fast-paced information age, the need for new and advanced electronic and photonic materials becomes a critical requirement for future leaps in performance, size, and speed. Simultaneously, however, with this drive for new advanced materials is the growing concern over the negative impact that these new technologies will have on the environment. Conventional conducting polymers are synthesized, for example, from reactions that involve strong chemical oxidants and the use of toxic solvents for solubilization and processing.

Earlier studies had shown that enzymes were an exciting, environmentally friendly alternative to the synthesis of many of these polymers. However, the mechanisms involved in these reactions only led to highly branched and often insoluble polymers that had very poor electrical conductivities and optical activity. While investigating new ways to overcome these limitations with the enzymatic approach, it was found that simple addition of a charged molecular species (polyelectrolyte or surfactant) to the reaction medium provides a type of biocompatible nanoreactor that not only optimizes enzymatic function and monomer coupling, but also provides water solubility of the final complex. The final polymers have enhanced electrical and optical properties and are processable, and the entire process is environmentally compatible. A number of templated polyanilines and polyphenols have been produced and characterized using this process. Enzymatic polymerization of anilinic and/or phenolic monomers is carried out in the presence of ionic templates to yield high-molecular-weight and water-soluble complexes of the polymer and the template used.

This approach is particularly attractive because it is completely benign and simple (one step) and uses very mild aqueous conditions. In addition, the process is general, as numerous ionic templates and derivatized monomers may be interchanged to build in desired functionalization. This process has the potential to revolutionize the use of electronic and photonic polymers because toxic catalysts or solvents are no longer required for the synthesis or processing of these polymers into useable forms. The technological applications for these enzymatically synthesized polymers are significant and diverse. Polyaniline is already well known as a promising material for electrochromic displays, electromagnetic interference (EMI) shielding, corrosion protection, electrostatic dissipation, and sensing. There is also great potential for these materials in photonic devices and batteries.

Polyphenols are currently being investigated in polymeric batteries that could be coupled to photovoltaic devices containing conducting polymers and light absorbing dyes to create environmentally friendly energy harvesting and storage devices. It was recently found that the mild and benign conditions of this biocatalytic approach even allow for the use of DNA as a template to form a conducting DNA/polyaniline complex. This material could have enormous opportunities in medical diagnostic devices, probes, and bioconductors. This technology offers both potential economic and environmental benefits to industry and society due to the commercial potential of the products made and the environmentally benign methods used to produce them.

Electrorefining of Spent Nuclear Fuel: Electricity generation using fossil fuels releases enormous amounts of airborne pollutants that can be avoided through substitution of nuclear power. There is, however, a minimal but non-negligible environmental impact from uranium mining and milling operations. Also, only a limited amount of electric energy can be derived from known uranium resources by using the present nuclear fuel cycle. Electrorefining of spent nuclear fuel addresses these drawbacks, making it an enabling technology for clean electric power generation. A fast reactor fuel cycle incorporating electrorefining would increase the efficiency of uranium usage a hundredfold and would permit reuse of depleted uranium now in waste storage, both of which could defer mining and milling of uranium for more than a millennium.

The electrorefining process recovers uranium and other actinides from spent fuel by electrotransport through a molten salt, which minimizes waste generation by avoiding the use of solvents and reagents. Recovered actinides are returned to the reactor, and fission products are placed directly into two durable waste forms that are suitable for long-term geologic disposal.

Electrorefining of metallic nuclear fuel has been demonstrated at the pilot plant scale and is currently being used to treat DOE&#;s inventory of sodium-bonded spent fuel.

Eliminating Air Pollution (VOC and HAP) at the Source through the Use of Ultraviolet and Electron Beam Polymerization: Paints, coatings, inks and adhesives have historically been based on the dispersion of polymers in solvents. These were then applied to substrates in thin layers. Commercial products, thus treated, were then subjected to heat to evaporate the solvents and convert the polymers to solids. These solvents, volatile organic compounds (VOC), thus became air pollutants and/or hazardous air pollutants (HAP). As such they reacted with Ox to generate ground level ozone, a major air pollutant. Minor changes to the polymers used have allowed some VOC reduction, which has been overcome by rising production levels. The emission levels of volatile solvents remain very high. The candidate technology described herein abolishes solvents completely.

Instead, it provides for oligomers that are dissolved in monomers of similar reactivity. This permits the formulation and application of the above listed products, which are then cured by the application of ultraviolet (UV) or electron beam (EB) energy that causes 100% copolymerization of the oligomers with the monomers forming high performance coatings, inks and adhesives. Since no solvents are used, the emissions are nearly zero. Converters to this technology are therefore free of VOC and HAP regulations even if their production increases substantially. Environmental and health benefits are great. This technology is currently in use in a wide variety of industries and is growing at a 10-12% annual rate.

Eliminating Solvents from Silicon Wafer Manufacturing: The process of plasma dry etching through silicon oxide layers to create sub-micron sized vias for inter-level metal contacts on silicon wafers patterned with photoresist leaves the wafer surface contaminated with polymer residues which must be removed. These residues are called "veils" because of their appearance in the SEM. Conventionally this has been done using special solvents and acids, materials that are very costly, hazardous, and environmentally a burden to discard. Ulvac technologies has developed dry plasma chemical ENVIRO(TM) processes for treating the polymeric residues which renders them 100% soluble in DI water, along with associated processing equipment for using this capability in manufacturing.

Together Motorola Corporation and Ulvac Technologies Inc. have performed a comprehensive program evaluating the equipment and processes in the manufacturing environment, and developed appropriate methods for employing the technology in the production environment to render it useful and available to the entire worldwide industry.

Process repeatability and reliability, integrity of devices manufactured in terms of electrical performance, yields, and operating lifetimes have been demonstrated to meet or exceed the levels of the conventional acid-solvent technology.

Adoption of this technology by the semiconductor industry is anticipated to have significant impact on reducing the environmental burden associated with this industry as well as offering major manufacturing cost savings.

Elimination of Hexavalent Chromium from Hydraulic and Pneumatic Tubing and Bar: Chrome-plated rods and tubes are the backbones of the hydraulic and pneumatic cylinders used in the fluid power market. These cylinders are used in applications from oil and gas production to food processing. Chrome plating is used widely because it has an excellent wear surface, great lubricity, and good corrosion resistance; it is also economical, time-tested, and readily available. The plating process is problematic, however, because plating produces a mist containing hexavalent chromium ions (i.e., Cr(VI), Cr6+) that are carcinogenic. Most large chrome-plating facilities currently meet or exceed EPA, OSHA, and other government standards for air quality, disposal, and containment of waste. There is a trend toward tighter regulatory controls, however, and more stringent regulations will increase the cost of chrome plating.

Commercial Fluid Power is taking steps to reduce the use of industrial hard chrome or engineered chrome in the fluid power market. The company is developing and marketing Nitro-tuff tubes as safe, environmentally friendly replacements for chrome-plated tubes. Nitro-tuff tubes are ferritic nitro-carburized steel. During their manufacture, the surface of the steel is converted to a nonmetallic epsilon iron nitride (e-Fe3N) in an atmosphere of ammonia and carrier gas. Following nitriding, an oxidizing atmosphere is introduced to produce a thin, corrosion-resistant, black surface film of Fe3NO3-4. The iron nitride layer is the basis for the steel&#;s extraordinary wear and corrosion resistance.

Advances in mechanical properties, size, and finish control now allow Nitro-tuff tubes to substitute for chrome-plated tubes without losing quality or strength. These efforts are reducing the use of hexavalent chromium. Recent research, development, and testing have overcome earlier challenges and opened new markets for Nitro-tuff tubes and bars. In conjunction with NitroSteel and Nitrex, Commercial Fluid Power continues to strive to bring an eco-friendly, cost-effective solution to the fluid power market.

Elimination of Ozone-Depleting Chemicals in the Printed Wire Board and Electronic Assembly and Test Processes: IBM-Austin is a manufacturing and development facility. Operations include the manufacture of printed wire board (PWB) in the Panel Plant facility and electronic circuit cards in the Electronic Card Assembly and Test (ECAT) facility. In , IBM-Austin completely eliminated the use of CFCs and other ozone depleting substances from its PWB and ECAT processes. This elimination program resulted in 100 percent reduction of CFC-113 ( peak usage of approximately 432,000 pounds) and 100 percent reduction of methyl chloroform ( peak usage of approximately 308,000 pounds) from IBMAustin&#;s PWB and ECAT processes.

These accomplishments were achieved by converting to an aqueous-based photolithographic process in the PWB facility in , an interim aqueous cleaning process in the ECAT facility in and , and a final No-Clean process (eliminating the aqueous cleaning process) in the ECAT facility. Changing from a solvent-based photolithographic process to an aqueous-based process eliminated methyl chloroform (MCF) from PWB panel manufacturing ( usage of 181,000 pounds). The interim process changes to aqueous cleaning eliminated MCF from manufacturing processes in ECAT ( peak usage of 196,000 pounds) and were largely responsible for eliminating CFC-113 from all manufacturing processes at the IBM site. Although CFC-113 was eliminated from the site in and MCF was eliminated in , ECAT&#;s ultimate goal was to convert all ECAT processes to No-Clean manufacturing processes.

Elimination of Ozone-Depleting Chemicals Through the Use of a Water Soluble Adhesive "Green Wax": MEMC Electronic Materials, Inc., a silicon wafer manufacturer, undertook to eliminate all Class I Ozone Depleting Chemicals (ODCs) from manufacturing operations in . Over 80 percent of the target ODCs used by MEMC were in direct silicon processing steps like slice mounting, polishing, slice demounting, and slice dewaxing. The mounting of silicon slices prior to polishing was performed with a material known as "wax" which was capable of controlled viscosity and thickness application.

The old wax formulation contained trichloroethylene (TCE), while the old block cleaning method utilized 1,1,1-trichloroethane (TCA), and the old slice dewaxing process utilized Freon 113. The wax formulation was changed to a water soluble one ("green wax"), that utilized a commercially available water soluble resin (a modified maleic resin in solution with ammonium hydroxide and water). Slice mounting (block cleaning) and dewaxing were modified to use a dilute basic solution (such as ammonium hydroxide) instead of TCA and Freon 113. The flatness, particle count, and metal concentration of slices produced with green wax are equal to or better than the old wax. It is estimated that, since , MEMC has avoided the production of almost 5 million pounds of ODC emissions worldwide through the use of green wax.

Elimination of Perfluorinated Alkyl Surfactants from Fire-Fighting Foams: Traditional fire-fighting foams for use on Class B (i.e., flammable liquid) fires, known as Aqueous Film-Forming Foams (AFFFs), typically contain perfluorinated alkyl surfactants, which extinguish fires quickly and resist re-ignition. Foams are used extensively in a wide variety of fire-fighting applications, including fixed systems (fuel loading docks, aircraft hangers, fuel storage tanks, etc.) and hand-line applications (municipal fire fighting trucks, airport emergency response, etc.). In general, fire-fighting foams are applied to quickly extinguish an ongoing fuel fire and to suppress re-ignition. Water alone cannot accomplish this.

When possible, containment systems capture residual foam liquid to prevent its release. Often, however, foam is applied to an unignited fuel spill as a safety precaution to prevent a flash fire while rescue workers perform their duties in and near the flammable fuel. In many cases, it is not feasible to contain the foam once applied. It is well-known that perfluorinated alkyl chains used in AFFFs are persistent in nature. There is an ongoing debate as to the human health and environmental effects of such chemicals released into the environment during normal use.

Chemguard developed ECOGUARD and its principle surfactant component in response to market requests for an organofluorine-free, alternative AFFF. ECOGUARD uses a novel hydrocarbon polymer surfactant (Chemguard HS-100) to substitute for and eliminate perfluorinated alkyl surfactants. The convergent, three-step synthesis of HS-100 has no byproducts and produces only water from the condensation polymerization. Because the properties of HS-100 eliminate the need for polysaccharide thickeners, the ECOGUARD formulation does not require a biocide. ECOGUARD is readily biodegradable and has a "low concern" for toxicity. ECOGUARD is registered by Underwriters Laboratories (UL) for hand-line operations and for use in sprinkler systems. Among organofluorine-free foams, only ECOGUARD has passed the UL sprinkler test. Chemguard was recently awarded two patents related to its organofluorine-free fire-fighting foam formulations.

Elimination of PFOS and PFOA in IBM Semiconductor Manufacturing Processes and Development of Photoacid Generators Free of Perfluoroalkyl Sulfonates: In , EPA restricted new applications of perfluorooctane sulfonate (PFOS) compounds because scientific evidence showed that PFOS persists and bioaccumulates in the environment. Because semiconductor manufacturers demonstrated limited release and exposure for PFOS, however, EPA allowed PFOS compounds "as a component of a photoresist substance, including a photoacid generator or surfactant, or as a component of anti-reflective coating, used in a photolithography process to produce semiconductors or similar components of electronic or other miniaturized devices."

Voluntarily, IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA). In , IBM issued a Corporate Directive to eliminate PFOS and PFOA from all manufacturing processes by . IBM worked with chemical suppliers to identify and qualify a non-PFOS replacement for the PFOS surfactant in buffered oxide etch (BOE) chemicals. In , after a multiyear investigation and extensive qualifications, both IBM fabrication plants finished replacing the PFOS surfactant in all BOE chemicals with perfluorobutane sulfonate (PFBS), for which EPA has fewer environmental concerns. IBM also sought replacements for specific photoresists and antireflective coatings (ARCs) that contained PFOS or PFOA as a surfactant or photoacid generator (PAG).

In January , after significant investment and qualification of replacement chemistries across many wet etch and photolithography processes, IBM completed its conversion to non-PFOS, non-PFOA lithographic chemicals. This change eliminates approximately 140 kilograms of PFOS and PFOA annually. Total annual PFOS consumption by the semiconductor industry worldwide is estimated at 8,000 kilograms. IBM believes it is the only company in the world to eliminate PFOS and PFOA compounds completely from semiconductor manufacturing. IBM has also developed PAGs free of perfluoroalkyl sulfonates (PFAS) for both dry and immersion 193-nm semiconductor photolithography processes, with equivalent performance in 45-nm and 32-nm semiconductor technology. IBM is pursuing technology transfer opportunities to commercialize its PFAS-free PAGs for a wider range of applications.

Elimination of Trichloroethylene, a Hazardous Air Pollutant (HAP), From A Production Process: Uniseal Inc. reformulated the primer portion of the lamination process in their closed cell sponge rubber (Foam) division in an effort to reduce the use / release of hazardous air pollutants (HAPs). The primary goal was to eliminate Trichloroethylene from the process. The lamination process involves running closed cell sponge rubber through custom-designed lamination machines, which apply primer and pressure-sensitive adhesive to the foam. Uniseal began by trialing the replacement of Silaprene Adhesive with the 3M Primer already in use.

The Silaprene Adhesive was also a contributor to their HAP emissions, with a composition of 20% HAPs (Toluene, CAS# 108-88-3). The reason Uniseal began with the replacement / elimination of Silaprene Adhesive is because the Silaprene Adhesive is carried by trichloroethylene. A small-scale trial conducted by hand indicated that both types of foam can be laminated with the same primer. The primary ingredient in the 3M primer already in use is cyclohexane, and was already being used in this combination on one type of foam, so that became the replacement chemical. Efficiency and quality problems soon surfaced because the cyclohexane was not flashing off quickly enough. Next, the trial went to acetate, which also did not flash off quickly enough. Uniseal then decided to try using acetone, which is working rather well. The workability of the acetone is a benefit not only in that it is not a hazardous air pollutant, and not a regulated VOC, but it is also not an ozone precursor.

Enabling Technology for Methacrylic Acid Production using Isobutane as the Feedstock: Methacrylic acid (MAA) and its methyl ester, methyl methacrylate (MMA), are high-volume commodity chemicals that are building blocks for polymers used widely in the construction, automobile, appliance, and coating industries. Since the s, the production of MAA and MMA in the United States has used the conventional acetone&#;cyanohydrin (ACH) process, whose feedstocks are acetone and highly toxic hydrogen cyanide (HCN). The production of one ton of MAA requires at least 0.31 ton of HCN along with 1.6 tons of concentrated sulfuric acid as both solvent and catalyst. It also generates 1.2 tons of ammonium bisulfate requiring disposal. In alone, the U.S. production of 1.82 billion pounds of MAA and MMA consumed at least 558 million pounds of HCN, used and regenerated about 2.88 billion pounds of concentrated sulfuric acid, generated and disposed of 2.16 billion pounds of ammonium bisulfate, and generated tens to hundreds of billion pounds of aqueous waste discharges.

EverNu has developed a patent-pending technology that uses proprietary, stable, metal oxide catalysts to produce MAA from isobutane and air as the only feedstocks. This technology has a significant economic benefit because isobutane costs only a fraction of the cost of acetone and HCN. It also saves tens of trillion Btu of energy per year because the partial oxidation of isobutane to MAA is an isothermic reaction. The environmental benefits are enormous. They include (1) completely eliminating the use of large quantities of HCN and sulfuric acid; (2) avoiding the generation and disposal of toxic, corrosive wastes from HCN and sulfuric acid; and (3) substituting the nontoxic feedstock isobutane, which is inherently much safer than HCN and sulfuric acid with regard to worker exposure and accident potential. Recent research indicates that isobutane can be obtained from renewable sources in the future.

Energy Savings from a New Manufacturing Route for Vinyl Methyl Ether: Glutaraldehyde is a broad-spectrum antimicrobial agent. Glutaraldehyde formulations address the antimicrobial needs of a variety of applications including agriculture, metalworking fluids, heat-transfer systems, oil and gas operations, water treatment, paper manufacturing, and medical and dental facilities. A key raw material in the production of glutaraldehyde is vinyl methyl ether (VME). Historically, VME has been produced using a two-step chemical process. The energy associated with the steam needed for this process is approximately 15,000 Btu per pound of VME or approximately 300 billion Btu per year.

Seeking more sustainable process conditions, Dow Process Research and Development identified the synthesis of VME as a prime candidate for reactive distillation technology. Reactive distillation combines chemical reaction and distillation in a single step. This technology is part of the separations roadmap supporting Vision for the U.S. chemical industry because it can significantly reduce the energy consumption of separation processes.

Applying reactive distillation to the VME process meant replacing one reactor and four distillation columns with a single reactive distillation column. The new process requires less steam, leading to energy savings equivalent to 54,000,000 kWh each year. This is enough energy to provide electricity for approximately 4,800 homes per year based on average household consumption reported by the Department of Energy. The primary aqueous waste stream from the VME process using reactive distillation contains much less byproduct and is efficiently cleaned by a wastewater treatment plant, eliminating chemical pretreatment. In addition, careful selection of plant location reduced the transit distance between the VME plant and its sister derivatization plant from 1,200 to 500 miles, which lowered fuel use per transported railcar by 60 percent as an added benefit. A VME plant based on reactive distillation was built at a contract manufacturing facility in early ; the conventional VME plant closed later that year.

Engineered Baker"s Yeast as a Means to Incorporate Biocatalysis Early in Process Design: Application to the Asymmetric Baeyer-Villiger Oxidation: While enzymes provide many advantages over traditional chemical reagents, they are generally applied to processes only during scale-up stages. It would make better economic and environmental sense to include biocatalytic methods during the initial discovery phase; however, this would require making biocatalysis accessible to bench chemists who often have no background in biochemistry or microbiology. Dr. Jon D. Stewart at the University of Florida has developed designer yeast, ordinary baker&#;s yeast cells that have been engineered to express one or more foreign proteins. Whole cells of these engineered yeasts can be used directly as a biocatalyst for organic synthesis.

As proof of principle, Dr. Stewart&#;s group has created a yeast strain that catalyzes a broad array of enantioselective Baeyer-Villiger oxidations. While this reaction plays an important role in laboratory-scale syntheses, the severe environmental and safety problems associated with current reagents prohibit its large-scale use. Acinetobacter cyclohexanone monooxygenase was expressed in Saccharomyces cerevisiae and whole cells of the engineered yeast were used to oxidize several ketones in good yields and with high enantioselectivities. This process uses atmospheric O2 as the oxidant and produces water as the only byproduct. Cell biomass and spent culture medium can be discarded in sanitary sewers after heat inactivation.

Enhance O2 Soil Remover for Commercial Fryers: Current technologies for cleaning commercial deep-fat fryers use acid, bleach, and caustic chemicals to break down the adhesion of protein-based fryer soils chemically and lift the soils away from the fryer surface. These technologies may leave hazardous chemical residues behind. They also may not remove all the original soils, which can then support additional bacterial growth and produce off-tastes. Traditional cleaning methods may also lead to employee contact with harsh acids, bleaches, or bases and to disposal problems after the cleaning process.

Rochester Midland Corporation&#;s (RMC&#;s) Enhance O2 formulation represents a revolutionary advance in the removal of charred soils from the surface of steel commercial fryers. These soiled fryers typically harbor baked-on hydrocarbon, protein-based surface contamination that both presents a potential food source for bacteria and limits effective heat transfer.

Enhance O2 uses environmentally friendly, renewable hydrogen peroxide and selected trace surfactants to oxidize and break down these protein-based fryer soils. Enhance O2 is a natural, green product. Once hydrogen peroxide does its soil removal job, it decomposes to water and oxygen gas, eliminating disposal issues at the plant. In addition, hydrogen peroxide is a known, traditional disinfectant for skin cuts and sterilization processes.

In one case study, Enhance O2 reduced caustic use by one-half in five large cookers and one chiller making pasta at Windsor Foods. Enhance O2 also eliminated an acid wash. Overall process improvements, including Enhance O2, reduced chemical, labor, and water costs by $25,000 annually.

RMC received a U.S. patent for its technology in March (Patent No. 7,507,697).

Enhancing the Efficacy of Totally Organic Wood Preservatives with Low-Cost, Benign Additives: Biocide treatment prevents the biodegradation of wood in outdoor exposures. Treated wood is both economical and sustainable, unlike its main competitors: plastic "lumber", steel, and concrete. Copper-rich preservatives are the current biocides for residential lumber, but these preservatives have environmental concerns. A few U.S. localities have restricted copper-treated wood, and increasing limitations are expected. Future preservatives will likely be totally organic; three European countries already mandate them. Organic biocides have two major problems: they cost more than metallic biocides, and they will themselves biodegrade over time, losing their effectiveness.

Professors Schultz and Nicholas found that combining butylated hydroxytoluene (BHT) with numerous commercial organic biocides significantly enhanced the efficacy of the biocides against wood-destroying fungi. (BHT is a low-cost, benign antioxidant approved for various uses including as a food additive.) Further, the addition of BHT significantly reduced depletion of an organic biocide in long-term, outdoor testing. Low-cost, benign, metal-complexing compounds also enhanced the efficacy of organic biocides in wood decay tests; adding BHT provided even greater enhancement.

Wood is also a hydroscopic material. Used outdoors, particularly as decking, wood swells during rainstorms and shrinks as it dries, causing undesirable warping, splitting, and growth of surface mold. Premium wood decking is treated with a water repellent made from petroleum-derived wax to minimize these dimensional changes. Professors Schultz and Nicholas have recently identified an inexpensive, safe, renewable, metal-complexing compound (tall-oil rosin) and have used it in a waterborne formulation for treating wood. Tall-oil rosin is a byproduct of the chemical pulping of southern pine trees. Initial decay tests combining this compound with several organic biocides showed enhanced efficacy. This compound also increases water repellency of wood and, thus, could replace current petroleum-based water repellents. Mississippi State University has licensed this technology to two international companies. Additional discussions on licensing are ongoing.

EnvirezTM Technology: Incorporating Renewable and Recycled Feedstocks into Unsaturated Polyester Resins: Unsaturated polyester resins are key components of fiber-reinforced plastic thermoset composites. The annual production of these resins in North America is approximately 1 billion pounds. Historically, these resins have been made almost exclusively from virgin petrochemicals.

Expanding on the pioneering work of Professor Richard Wool at the University of Delaware, Ashland developed EnvirezTM resins, a novel, versatile family of unsaturated polyester resins made from either renewable or recycled raw materials or both. Ashland uses biobased building blocks including soybean oil, ethanol, 1,3-propanediol, and other proprietary monomers from soybeans, corn, and other renewable raw materials. Additional building blocks for EnvirezTM resins are recycled monomers and polymers including postconsumer poly(ethylene terephthalate) (PET). Ashland recently developed the first EnvirezTM resins that employ recycled raw materials and use combinations of both recycled and renewable raw materials.

EnvirezTM resins now contain more types and higher percentages (up to 40 percent) of renewable raw materials. Ashland has developed formulations for a wide variety of composite fabrication methods including infusion, pultrusion, casting, and gelcoats. These formulations expand the reach of EnvirezTM into an assortment of products and markets including green buildings and wind energy devices. They enable composite fabricators to use sustainable components. EnvirezTM technology leads to reduced dependence on petroleum, lower emissions, energy savings, and a smaller carbon footprint. In the last three years, EnvirezTM resins have incorporated over 12 million pounds of recycled PET.

Using a novel, biobased reactive intermediate, Ashland has developed EnvirezTM low styrene resins that lower the traditional styrene content by one-third and reduce both hazardous air pollutants (HAPs) and volatile organic compounds (VOCs). The EnvirezTM product line has experienced double-digit growth in the past several years. EnvirezTM low styrene resins have completed review under the Toxic Substances Control Act (TSCA) and are undergoing field trials at numerous composite fabricators.

Enviromask - A Zero VOC Method to Aircraft Metal Forming: Chemical milling is a process of forming metal. The primary metal used is aluminum. Milling is a fundamental step in the production of airplanes and other items that are composed of metal parts with precise specifications of weight and dimension. The most important material in the process is called maskant. Maskant is the coating applied to the metal part. It stops hot caustic or acid from contacting and dissolving the metal. After the milling process, it is hand-peeled to make a finished part.

Today&#;s available maskants are chiefly rubber type polymers dispersed in solvents such as xylene, toluene, and perchloroethylene. In order to be a viable product for milling, a maskant must completely stop all acid or caustic from passing through it, and be able to be peeled easily after the process is complete.

Our project entry, Enviromask, consists of 100% solids, solvent-free-polyurea technology. Similar technology exists today and is used in different industries, but we are not aware of any application where the thickness of film and consistency of performance properties such as peel strength and instant chemical resistance are so critical. Controlling such properties of a polyurea material makes our project a true chemical and mechanical breakthrough.

Environmental Advantages Offered by Boric Acid Mediated Amidation Between a Carboxylic Acid and an Amine to Form a Carboxamide, a Basic Unit of Peptides and Proteins: A practical and environmentally friendly alternative synthetic pathway has been developed to accomplish the direct amidation between a carboxylic acid and an amine to form a carboxamide using a catalytic amount of boric acid as the mediator. Boric acid is a "green" catalyst. It is nontoxic, environmentally safe, renewable and inexpensive. Carboxamides generate great interest within the synthetic organic chemistry community, and the research directed to their formation is actively pursued. The chemistry of amide bond formation is a vital chemical transformation in organic chemistry. Amide bonds are responsible for linking amino acids to form proteins.

Currently, the uses of carboxamides as delivery agents for the delivery of protein and macromolecular drugs in a wide range of settings are being sought and discovered. The amidation mediator, boric acid, has many promising and beneficial properties. The conventional methods reported in the literature for making carboxamides require the use of environmentally harmful reagents and generate hazardous wastes. This boric acid-mediated amidation employs only environmentally benign reagents and generates no by-products. This new alternative green synthetic pathway, using only a catalytic amount of boric acid, guarantees uncontaminated waste flow, thus assuring significantly reduced impacts on human health and the environment relative to the current state of art.

Environmental Advantages Offered by Indium-Promoted Carbon-Carbon Bond-Forming Reactions in Water: In view of increasing demands to reduce emissions during the production of chemical and pharmaceutical end products, it is imperative to consider the development of effective carbon carbon bond forming reactions in aqueous media. The work of Dr. Leo A. Paquette at The Ohio State University demonstrates not only that the counter intuitive notion of organometallic carbon carbon bond forming reactions performed in water is indeed workable, but also that high levels of stereocontrol are attainable. The key to this safe, environmentally friendly technology is the utilization of metallic indium as the promoter.

The metal indium, a relatively unexplored element, has recently been shown to offer intriguing advantages for promoting organic transformations in aqueous solution. The feasibility of performing organometallic/carbonyl condensations in water, for example, has been amply demonstrated for the metal indium. Indium is nontoxic, very resistant to air oxidation, and easily recovered by simple electrochemical means, thus permitting its reuse and guaranteeing uncontaminated waste flow. The power of the synthetic method, which often can exceed performance levels observed in purely organic solvents, includes no need for protecting groups, greatly enhanced ease of operation, and greatly reduced pollution risks.

Environmental Improvements from Redesigning the Commercial Manufacture of Progesterone: For more than 40 years, the steroid bisnoraldehyde (BNA) has been produced at Pharmacia & Upjohn because it is a key intermediate for the commercial synthesis of progesterone and corticosteroid classes of pharmaceuticals. Recently, a redesigned route to BNA was implemented. This new synthetic route to progesterone is founded on both the development of a new fermentation process which improves the utilization of a renewable, naturally-derived feedstock from 15 to 100 percent, and the development of a chemical oxidation process that offers high selectivity and reduced waste streams. The fermentation employs a genetically modified bacterium to convert soya sterols directly to a new synthetic intermediate, bisnoralcohol. The new chemical process oxidizes bisnoralcohol (BA) to bisnoraldehyde, a key intermediate for the registered, commercial manufacture of progesterone.

Contrary to standard chemical methods for oxidizing alcohols to aldehydes, the new oxidation process does not use hazardous or noxious materials and does not generate toxic waste streams. The reaction conditions developed to oxidize BA to BNA are environmentally superior to the standard methods used to convert primary alcohols to aldehydes. During the development of the process, considerable focus was placed on waste minimization, not just for that step but also for the production of the substrate and the catalyst. The process minimizes solvent use and maximizes solvent recovery as well. The new bisnoralcohol route eliminated a process with a running, recycled inventory of 60,000 gallons of ethylene dichloride (EDC), a known carcinogen, which needed up to 5,000 gallons of EDC input annually. The new route produces the same amount of product as the previous route with 89 percent less nonrecoverable organic solvent waste and 79 percent less aqueous waste. The new route also has the chemical selectivity required for high quality bulk pharmaceutical manufacture and can be applied to the oxidation of other primary alcohols.

The development and implementation of the new chemical oxidation process allowed for the utilization of the new bioconversion, thereby creating a new synthetic route from soya sterols to therapeutic steroids. The new bisnoralcohol route exemplifies the synergism possible between biochemical and chemical process development. By implementing this redesigned, commercial synthesis of BNA, Pharmacia & Upjohn has substantially reduced the chemical waste associated with manufacturing progesterone, while simultaneously improving process economics through a dramatic increase in feedstock utilization.

Environmentally Advantaged Formulations for Aircraft Ice Control: During the &#; deicing season, the 20 largest airports in the United States used over 11 million gallons of aircraft deicing fluids (ADFs). The large quantities of effluents that are released into the environment during aircraft deicing operations have resulted in several reportable incidents of environmental damage in the vicinity of airports throughout the world. This damage is caused by the high biological oxygen demand (BOD) of current ADFs that deplete oxygen levels in receiving waters sufficiently to distress and kill aquatic life. Airports are now required to obtain National Pollutant Discharge Elimination System (NPDES) permits to discharge ADFs into storm water sewers. Regulations under development by the U.S. EPA are expected to be much more restrictive. In addition, treatment costs of current ADFs are between $12 and $20 per gallon of deicing fluid, several times the purchase price of approximately $5 per gallon.

LBOD, Foster-Miller&#;s new ADF formulation, consists of a mixture of triethylene glycol and glycerol. Foster-Miller designed it to have unique BOD characteristics that do not impose an environmental threat: its 5-day BOD is as much as 85 percent lower than that of current ADFs based on propylene glycol.

The new formulation can also be modified to have a high degradation rate with a reduced BOD, making it advantageous for high-volume users with onsite treatment facilities. The flexibility of the new ADF technology provides airport authorities with the option of either treating their waste or discharging it without treatment, depending on their size and situation. In either case, the new technology will substantially reduce life-cycle costs for deicing fluids. The new technology is also expected to expedite the associated environmental permitting process. Foster-Miller&#;s technology is currently being demonstrated at the Niagara Falls Air Reserve Station in Niagara Falls, NY.

Environmentally and Toxicologically Safe Firefighting Gel: Liquid firefighting gel had its genesis in the s, when John Bartlett, President of Barricade International, Inc., observed that used, disposable baby diapers survived a house fire in which even the appliances melted. The superabsorbent polymer and water content of the diapers prevented their combustion. Mr. Bartlett, a professional firefighter, realized that a superabsorbent polymer might change the way fires are fought. He then looked for liquid forms of the superabsorbent polymer that might be easily introduced into firefighting water to produce a fire retardant and suppressant gel. In the late s, Mr. Bartlett identified a printing paste thickener used in the textile industry that produced a thickened water gel that significantly improved fire extinguishing and prevention. Barricade&#;s competitors now use that product, but it contains two components, petroleum distillate and nonylphenol ethoxylate (NPE), that have environmental and health concerns.

Data have linked NPEs to endocrine disruption and mammalian reproductive concerns. Barricade International, with E.T. Sortwell conducting R&D, has developed a product to match the firefighting properties of the existing gel without its environmental and health concerns. The product is Barricade II, a dispersion of superabsorbent polymer in foodgrade vegetable oil (i.e., canola), sorbitan monooleate, and fumed silica. The superabsorbent polymer is typically a copolymer of acrylamide and acrylic acid derivatives such as salts.

Barricade II is more effective at fire prevention than its NPE&#;petroleum distillate competitor. In aerial applications, Barricade costs only about half as much as traditional retardants and is effective at about 1/18 the application rates. The U.S. Forest Service has placed Barricade II on its Qualified Products List. A U.S. patent has been allowed, and Barricade International has begun full-scale commercial production of this product. California&#;s Department of Forestry used Barricade II in aerial applications during the fire season with spectacular results.

Environmentally Benign Antibacterial Agents: Water-dispersable products were prepared by reaction of readily available, water-soluble reactants (magnesium acetate tetrahydrate and hydrogen peroxide; mole ratios 1:2 to 1:40). These new compositions (magnesium hydroperoxyacetate&#;HOO-Mg-OAc and magnesium dihydroperoxide&#;HOO-Mg-OOH) have peroxide contents of 1-35%. Molar amounts of hydrogen peroxide used (70% less) and reaction time (reduced from 90 to 10 minutes) were dramatically reduced by microwave synthesis compared to conventional heating. These new compounds exhibit antibacterial activity against representative gram-positive (Staphylococcus aureus) and gram-negative bacterium (Klebsiella pneumoniae), are hydrolytically stable at ambient temperatures for at least 60 days and thermally stable below 350?C.

These environmentally benign antibacterial agents (containing only magnesium and peroxide) are affixed as aqueous dispersions to textiles to impart antibacterial activity to natural, synthetic fibers and blends by pad-cure processes (10-17% active ingredients cured at 2-4 min. at 120-150?C). Modified textiles containing bound peroxide (0.1-1.7% by weight) are active against bacteria as low as 0.10% peroxide. Renewable fibers (cotton, others cellulosics) have the best affinity for the agents with cotton fabrics retaining their antibacterial activity up to 50 launderings. Marked improvements in fixation and durability of these agents to synthetic fibers have also been recently made by incorporating selected softeners in treating formulations.

Environmentally Benign Deicing/Anti-Icing Agents: Each year, the U.S. market for deicing/anti-icing (D/A) products consumes over 100 million gallons of liquids and 20 to 25 million tons of salt. Historically, rock salt and glycol solutions have represented the bulk of D/A chemicals. Over time, however, it has become apparent that these effective, low-cost, but corrosive chemicals carry a severe cost in damage to infrastructures, vehicles, and the environment. For example, highway salt has found its way into both surface water and underground aquifers, whereas the high biological oxygen demand (BOD) of glycols has had negative effects on marine organisms. MLI D/A technologies are based on an innovative chemical method that prevents pollution through source reduction. This method uses abundant natural resources, agrochemical waste streams, and low-value streams such as carbohydrates derived from corn, glycerin-containing byproducts of biodiesel manufacture, and biopolymer wastes. Some of these D/A agents represent a new class of materials designed as alternatives to traditional salt and glycol-based fluids.

The MLI chemistry has led to development of a wide array of products, many of which are now in or near commercial use. These products reduce the nation&#;s reliance on petroleum, assist the commercialization of biofuels, and reduce impacts on health and the environment relative to traditional glycol-based fluids. The MLI biomass-based fluids are infinitely soluble in water, are nontoxic, and act as corrosion inhibitors for ferrous metals. During , MLI received a patent for D/A agents made from byproducts of biodiesel manufacture. Also in , MLI released Caliber® FC-B antifreeze and Caliber® SBA-2 additive for chloride D/A products in collaboration with Archer Daniels Midland. Current sales of MLI D/A agents are 15 million gallons per year. Applications for these products include aircraft-related uses, airport runways, roadways, bridges, facilities, landscape, and consumer markets.

Environmentally Benign Enzyme Reactor for Polymer Synthesis: Most common methods for commercial polymer synthesis are using chemicals to oxidize monomer. During this process, large amount of by-products and waste are generated with the polymer production. There has been great interest in development of alternative pathways to reduce or eliminate waste generation in polymer synthesis, such as using biological route for polyaniline synthesis, with only products of polyaniline and water. However, the current biological techniques using enzyme solution for polymer synthesis suffer from significant limitations. When enzyme is directly used in solution format in the reaction process, it is hard to recover the enzyme from the final products and almost impossible to reuse the expensive enzyme. In this work, we have developed a novel technology for polymer synthesis through biological route, with an example of polyaniline.

The technique takes full advantages of the solution enzymatic synthesis method but overcome its limitations by immobilizing the enzyme on a solid support as a catalyst. The stability of the enzyme is significantly increased through the immobilization process. Furthermore, the catalyst enzyme can be easily recovered and reused with the immobilizing technique. Since the solid support is used, it is ideal to fabricate an enzymatic reactor for polymer synthesis. Most importantly, the newly developed technology in this research makes the biological route for polymer synthesis become usable and practical in commercial production process. A patent application for this new technology was filed at USPTO in year .

Environmentally Benign Lithography for Semiconductor Manufacturing: Revolutionary processes for high-performance and environmentally benign patterning of semiconductors are the focus of a collaborative research effort. The technical motivation for this work is the integration of new processes and materials that eliminate environmentally undesirable wet processes used in today&#;s fabrication facilities. The primary goal is to replace conventional processes with superior, "dry" CVD methods and CO2-based processes. Secondary goals go beyond environmental advantages and address critical challenges facing the microelectronics industry:
· The high surface tensions and viscosities of organic solvents and water used for current deposition and removal processes damage next-generation < 100-nm-sized structures;
· The high viscosity of conventionally used solvents makes it challenging to spin uniform, thin films onto large, next-generation >500 mm wafers- the low viscosity of CO2 allows the deposition of thin films with fewer defects and greater uniformity;
· The polymers needed for state-of-the-art lithography (157 nm), antireflective coatings, and low-k dielectrics are insoluble in most traditional solvents-novel CVD based processes and liquid CO2 spin-coating and free-meniscus coating methods eliminate this problem;
· Solvents and water used today in manufacturing do not lend themselves to integrated "cluster tool" approaches, necessitating expensive clean room facilities- these integrated systems reduce the amount of clean room facilities needed.

Environmentally Benign Preparation and Polymerization of Phosphazene Polymers: Our newly developed, innovative, polymer synthetic method eliminates use of all halogenated hydrocarbon solvents in the synthesis of polyphosphazenes. This synthetic breakthrough offers significant environmental benefit in the preparation of these important inorganic polymers. Polyphosphazenes&#;one of the most versatile classes of inorganic polymers known&#;are unique in their broad spectrum of properties and related commercial applications. For example, they offer the chemist great flexibility in tuning the polymer physical properties. In addition, polyphosphazenes are well known for their stability when exposed to heat, radiation, and chemicals.

The synthesis of polyphosphazenes can occur by three routes: (1) traditional ring-opening synthesis; (2) living polymerization, which proceeds through formation of a silylphosphoranimine; and (3) the "DeJaeger" method. Each of these three types of synthesis has advantages and disadvantages. All of them, however, as now practiced by industry, require high-boiling halogenated solvents both for thermal control and dispersal. Our approach eliminates use of all halogenated hydrocarbon solvents and produces phosphoryl chloride, a byproduct chemical having commodity uses within the chemical industry.

Environmentally Benign Pressure Sensitive Adhesive Program: Every year the U.S. Postal Service (USPS) sells about 42 billion stamps. These sales bring in revenue of up to $7 billion. In all, the USPS spends about $200 million to produce about 50 billion stamps annually. Due to public demand, the USPS has issued different non-lick (self-adhesive) stamp products. The removal of pressure sensitive adhesives (PSAs) from recovered paper is a major problem facing the paper recycling industry. Because the USPS currently purchases about 12 to 15% of domestic PSA production and produces a high percentage of self-adhesive stamps (82%), and due to the public demand for convenience as well as hygienic considerations, environmental issues have to be addressed. With the development of these new stamp products, concern has been raised by a certain segment of the industry and by the general public about the environmental impact of PSA stamp products. Neither the adhesive nor the release liner backing are repulpable or recyclable.

The Environmentally Benign PSA Program was initiated by the USPS as part of its commitment to develop stamps and postal products that do not adversely affect the environment. The purpose of this program is to develop a PSA that is benign to the environment and is able to meet the USPS requirements. This means that each component of the pressure sensitive construction (i.e., the face stock, the adhesive layer, and the release liner backing) will not only be able to perform to the USPS requirements for postage stamps, but will also possess those properties that are capable of being defined as environmentally benign. Once the adhesive is developed, demonstrated, and implemented, the USPS intends to expand the use of its application to other postal products.

The USPS takes a leadership role in addressing this complex problem because of popularity and high visibility of PSA postage stamps. USPS is also one of the largest single PSA materials purchasers. Identification and development of improved PSA materials to meet stringent postage stamp performance requirements allows USPS to mandate use of these materials for all postal products in future purchases and helps resolve contaminant issues in recycling postal/consumer waste paper.

Environmentally Benign Supramolecular Assemblies of Hydroquinones in Polaroid Instant Photography: The work of Professor John C. Warner at the University of Massachusetts, Boston represents the first example of supramolecular synthesis in a manufacturing system for pollution prevention. Using the concepts of molecular recognition and self-assembly, a new technique has been developed for the control of molecules within films and coatings. This process has a number of environmental benefits including reduced synthetic steps, reduced waste generation, reduced solvent usage, and the introduction of solventless or aqueous processing.

Instead of performing several time consuming, solvent-based, chemical reactions in order to synthesize a series of candidate compounds for structure activity studies, this technique allows for the addition of simple, inexpensive, readily available 'complexing reagents.&#; For this to be successful as pollution prevention, these assemblies must significantly reduce the number of synthetic reactions carried out. Often the formation of these assemblies involve no organic solvents. The supramolecular structures can be constructed via solid state grinding or aqueous dispersing techniques.

Environmentally Benign Synthesis of Monoglyceride Mixtures Coupled With Enrichment by Supercritical Fluid Fractionation: This nominated process differs from more conventional synthesis methods or processes utilizing supercritical fluids in that it embodies carbon dioxide as a catalyst or as a transport medium, coupled in one case with a lipase biocatalyst, to produce mixtures of varying monoglyceride content. Further, the same carbon dioxide medium can then be used tin a sequential fashion, to affect an enrichment of the synthesized glyceride mixtures, to yield products having a monoglyceride content in excess of 90 weight percent that have high value as emulsifiers, lubrication aids and as food additives. Using carbon dioxide under pressure, we have shown that metal-based catalysts can be eliminated from the traditional batch, stirred reactor glycerolysis to yield a product that is lighter in color, less odoriferous and having a monoglyceride content between 35-45 wt.%. Alternatively, we have demonstrated and patented a synthesis which uses CO2 in the supercritical state to dissolve vegetable-based oils prior to transport over a supported enzyme catalyst to produce mixtures having a 90% monoglyceride content.

Environmentally Benign Two-Step Synthesis of Fatty Alcohol Mixtures Using Supercritical Carbon Dioxide (SC-CO2) and SC-CO2/Hydrogen Mixtures: The nominated process differs from reported synthetic methods using utilizing supercritical fluids in that it embodies two distinct sequential reactions to esterify vegetable oils followed by high temperature/pressure hydrogenation using a chromium-free catalyst. Transesterification is also accomplished with a "green catalyst," a commercially-available lipase. The hydrogenation of the methylated oil is much more rapid in the supercritical fluid media compared to traditional technology and produces methanol as a product which can be reused as a starting reactant in the initial transesterification step. Fatty alcohols can be produced in over 98% yield with minimal by-products (n-alkanes) via this process. The described synthesis can be accomplished using only two sequential flow reactors to convert a renewable resource, soybean oil, to a mixture enriched to over 90% in steryl alcohol.

Environmentally Friendly Aircraft Deicing Fluid: METSS Aircraft Deicing Fluid-2 (ADF-2) represents a new class of aircraft deicing fluid designed as an environmentally friendly alternative to traditional ethylene and propylene glycol-based fluids. METSS ADF-2 is composed primarily of food-grade materials derived from abundant and renewable agricultural feedstocks that are both economical and readily available. Unlike ethylene glycol-based fluids, METSS ADF-2 is nontoxic and nonhazardous to plant and animal life. It contains neither phosphates nor urea, which tend to promote eutrophication of natural waterways and may lead to fish kills. METSS ADF-2 biodegrades readily and completely to carbon dioxide and water. METSS ADF-2 has a lower Biological Oxygen Demand (BOD) and biodegrades at a slower rate than propylene glycol.

Commercial airports and military bases are increasingly concerned about the quality of storm water runoff and the effect of deicing chemicals on receiving waters. If storm water drains directly from runways and taxiways into a body of water, discharge permits require regular monitoring to determine BOD, contaminants, and other properties. Due to its low BOD, METSS ADF-2 can help airport managers achieve environmental compliance. METSS ADF-2 meets all requirements of the SAE AMS D for aircraft deicing fluids. The U.S. Air Force, the Federal Aviation Administration, and Transport Canada have all approved METSS ADF-2; this product has been in commercial use since October .

Environmentally Friendly Antacid Formulations for Wastewater Treatment: For centuries, humans have used limestone and milk of magnesia (magnesium hydroxide) for medicinal antacid relief in their digestive systems. More recently, people have been using commercially formulated antacids that contain blends of metal hydroxides and metal carbonates. Despite these well-known medicinal benefits, no one thought until recently of using formulated antacid products for large-scale municipal and industrial wastewater treatment processes, which typically use hazardous alkaline chemicals such as caustic soda, lime, or soda ash.

Inland Environmental Resources, Inc. (IER) has invented antacid slurry formulations to treat wastewater on an industrial scale. These formulations use chemicals that are non-hazardous, environmentally friendly, and safe to handle. Each of IER"s formulations (called Amalgam® products) contains a blend of hydroxides or carbonates of magnesium, aluminum, calcium, or potassium. Amalgam® products reduce phophorus, total suspended solids (TSS), and biological oxygen demand (BOD) in wastewater, simultaneously boosting the pH of acidic wastewater streams. The reuse of Amalgam®-treated wastewater for land irrigation provides mineral nutrients to the soil, as opposed to the negative environmental impacts of irrigating crops with reclaimed water containing caustic or soda ash. Finally, Amalgam® formulations are less expensive to use than caustic soda, the industry standard.

With products that are much safer to handle, environmentally beneficial, better performing, and less expensive, IER has been growing very rapidly into the wastewater treatment market. Currently, IER is exploring other processes that require pH buffering as markets for its green chemical antacid formulations. It is developing new Amalgam® formulations to replace caustic soda in the recovery of chromium in the tanning process and to increase the yield of ethanol in the fuel ethanol industry. Since , IER has constructed two manufacturing plants and a pilot plant. It has also filed a patent for its technology.

Environmentally Friendly Antimicrobial Surface Treatment: DuraBan International has improved upon 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride (Si-QAC), an amino-functional silane developed originally by the Dow Chemical Company. Dow&#;s product had antimicrobial activity, but was unstable and polymerized in water; it required methanol for stability as well as certified applicators.

DuraBan International developed the first water-stabilized Si-QAC that does not incorporate any chemical stabilizer and, thus, does not leach off treated surfaces. Unlike other antimicrobials that can leach toxic chemicals into the environment, DuraBan is virtually nontoxic. DuraBan does not release any toxic gases, volatile organic chemicals (VOCs), heavy metals, formaldehyde, or phenol. Either standing alone or built into products during manufacture, DuraBan&#;s Si-QAC inhibits the growth of microbes (e.g., bacteria, mold, and mildew) that can cause stains, odors, and product deterioration.

Once applied, DuraBan bonds chemically to the product surface, creating a permanent antimicrobial barrier that destroys microorganisms upon contact by rupturing their cell membranes. DuraBan&#;s proprietary, patented antimicrobial technologies deliver unmatched performance, durability, and efficacy through a unique formulation based on surface-modifying nanotechnology.

DuraBan products serve as powerful antimicrobial barriers for consumer, industrial, and medical products. This technology can be engineered into many surfaces and materials including coatings, polymers, textiles, lumber, plastic, and adhesives. DuraBan antimicrobials have never been shown to allow or cause microbial adaptation, resistance, mutation, diffusion, or migration. When incorporated into everyday products that often encounter bacteria, DuraBan can positively benefit the environment and prevent the spread of superbugs, including MRSA (methicillin-resistant Staphylococcus aureus) and VRE (vancomycin-resistant enterococcus). Henry Ford Hospital recently completed an extensive study in which DuraBan reduced MRSA and VRE contamination by over 85 percent compared to untreated surfaces. The hospital also found that clothing treated with DuraBan remained 94 percent effective after 50 washes.

Four of DuraBan&#;s products are registered as pesticides by the EPA: MicrobeGuard, DuraBan I, DuraBan, and Mold Shield.

Environmentally Friendly Isonitrile-Based Syntheses: Professor Pirrung&#;s technology has two main components. The first is the significant acceleration of isonitrile-based multicomponent reactions in water. The technology not only replaces organic solvents with water, but in some cases also promotes reactions that do not occur in organic solvents. This technology shows that water is superior to organic solvents for certain chemical processes. The simultaneous chemical processes that occur in multicomponent reactions also reduce the number of steps required to prepare useful products, decrease their production costs, and increase efficiency in both unit time productivity and absolute chemical yield.

Professor Pirrung&#;s multicomponent reactions are 100 percent atom economical: they do not generate any byproducts. Because the reaction products are frequently insoluble in water, this technology also significantly facilitates product isolation and eliminates traditional energy- or material-intensive purification procedures such as chromatography or distillation. The only initial drawbacks of the technology were (1) the highly offensive odors of the isonitriles that are essential to the most powerful and commonly used multicomponent reactions and (2) their problematic preparation.

The second component is Professor Pirrung&#;s development of a much more environmentally friendly route to prepare isonitriles that also eliminates their stench. Traditional routes to isonitriles involve dehydration of formamides with phosgene. Phosgene is a highly toxic gas that was used as a chemical warfare agent; thus, there is strong resistance to using it in any chemical process. Other dehydrating agents used in its place are not as efficient. Professor Pirrung&#;s alternate route treats readily available oxazoles with a strong base to form isonitriles, eliminating formamide dehydration. The resulting isonitrile esters exhibit uncompromised chemical reactivity and do not have offensive odors. This safer route to isonitriles allows them to replace carbon monoxide in some reactions. Professor Pirrung&#;s technology should increase economy in the production of drug candidates, combinatorial libraries, and active pharmaceutical ingredients.

Environmentally Friendly Organic Synthesis Using Bismuth Compounds: Synthetic organic chemistry provides access to literally thousands of useful molecules including life saving drugs differing widely in their structural complexity. Work continues to be done to develop new reagents, catalysts and reactions, which are then used in the assembly of complex target molecules. However, most of these efforts have focused on achieving the synthetic processes in an efficient manner and not enough consideration has been given to the effects that the reagents used in chemical syntheses have on human health and the environment.

In , Congress passed the Pollution Prevention Act, which introduced the concept of pollution prevention through proper waste disposal, waste treatment, source reduction and source prevention. In this regard, bismuth compounds are particularly attractive candidates for use as reagents in synthetic organic chemistry for several reasons: Bismuth is the least toxic of the heavy metals. The biochemistry, toxicology and environmental effects of bismuth compounds have been well documented. The majority of bismuth compounds are relatively non-toxic (e.g., the LD50 (g/kg) of BiOCl is 22 and that of Bi2O3 is 5 (compared with a LD50 of 3.75 for NaCl). Bismuth and several of its compounds are commercially available and are relatively inexpensive. This project is aimed at developing new applications of bismuth compounds in organic synthesis.

Environmentally Friendly Water Treatments for Control of Corrosion, Scale, and Bioactivity in Heating and Cooling Systems: Presently, heating and cooling water treatment requires manual handling of toxic and corrosive chemicals, some of which (hydrofluoric acid, for example) are extremely hazardous. The U.S. Army Corps of Engineers Engineer Research and Development Center (U.S. Army ERDC) led a team of researchers to develop green water treatments to control corrosion, scale deposit, and microbiological growth in heating systems (boilers and condensate lines) and cooling systems (cooling towers). The goal was to provide a safer and more environmentally friendly water treatment program that exceeded industry standard performance criteria and at a cost equal to or less than conventional water treatments for heating and cooling systems. U.S. Army ERDC teamed with: the Garratt-Callahan Chemical Company; Trevino Mechanical, a small business mechanical sub-contactor; SurTech Corporation to perform the field demonstrations; and the Illinois State Water Survey for verification of field data.

The research team worked to develop, run field demonstrations on, and evaluate three formulations based on two chemicals previously recognized as Presidential Green Chemistry Challenge Winners: tetrakis hydroxymethyl phosphonium sulfate (THPS) for control of biological growth and polyaspartate for control of mineral scale. In addition, the formulations contained a filming soya amine to control corrosion in condensate pipelines. The team also used state-of-the-art automated equipment to minimize the hazards of chemical handling. The researchers applied the water treatment formulations and monitored their performance at three military installations for a period of two years. As a result, U.S. Army ERDC developed performance specifications for the use of green chemicals in water treatment for heating and cooling systems at public and private central energy plants.

Environmentally-Driven Preparation of Insensitive Energetic Materials: The Vicarious Nucleophilic Substitution (VNS) of hydrogen is a well-established procedure for the introduction of carbon nucleophiles onto electrophilic aromatic rings. An innovative approach was developed at Lawrence Livermore National Laboratory to synthesize 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and other insensitive energetic materials through the use of VNS. TATB is a reasonably powerful insensitive high explosive (IHE), whose thermal and shock stability is considerably greater than that of any other known material of comparable energy. The high cost of TATB ($100 per pound) has precluded its use for civilian applications such as deep-hole explorations. TATB is manufactured in the United States by nitration of the relatively expensive and domestically unavailable 1,3,5-trichlorobenzene (TCB) to give 2,4,6-trichloro-1,3,5-trinitrobenzene (TCTNB), which is then aminated to yield TATB.

The new VNS method developed at Lawrence Livermore National Laboratory for the synthesis of TATB has many 'environmentally friendly" advantages over the current method of synthesis of insensitive energetic materials. The new synthesis of TATB uses unsymmetrical dimethylhydrazine (UDMH), a surplus propellant from the former Soviet Union, and ammonium picrate (Explosive D) as starting materials in lieu of the chlorinated species, TCB. Several million pounds of Explosive D are targeted for disposal in the United States; 30,000 metric tons of UDMH also await disposal in a safe and environmentally responsible manner. The use of these surplus energetic materials as feedstocks in the new VNS method of synthesizing TATB allows an improved method of demilitarization of conventional munitions that also should offer significant savings in production, thereby making this IHE more accessible for civilian applications.

Enzymatic Catalysis for Biodiesel Production: Biodiesel is comprised of monoalkyl esters of long-chain fatty acids derived by transesterification or acid esterification of vegetable oils or animal fats. High-quality feedstocks for biodiesel are primarily triglycerides (e.g., vegetable oils), which are easy to process by alkaline transesterification. Low-quality feedstocks (e.g., yellow and brown greases) have higher levels of free fatty acids (FFAs). They are difficult to process and thus largely underused. The decomposition of fats and oils also creates FFAs. Alkaline transesterification catalysts (e.g., potassium and sodium hydroxide) react with FFAs to produce soaps that complicate downstream processing and reduce the yield of biodiesel. Using a strong acid to catalyze esterification reduces soap formation and improves yields but generates an acidic methanol waste.

Enzymes can easily convert both triglycerides and free fatty acids into fuel-grade esters. In collaboration with Novozymes A/S, Piedmont developed three techniques for enzymatic biodiesel production: (1) lipase transesterification to replace alkaline transesterification for high-quality feedstocks; (2) bulk lipase esterification to replace acid esterification for feedstocks with high levels of FFAs; and (3) an acid-value reduction process for low amounts of FFAs. Piedmont&#;s enzymatic process accommodates low-quality and high-quality feedstocks without loss of biodiesel yield. Enzymatic catalysis operates near room temperature and does not form soaps, require vacuum or pressure, or produce unintended side-reactions.

The process eliminates water use, requires little excess methanol feedstock, and significantly improves glycerin quality to low-ash, technical grade with over 97 percent purity. The soap-free, enzymatic biodiesel process improves separation between biodiesel and glycerin phases because the emulsifier (soap) is not present. The new process also uses less energy than the current process or other second-generation processes (e.g., metal oxides). Piedmont&#;s biodiesel meets ASTM (American Society for Testing and Materials International) standards and is economically viable for existing biodiesel processors. During , Piedmont Biofuels and Novozymes A/S will commercialize this process.

Enzymatic Degumming of Vegetable Oils: Reducing Environmental Impact and Improving Oil Yield: Typical production of refined, bleached, deodorized vegetable oil, particularly soy oil, involves removing lecithin and phospholipid (the naturally occurring gums) with phosphoric acid and caustic in succession. Centrifugation of the final aqueous-oil mixture removes the aqueous phase along with the gum. The process uses a final pH in excess of 7, which saponifies the oil and generates soapstock (a mixture of fatty acid salts and gums). This soapstock has no value, and it is often sent to landfills.

The new Bunge/Novozymes process uses relatively small amounts of citric acid and caustic along with a phospholipase (Lecitase® Ultra) and about 2 percent water. Lecitase® Ultra cleaves the fatty acid from the 1-position, yielding a lyso-phospholipid and a fatty acid. Centrifugation then readily removes the aqueous mixture containing lyso-lecithin, which is of value for animal feed. Finally, the deodorization step removes the free fatty acids, which can be used as a valuable coproduct or processed into other products such as biodiesel fuel.

Enzymatic degumming of vegetable oil reduces the phosphorous content of the oil (a measure of residual gums) to below 5 ppm. The process generates less water and soapstock waste and increases oil yield, reducing the environmental impact with respect to traditional processing.

The average annual production of soy oil in the United States is approximately 9.5 million metric tons. Lifecycle analysis shows that if all of this oil were refined using the Bunge/Novozymes enzymatic process, carbon dioxide (CO2) emissions would be reduced by an amount equal to the average population environmental effects of over 200 million people and energy would be saved by an amount equal to over 2 million barrels of refined gasoline.

Enzyme-Assisted Conversion of Aromatic Substances to Value-Added End Products. Exploration of Potential Routes to Biodegradable Materials and New Pharmaceuticals: The combination of enzymatic transformations performed in aqueous media with efficacious, brevity-based design has been shown to yield unprecedented efficiency in the attainment of important pharmaceuticals from metabolites of the arene cis-diol type, more than 200 of which are known. Such processes lead to pollution reduction at the manufacturing source by drastically shortening the synthetic process, thus requiring less reagent and solvent input. Because one or more steps are performed in water with whole cells of common soil bacteria, the residual mass of such steps is, after sterilization, judged suitable for disposal to municipal sewers, thus further reducing the amount of actual waste. This program has potentially global impact with attendant benefits to the health and economy of society at large through managed processing of aromatic waste.

Enzyme-Based Technology for Decontaminating Toxic Organophosphorus Compounds: Current field military or civilian decontaminants such as Decontaminating Solution 2, Super Tropical Bleach, and Sandia Foam are quite efficient against chemical and biological agents, but they are also toxic and corrosive. They are nonspecific oxidizing agents that must be used in stoichiometric amounts.

The U.S. Army Edgewood Chemical Biological Center (ECBC) has developed and patented a technology using enzymes to neutralize chemicals such as nerve agents and related pesticides. The technology consists of two enzymes in a dry granular form that can be added to water or water-based application systems (e.g., fire-fighting foams and sprays, aircraft deicing solutions, and aqueous degreasers). The enzymes quickly detoxify these hazardous chemicals before they can contaminate wider areas. Because the enzymes are catalytic, only small quantities are required, greatly reducing transportation and storage requirements (by as much as 25- to 50-fold). The enzymes are also nontoxic, noncorrosive, and environmentally safe. Initially intended to decontaminate equipment, facilities, and large areas, these enzymes could potentially be used in shower systems to decontaminate personnel and casualties.

The specific bacterial enzymes are organophosphorus hydrolase (originally called parathion hydrolase) and organophosphorus acid anhydrolase (an X-Pro dipeptidase, EC 3.4.13.9). These two enzymes are effective against V- and G-type nerve agents, respectively. Genencor International, the premier manufacturer of industrial and specialty enzymes in the United States, is using its state-of-the-art fermentation manufacturing technology to produce the enzymes.

Genencor has begun commercial production and now has industrial-scale quantities of the enzymes available under the trade name DEFENZTM. The enzymes will be sold to companies that produce and sell fire-fighting foams, sprays, and other potential matrices. These companies will formulate the enzymes into products for purchase by fire departments, HazMat groups, and other first-responders. Kidde Fire Fighting introduced the first such commercial product, All-ClearTM, in August .

Enzymes as an Alternative to Toxic Materials for Treatment of Slime Deposits in the Paper Industry: The accumulation of biofilm is a serious operational problem in papermaking systems, and can cause fouling in many other industrial systems as well. In such systems where large amounts of water are used, microorganisms attach to surfaces and form a "biofilm," composed of carbohydrates and protein. This can foul machinery, reduce heat transfer, and cause many other problems. In the past, the only viable solution was the use of toxic chemicals such as bactericides and fungicides, which involve significant risks in handling and transportation.

This nominated technology utilizes stabilized enzymes to clean surfaces, removing the deposit, in many cases eliminating the use of toxic materials currently required. These enzymes are biodegradable, nontoxic, and produced from renewable resources. They do not function by killing microorganisms&#;they are nontoxic. The active ingredients are specific protease enzymes.

We will show how this innovation provides products that are significantly less toxic to our environment than the chemicals it can replace. In addition, this new technology is much safer to handle, to manufacture, transport, and use than the conventional chemistries.

Enzymes to Reduce Energy Use and Increase Recycling of Paper: Buzyme® from Buckman Laboratories is a novel enzymatic technology to modify the wood fibers used to manufacture paper. Buzyme® consists of a group of new cellulytic or hemicellulytic enzymes made by fermentation in bacteria or fungi. For each grade of paper, Buckman selects the enzyme that provides optimum results. This enzymatic treatment of the wood fiber reduces the amount of mechanical refining required to reach desired fiber properties. In various commercial applications in paper mills, this invention has given benefits such as increased use of recycled paper, reduced energy needed to produce paper, and improved quality of paper goods.

This technology improves the strength of paper and paperboard, reducing the use of chemicals to improve strength. Less energy is needed to give the required strength to paper products. The technology is already in use successfully in about 10&#;15 paper machines in North America, producing tissue papers, napkins, corrugated boxes, and other grades of paper. One paper mill that makes dinner napkins was able to use recycled fiber exclusively and save $1 million that it had been spending for virgin wood pulp each year.

Buzyme® products make it possible to recycle more paper, produce paper more efficiently, and manufacture higher quality paper. Enzymes produce several benefits: enzyme biotechnology comes from renewable resources, is safe to use, and is itself completely recyclable. Use of these enzymes reduces requirements for chemicals derived from petroleum feedstocks. These enzymes are nontoxic to human health and the environment. They are produced by fermentation from readily available renewable resources. Although this technology has been studied in laboratories for some years, Buckman has recently found the keys to make it successful on a full-scale industrial basis.

EquinoxTM: A Greener Approach to Microbiological Control: Because of its high biocidal efficacy and low cost, chlorine is one of the most predominant biocides used by the U.S. papermaking industry, with an estimated 60 million pounds of chlorine biocides used annually. The widespread use of chlorine in papermaking creates highly toxic chlorinated byproducts, such as trihalomethanes and dioxin, which are broadly referred to as absorbable organic halogen (AOX). Lonza has developed Equinox® as a nontoxic alternative to reduce the amount of chlorine biocides used by the papermaking industry. Equinox® is based on 5,5-dimethyl hydantoin, which interferes with the natural tendency of chlorine to random oxidations and in the process enhances chlorine&#;s bactericidal properties. By markedly improving the stability of chlorine, Equinox® has shown that it can reduce chlorine use by over 90%.

Because chlorine is reduced, the amount of AOX is similarly reduced by up to 95%. Since its commercial introduction in , Equinox® has treated over 36 billion gallons of paper mill water, eliminating the use of an estimated 2.4 million pounds of chlorine and preventing the generation and release of over 128,000 pounds of AOX into the environment. Equinox® is now used in paper mills throughout the U.S. and Europe. Equinox® has other uses as well, but in the papermaking industry alone it has the potential to eliminate the formation of 3.3 million pounds per year of AOX pollutants. By reducing the amount of toxic AOX compounds released into the environment, Equinox® provides an environmentally safer alternative to the historically high use levels of chlorine biocides.

Equipment Flushing Agent for the Polyurethane Industry: The product IFS 283 is designed as a flushing agent for isocyanate contaminated equipment frequently encountered in the polyurethane industry. Any equipment that handles isocyanates can utilize IFS 283 as flushing agent. This includes tanks, hoses, vessels, piping, flow meters, pumps and other equipment. Equipment contaminated with isocyanates, especially polymeric methylene diphenyl diisocyanate, is subject to the formation of solids due to the reaction of the isocyanate with moisture, forming intractable polyureas. These solids can effectively destroy sensitive flow meters, block hoses and necessitate rebuilding of pumps.

IFS 283 reacts preferentially with the isocyanate, eliminating the chemically hazardous moiety and generating a water washable urethane liquid. Equipment flushed with IFS 283 is decontaminated and thereby much safer to handle. The contaminated flush material, if used properly, will not have residual isocyanate species and can be discarded at a saving of about $500 per drum compared to disposal of a hazardous waste material. The total volume of more hazardous solvents that IFS 283 can replace is uncertain, but estimated to be about 2 to 4 million pounds.

EthosTM Modular Commercial Floor Coverings: Polymeric poly(vinyl butyral) (PVB) is a thermoplastic terpolymer of vinyl acetate, vinyl alcohol, and vinyl butyral that provides shatterproof properties to windshields and other safety glass. Although recyclers have recovered the glass from safety glass and sold it into other markets for years, most of the PVB film has been sent to landfills or burned for energy. Tandus Flooring is the first manufacturer to use the abundant PVB waste stream and recycle it into high-performance carpet backing.

EthosTM secondary backing, made from PVB film reclaimed from windshields and other safety glass, can replace other structured carpet backings such as poly(vinyl chloride) (PVC), ethylene&#;vinyl acetate (EVA), polyurethane, polyolefin, and bitumen. Producing ethosTM backing from recycled material reduces the energy and environmental impacts associated with extracting, harvesting, and transporting virgin raw materials. Tandus evaluated PVB against 10 other polymer-based materials using stringent performance and environmental criteria. In these tests, PVB was superior to the other polymers in material availability, recyclability, reduction of virgin resources, avoidance of hazardous emissions (e.g., dioxin), and elimination of chemicals of concern such as chlorine, fly ash, and phthalate plasticizers. In addition, ethosTM backing has extremely low environmental lifecycle impacts compared to other products.

Tandus&#;s patented, closed-loop process can also recycle postconsumer carpet with ethosTM backing and other manufacturing waste into new floor coverings. Initially, Tandus successfully introduced a six-foot-wide ethosTM cushion backing, Powerbond, to meet the needs of Kaiser Permanente for high-performance, PVC-free, soft-surface flooring. In November , the company introduced ethosTM modular. Its production has increased 18-fold in the last two years. Every square yard of ethosTM modular replaces approximately 5.25 pounds of PVC in carpet backing. To date, Tandus has recycled more than 10 million pounds of PVB into flooring products, keeping PVB from landfills, and potentially replacing 52 million pounds of PVC.

Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of Diaryl Aldimines: Imines are essential intermediates in many pharmaceutical syntheses. For example, diaryl aldimines are feedstocks for blockbuster drugs such as Taxol® (used for chemotherapy) and Zetia® (used to reduce cholesterol). Diaryl aldimines added to polyethylene increase its photodegradation in the environment. Unfortunately, traditional syntheses of diaryl aldimines often require hazardous solvents and include energy-intensive, multihour reflux steps. Although some imine syntheses use more benign solvents or conditions, they still require long reaction times, recrystallization, or other environmentally unfriendly procedures.

Recently, Professor Bennett found that ethyl L-lactate, an FDA-approved food additive, can replace the hazardous solvents commonly used to synthesize imines. Her method is extremely efficient under ambient conditions and requires less solvent than published methods. It has a median yield of over 92 percent and a median reaction time of less than 10 minutes. The resulting imines are usually pure enough without recrystallization, avoiding additional waste. Professor Bennett&#;s method "tunes" the polarity of ethyl L-lactate by adding water.

The starting materials remain dissolved, but the imine crystallizes out of solution as it forms. Although traditional methods often drive reactions forward by removing water, Professor Bennett&#;s method drives the reaction forward by removing the product through crystallization. To date, she and her undergraduate research students have synthesized nearly 200 imines using this method; her students in teaching labs have made more than half of these in a green chemistry project. In summary, the ethyl L-lactate method is faster, usually results in higher purity and yield, uses less energy, uses less solvent, generates less waste, and uses a more benign solvent than published methods. A patent application for this method was published in . Professor Bennett is now studying these imines in biological and other applications. All are fluorescent and some are photochromic. Several show promise as fluorescent cell markers and antibacterial agents.

Ethylene: A Feedstock for Fine Chemical Synthesis: New carbon&#;carbon bond-forming processes have been responsible for significant advances in organic synthesis. Practical methods using feedstock carbon sources as starting materials to form enantioselective carbon&#;carbon bonds are rare, however. Ideally, any new reaction must: (1) use abundantly available, carbon-neutral sources; (2) produce a functional intermediate for other common organic functional groups; (3) be highly catalytic, generating little or no waste including toxic metals; (4) provide high, reagent-dependent selectivity to produce all isomers including enantiomers; and (5) include easy product recovery.

A broadly applicable reaction using ethylene to install highly versatile vinyl groups enantiomerically could thus have significant impact in organic synthesis. Professor RajanBabu and his group have developed highly catalytic (substrate&#;catalyst ratio up to 7,412:1) protocols for nearly quantitative (isolated yields can be over 99 percent) and highly selective (approximately 100 percent regioselectivity; enantiomeric ratios of over 99:1) co-dimerization of ethylene and various functionalized vinylarenes, 1,3-dienes, and strained alkenes. These reactions proceed under mild conditions (-52 °C to 25 °C; 1 atmosphere of ethylene) to produce intermediates such as 3-arylbutenes, which can be transformed to nonsteroidal anti-inflammatory drugs (NSAIDs) in two steps.

These reactions consume both starting materials, leaving no side products. Successes include highly enantioselective syntheses of common NSAIDs, such as ibuprofen, naproxen, flurbiprofen, and fenoprofen, from the corresponding styrenes and ethylene. Cyclic and acyclic 1,3-dienes also undergo efficient enantioselective addition of ethylene. Syntheses of several 1-vinylcycloalkenes and 1-substituted-1,3-butadienes achieve yields up to 99 percent. Professor RajanBabu has found expeditious routes to biologically relevant classes of compounds including bisabolanes, herbindoles, trikentrins, steroid D-ring 20S- or 20R-derivatives, (-)-desoxyeseroline, pseudopterosin A&#;F, G&#;J, and K&#;L aglycones, and helioporins. These syntheses require fewer steps than traditional methods and produce uncommon configurational isomers. In and , Professor RajanBabu published five papers on this work.

Evapo-RustTM: Nonhazardous Rust Removal by Selective Chelation: Economic loss in the U.S. to corrosion costs $276 billion annually. Traditional methods of corrosion (or rust) removal include acids, caustics, converters, electrolysis, and mechanical. Their low purchase price is only a small portion of their true cost. These methods are major contributors to hazardous disposal, emissions, and human health problems. They use materials that are toxic, are corrosive, and can create explosive gasses and release volatile organic compounds (VOCs) and hazardous air pollutants (HAPs). Waste from these methods may contain heavy metals, paint, grease, oil, and various organic materials.

Harris Labs has invented an industrial replacement to remove and control corrosion in iron preparations. Evapo-RustTM is nontoxic, nonhazardous, nonflammable chemical with a targeted process of removing rust (iron oxide). Evapo-RustTM removes the iron oxide into solution by a proprietary process called selective chelation. The active ingredient in Evapo-RustTM is an ester of a polyphosphoric acid with an amine. Following chelation, a sulfur compound removes the iron from the chelator to form a ferric sulfate complex, regenerating the chelator. As the normal operational pH is between 6 and 7, the solution is never hazardous to handle, store, or dispose of in neat form. Personal protective equipment (PPE) is not required with Evapo-RustTM, making it an excellent industrial and consumer product. There are no air or ground transportation restrictions for Evapo-RustTM. Waste generated by Evapo-RustTM is typically nonhazardous; the spent ferric sulfate has potential for use as a lawn and garden fertilizer. Evapo-RustTM has been implemented in general industrial and strategic Department of Defense installations.

Everdex-Enhanced Alowood: Deforestation of old-growth forests and rainforests is of growing concern given today&#;s far-ranging debates on climate change. Although only 22 percent of the world&#;s old growth forests remain intact, consumers still want the look of exotic hardwoods in products such as flooring and furniture.

Alowood offers an environmentally friendly alternative: an exotic look and performance using fast-growing plantation softwoods impregnated with the Everdex formulation, an innovative green chemistry. Everdex is a polymeric formulation made from urea, glyoxal, and starch in water along with environmentally friendly dyes and pigments; it does not contain any formaldehyde. Softwoods, particularly sustainably grown, plantation softwoods, are impregnated with dilute solutions of Everdex by a vacuum-pressure treatment. Next, the impregnated wood is heated, causing the starch polymer to cross-link with the wood cellulose through the urea-glyoxal groups. This creates Alowood: a denser, harder, more workable wood product akin to a natural hardwood. During , Alowood received GREENGUARD Indoor Air certification and class A fire retardant certification.

EverTech is currently selling Everdex-enhanced Alowood to the building industry as an alternative to natural hardwood. This innovative product is making a significant positive environmental impact: every piece of Alowood sold replaces a piece of hardwood lumber or exotic wood that can remain a part of the ecosystem. Alowood, made from plantation wood grown in 10&#;20 years, is preferable to exotic hardwoods that often take hundreds of years to grow. In the time it takes a hardwood forest to rejuvenate, a softwood plantation of the same size could be harvested up to 100 times for use in Alowood. To date, over 2 million board feet of Alowood are on the market, saving over 10,000 hardwood trees.

ExSact &#; A "Green" Gasoline Technology: Alkylate is a clean, high-octane, blending component of gasoline made primarily by alkylating isobutane with butenes. Alkylate is an ideal replacement for MTBE (methyl t-butyl ether) in reformulated gasoline. It has a low vapor pressure, a high octane value, and is not water-soluble. Most U.S. refineries produce alkylate. The current technology for alkylation, however, requires either hydrofluoric acid (HF) or concentrated sulfuric acid as the catalyst. These liquid acid catalysts pose many problems. HF is deadly, causing severe burns and tissue damage. It also tends to form stable aerosols, so that an accidental release can create a lethal cloud. The 50 HF units in the United States threaten as many as 15.6 million people living nearby. Sulfuric acid is somewhat safer, but its use creates a byproduct mixture of hydrocarbons and sulfuric acid that must be disposed of or regenerated. Sulfuric acid units use considerable amounts of the acid as catalyst, requiring the transport and storage of large amounts of this acid.

ExSact solves these problems by replacing dangerous liquid acids with a noncorrosive, environmentally friendly, solid acid. This breakthrough catalyst is safe enough to be held in hand and is benign in the open environment. Previous solid acid catalysts have not been commercially successful because they tend to deactivate rapidly by coking during alkylation. Exelus has engineered every aspect of its new catalyst to reduce coke formation. It has optimized both the distribution and strength of the acid sites and has chosen a pore structure that creates the proper reaction environment near the active sites. Its ExSact technology represents the first commercially viable solid acid alkylation process in the world. Exelus has successfully demonstrated the ExSact technology in a 1,000-hour pilot program and has licensed its technology to a European refiner. The first commercial plant is expected to start up in early .

ExSyM &#; The Next Generation of Styrene Monomer Technology: Styrene monomer is a large-volume commodity chemical with a current global demand of about 25 million metric tons per year. The current technology is over 70 years old. It relies on the dehydrogenation of ethylbenzene, which is a highly endothermic and thermodynamically limited reaction. Styrene production consumes about 10 times more energy than does the production of most other industrial chemicals and is a major contributor to methane emissions.

Exelus is developing ExSyM (Exelus Styrene Monomer Technology), a technology to produce styrene monomer directly by the alkylation of the toluene side-chain with methanol. Others have studied this route for over 30 years, but they could not overcome the high rate of methanol decomposition and low yields of styrene that have prevented its commercialization.

Exelus has invented a new zeolite catalyst technology and made other breakthroughs that, for the first time, permit commercially viable reaction yields of 80 percent. The technology uses a simple fixed-bed process. Substituting toluene and methanol for the traditional process feedstocks (benzene and ethylene) leads to a 30-percent reduction in operating costs. This new technology also reduces the reaction temperature by over 200 °C, resulting in much lower capital costs than conventional plants.

Perhaps the single biggest benefit to society, however, is a massive reduction in energy use. This process would save up to 186 trillion British thermal units per year (Btu/yr) in the United States alone, cutting CO2 emissions by 4.34 billion kg per year. These savings represent over 5 percent of the U.S. greenhouse gas reductions stipulated by the Kyoto Protocol. In addition, the hydrogen byproduct of the reaction can be used as fuel to produce all of the heat of reaction and most of the distillation energy for the process without generating any CO2. Exelus has demonstrated its technology at the bench scale and expects to begin pilot plant tests in mid-.

Fertilizer From Photowaste: More than 100 million gallons of photographic wastes are generated in the United States annually. According to U.S. Environmental Protection Agency studies in the early &#;s, these wastes represented approximately 40 percent of all liquid toxic waste produced by American industry. This waste is a significant environmental hazard to the nation&#;s bodies of water because photographic wastes contain silver and other heavy metals. Silver is potentially toxic to fish and other aquatic life. The waste, from photo finishers, photo labs and studios, X-ray laboratories, and printers, is dumped into the environment without pre-treatment, although rules are being tightened in many states and municipalities to curtail this or to require more intensive treatment.

Itronics, Inc. is the world&#;s only fully integrated photochemical recycling company. It provides photochemical waste collection services, recovers and refines silver from the photochemicals, manufactures and blends liquid fertilizers from the processed residual, and sells and distributes lines of liquid fertilizers designed to meet specific plant nutrition needs. Since virtually all the toxic metals have been extracted, the fertilizer manufactured from this clean liquid base, is environmentally beneficial, helping to solve the major national concern of heavy metals from fertilizer contaminating farm fields or bodies of water.

Filter Leak Test Using Ozone-Benign Substances: Air purification filters operate by adsorbing impurities from flowing contaminated streams onto high-surface-area microporous materials, such as activated carbon. For such a filter to operate properly, it must be packaged so that leak channels are eliminated. Testing to ensure proper adsorbent material filling of manufactured fibers is routine and has traditionally been performed using substances such as chlorotrifluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12). It is now well known that small chlorocarbons, chlorinated fluorocarbons (CFCs), and certain bromine-containing, fire-extinguishing materials (halons) are detrimental to the environment because of their extreme environmental stability in the lower atmosphere and their ability to release chlorine and bromine atoms upon vacuum ultraviolet irradiation in the stratosphere. Chlorine and bromine atoms produced in the stratosphere destroy ozone catalytically, thereby compromising the UV-protection that the stratospheric ozone provides.

With the advent of the Montreal Protocol eliminating production of ozone-depleting substances, the search for substitute materials for common items including air-conditioning and fire extinguisher fluids has to be intensive. Work at the U.S. Army Edgewood Research, Development, and Engineering Center was directed at finding filter leak test materials that were not destructive to earth&#;s stratospheric ozone layer and were capable of rapidly identifying filter assembly problems. Materials investigated included several hydrogenated fluorocarbons (HFCs) of differing volatility. HFCs do not contain chlorine or bromine, which have been implicated as potent stratospheric ozone destroyers. Two HFCs were identified as substitute filter leak test vapors: 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-mee) for in-service filters and 1,1,1,2-tetrafluoroethane (HFC-134a) for new filters. These materials have been adopted by the U.S. Army to test the integrity of filters used to provide respiratory protection against chemical warfare agents.

FIREBLOCKTM Intumescent Resin: Composites used to manufacture interior and exterior parts for applications in trains, tramways, subways, and other rolling stock must meet fire retardant specifications. Traditional chemicals used in fire retardant composites are decabromodiphenyl ethers and antimony trioxide, which are carcinogens, mutagens, and reproductive toxins. The manufacturing of these fire retardant composites requires handling highly toxic substances. In case of accidental combustion, polybrominated aromatic compounds release free radicals that act in synergy with antimony trioxide to produce bromide radicals and toxic fumes. Intumescent coatings swell with heat, offering passive fire protection. Intumescent coatings have been known for years, but these products were very difficult to formulate and apply. In , CCP Composites developed a breakthrough product, FIREBLOCKTM intumescent unsaturated polyester resins (UPRs), which can be molded with glass fiber to manufacture fire retardant parts. In the intumescence mechanism, high temperatures cause ammonium polyphosphate to release an acid that simultaneously reacts with melamine in the resin to liberate a gas. The gas diffuses into small bubbles and carbonizes the carbon-rich polyalcohol.

These actions form foam that solidifies into a char and shields the underlying material to stop the combustion cycle. FIREBLOCKTM resin is a commercially viable alternative to bromine-containing fire retardant UPRs used in a wide variety of composites. It is completely free of halogens, mutagens, carcinogens, and reproductive toxins. In addition to meeting the same standards on materials fire behavior as do traditional fire retardants, FIREBLOCKTM intumescent resin also has a lower density than standard unsaturated polyester resins. It is environmentally friendly, with a 13 percent reduction in carbon dioxide (CO2) emissions compared to standard fire retardants in the railway industry. A significant portion of today&#;s estimated 10 million pounds annual use of brominated UPRs could be converted into FIREBLOCKTM technology in the next five years in the United States.

Flexible NORYL* Resins for Wire Coating: Poly(vinyl chloride) (PVC) has been widely used in the wire and cable industry as both insulation and jacketing material for decades. The current annual U.S. consumption of PVC for these applications is about 300,000 metric tons. During its product cycle, PVC contributes significantly to ozone depletion, global warming, and the release of cancer-suspect dioxin and phthalate. It releases toxic smoke containing hydrogen chloride and cancer-suspect dioxin during its manufacture and incineration.

GE Plastics has invented and commercialized ten grades of flexible poly(arylene ether) resins that substitute for PVC in coatings and coverings for wire and cable. They market them as Flexible NORYL* resins. GE&#;s Flexible NORYL* resins are based on proprietary compositions containing poly(arylene ether), polyolefin, and a nonhalogenated flame retardant. Flexible NORYL* resins totally eliminate halogenated compounds, heavy metal stabilizers, pigments, and phthalates. Moreover, Flexible NORYL* resins may facilitate the reuse of wire coating to benefit the environment. Wire coatings made with Flexible NORYL* resins have helped the consumer electronics and automotive industries meet stringent environmental initiatives, such as the European Union&#;s ISO and ISO and EcoMark in Japan.

For the consumer electronics industry, wire coatings made from Flexible NORYL* resins offer better heat performance, increased flame retardant properties, and lower costs due to reduced weight. In the automotive industry, NORYL* resins can improve vehicle performance by improving abrasion resistance, improving heat performance, and allowing more compact electronics. The light weight of Flexible NORYL* resins and their outstanding abrasion resistance enable ultrathin wall wire construction. They may reduce an automobile&#;s wire-resin weight by as much as 25 percent. Flexible NORYL* resins can make a significant contribution to helping global automotive manufacturers meet end-of-life and take-back requirements including the European Union&#;s Restriction of Hazardous Substances and End-of-Life Vehicle directives, Japan&#;s Automobile Recycling Law (), and the Japan Automobile Manufacturers Association (JAMA) guidelines.

Fluorous Biphasic Catalysis: A New Paradigm for the Separation of Homogeneous Catalysts from Their Reaction Substrates and Products, as Demonstrated in Alkane and Alkene Oxidation Chemistry: Fluorous biphasic catalysis (FBC) is a new concept for homogeneous catalysis where the fluorocarbon soluble catalyst and the substrates/products reside in separate phases. The work of Dr. Richard H. Fish, Lawrence Berkeley National Laboratory, presents the synthesis of a novel fluoroponytailed ligand, tris-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)-1,4,7-triazacyclononane (RfTACN), that is soluble in perfluoroalkanes, [Mn(O2C(CH2)2C8F17)2] and [CO(O2C(CH2)2C8F17)2].

The initial results on the functionalization (oxidation) of alkanes/alkenes, using in situ generated fluorous phase soluble RfMn2+-RfTACN and RfCO2+-RfTACN complexes (Rf = C8F17) as the precatalysts, in the presence of t-butyl hydroperoxide (t-BuOOH) and O2 gas as oxidants, demonstrated that alcohols, aldehydes, and ketones could be produced catalytically and that the oxidation products and fluorous phase soluble precatalysts were indeed in separate phases. The fact that fluorocarbon solvents are relatively non-toxic provides the FBC concept with an entry to the new "Green Chemistry" regime of being environmentally friendly, and therefore, attractive to a wide variety of industrial processes for the ultimate catalytic production of important organic chemicals worldwide.

Formaldehyde-Free, High-Strength Biocomposites from Sustainable Resources: The formaldehyde and volatile organic compounds (VOCs) used to make conventional coatings, binders, and laminates for the wood composites in furniture contribute significantly to indoor air pollution. e2e Materials is commercializing biocomposite products that contain no formaldehyde or VOCs and are made without hydrocarbons or toxic feedstocks. e2e&#;s biocomposites are made from lignocellulosic bast fibers, soy protein, and plant polysaccharides; they are biodegradable at the end of their useful lives. The long bast fibers, from sources including kenaf, jute, flax, and hemp, are lightweight and contribute to higher strengths in ways that the short wood fibers used in particleboard and medium-density fiberboard (MDF) cannot.

The soy protein and plant polysaccharides are feedstocks for a natural resin system that binds the fibers together into biocomposites. e2e&#;s biocomposite material is 3&#;4 times stronger than today&#;s wooden particleboard and MDF. e2e can mold its biocomposites into three-dimensional parts (i.e., net-shape them into whole, structural components) that replace traditional 4 x 8-foot sheets. Net-shaping can create stronger components by molding them as one part rather than assembling them from pieces. The e2e biocomposites also retain screws better than wood composites. These features combine to create stronger furniture while reducing the total amount of material and weight. e2e&#;s biocomposites are inherently fire-resistant because they contain a modified soy protein instead of petrochemical resins.

They use only 19 percent of the embodied energy of today&#;s products because the manufacturing process requires less energy and regionally integrated manufacturing minimizes transportation costs. Products made from today&#;s wood composites have a $100 billion market. e2e is replacing those products with higher performing, safer, more efficient, and more cost-effective biocomposite-based products. These products complement its proprietary biocomposite core with green, cost-effective coatings. Following successful pilot production in and responding to strong demand for its commercial office furniture products, e2e recently announced a 100,000 square foot manufacturing expansion.

Formamide Replacement in Genetic Sequencing: The process to determine a nucleotide sequence for a segment of DNA requires multiple steps and chemicals. Formamide was used in the past to resuspend DNA after it had been denatured prior to sequencing. However, formamide is a hazardous chemical with an unpleasant scent that could potentially harm a fetus according to its Material Safety Data Sheet. Researchers at the Los Alamos National Laboratory searched for a non-hazardous replacement for formamide to reduce potential adverse exposure to employees. The research team discovered that a water-based solution gave even better results than formamide for resuspending DNA during the sequencing process. The water-based solution is called Tris-EDTA (TE), and it is easy to mix in any biochemistry laboratory. Formamide was the only hazardous chemical associated with genetic sequencing, so eliminating formamide substantially reduces the amount of hazardous waste and paperwork involved with operations. Total annual savings on reduced waste disposal, procurement costs of distilled formamide, and labor are approximately $78,000.

Formation of Ene-Diyne Molecules Under Indium Mediated Aqueous Barbier-Conditons: The discovery that natural products containing ene-diyne reactive centers inhibit growth of mutated DNA strands, retarding the development of cancer cells and tumors, has prompted much excitement in the scientific community. Although this research appears promising, it is presently slowed by difficult synthetic routes and low yields of target ene-diyne structures.

This proposal addresses the use of novel synthetic routes which will alleviate this impediment. Use of water as a solvent in the formation of ene-diynes will introduce an environmentally benign methodology allowing for rapid advances in a very stimulating, important, yet untapped area of chemistry.

Use of indium mediated Barbier reactions to form C-C bonds has developed into a new and exciting area of chemical synthesis. Use of water as a solvent in these transformations has become an area of focus for a number of reasons: 1) Water is the cheapest solvent on earth, making it economically favored. 2) Synthetic efficiency may be increased by eliminating the need for traditional protecting groups. 3) Simplicity of controlling reaction conditions. No inert atmospheric requirements, no exclusion of moisture needed. Easier temperature control due to the high heat capacity of water. 4) Elimination of pollution historically caused by use and subsequent disposal of traditional organic solvents.

Indium metal has been shown to form chelates in aqueous solutions, thus allowing for good stereocontrol in the formation of coupling products, an attribute utilized in a variety of procedures. The electrophilic agent has commonly been designed to enhance diastereofacial control in these coupling reactions by placement of a chiral center - to a carbonyl functionality. While this approach has met with good success giving ratios as high as 13:1 in favor of one diastereomer, it is somewhat limiting by the fact that the nucleophilic species does not project any stereochemical control of newly formed centers.

Previous studies in our laboratories have revealed that -chlorosulfide species may be used to control stereoselectivity in indium mediated Barbier reactions conducted under aqueous conditions (Scheme 1). The chlorosulfide species used for these C-C bond formations are attainable in one step from purchased materials and expand the scope of indium promoted couplings a great deal. -Hydroxy thioethers formed in this reaction may be transformed into epoxide functionalities

If a quick, controlled, more environmentally friendly method could be found to form ene-diyne skeletal structures, work in this area could progress at a much quicker rate. It is with this goal in mind, that I propose to utilize the new, exciting, environmentally benign chemistry from our laboratory to form ene-diyne structures in order to elucidate a good skeletal structure for use in targeting mutated DNA to halt the replication of cancerous tumors.

Formula 1TM Laundry System: Formula 1TM is a new, single-product system designed for on-premises commercial laundry operations. Its unique dispensing and packaging system (patent pending) produces a dilute detergent solution from a 100% active concentrate on-site. The concentrate is a nonaqueous, heterogeneous slurry that contains C12-14 linear alcohol ethoxylates, two polymeric water conditioning agents, a proprietary enzyme support matrix, and sodium carbonate. This single-product system can replace three or four current products with no loss in performance. The Formula 1TM technology delivers many benefits to the consumer and to the environment. These include fewer wash steps and, therefore, water savings, energy savings, and shorter cycle time; fewer different products required; reduced product waste; reduced plastic packaging; significantly lower shipping weight; and increased worker safety. Formula 1TM contains no caustic soda, chlorine, or nonylphenol ethoxylates. The marriage of product chemistry, dispenser, and packaging gives on premise laundry operators a revolutionary new way to clean that is significantly more environmentally friendly.

The Formula 1TM Laundry System has been in commerce since January ; there are currently over 1,000 users in North America. If half of the over 50,000 potential user locations in North America used the Formula 1TM Laundry System, they would save 8.2 billion gallons of water, 47 million therms of natural gas, and 5 million pounds of plastic each year.

From Waste-to-Energy: Catalytic Steam Gasification of Poultry Litter: UTSI&#;s poultry litter gasification concept is based on the Exxon&#;s Catalytic Coal Gasification Process. In this concept, poultry waste or any other animal waste is mixed with the other biomass waste and suitable source of additional potassium. The resulting mixture is gasified in "as-is" or slurry form at - °F and at 50-150 psi pressure in a suitable gasifier. The steam for gasification can be produced externally and supplied to the gasifier or can be produced in-situ from the wet/slurried feedstock. Depending upon the pressure, the resulting fuel gas will be rich in CH4 or in CO and H2 and after separating from the solid/char residue can be used as a fuel for heating purpose or to produce electricity. The solid/char residue is significantly small in volume (by a factor of 5 to 10) than the starting waste, and therefore, can be used in cement/concrete manufacturing or as fertilizer to provide concentrated source of K and P-bearing salts. Potassium present in poultry and certain animal wastes such as from swine, cows, horses, and sheep can provide the necessary catalyst. If necessary, additional supplemental potassium can be obtained from other cheap sources such as langbeinite and feldspar.

Fully Biodegradable Vegetable Oil-Based Electrical Insulating Fluid (BIOTEMPTM): The electrical industry uses millions of gallons of petroleum-based insulating fluids in transformers and other electrical apparatus. These fluids have low biodegradability, and in recent years, environmental concerns have been raised regarding the use of these fluids in equipment located in housing areas, shopping centers, and major water-ways. Spillage of the fluid by leaks and other means would contaminate the surrounding soil and water, posing a threat to living organisms. A safer, environmentally friendly fluid has been sought by electrical utilities.

To meet this challenge, ABB, a major worldwide electrical equipment manufacturer, initiated a R&D program in . Agriculturally based oils were considered the best choice. However, none of the vegetable oils commercially available were found to be suitable for immediate use because of the presence of undesirable components, poor oxidation stability, and high level of conducting impurities. The research project focused on 1) selection of a suitable base oil, 2) refining of the oil to electrical-grade purity, and 3) providing oxidation stability for long-term use when exposed to air periodically.

High monounsaturated oils with more than 75% monounsaturated content were selected. These oils are mostly high oleic oils derived from genetically modified oil seeds. They are inherently more stable than oils with significant di- and tri-unsaturate content. Further refining was achieved by the use of adsorbents derived from high-surface-area clays. Oxidation stability was the hardest to achieve because many antioxidants that are available are also highly conducting. A three-component system of antioxidants that would not significantly increase the conductivity was developed by extensive testing. The level of additives is below FDA regulatory limits, and these were food grade additives.

The newly developed fluid was tested extensively. The biodegradability was 97% or more, comparable to pure vegetable oil. The fluid is stable at elevated temperatures due to high fire point (above 300 C), adding more safety. The beneficial environmental impact of the new fluid, now commercially available, would be significant. For the first time in the last 100 years of use of insulating fluids, a truly biodegradable fluid has been developed for use in electrical apparatus with emphasis on environmental safety.

G2 Catalyst for New and Improved SURFONIC® Non-Ionic Surfactants: Two billion pounds of surfactants are used in the United States annually. Nonionic surfactants, which comprise 40 percent of this total, are among the fastest-growing types of surfactants due to their compatibility in blends and efficacy in liquid formulations. The desire for nonionic surfactants that have both lower cost and higher efficiency (i.e., lower foaming) necessitates the use of renewable, low-cost feedstocks.

Ethoxylates of vegetable oils, their esters, and their alcohols are attractive nonionic surfactants that meet industry&#;s needs. Detergent-range alcohols (C12&#;C18) derived from vegetable oil are used widely as hydrophobes to manufacture nonionic surfactants, but they require multiple manufacturing steps. Ethoxylated surfactants derived from vegetable oils or their esters require fewer manufacturing steps, but making them with standard catalysts produces slow, low-yield reactions that are impractical for commercial development.

Huntsman&#;s team developed G2, a novel, alkaline earth based catalyst that enables the direct insertion of ethylene oxide into fatty acid methyl esters (biodiesel) and vegetable oils in yields over 95 percent for the production of sustainably derived nonionic surfactants. Huntsman has demonstrated that its catalyst can ethoxylate a wide variety of sustainable, natural feedstocks from sources including coconut, palm kernel, soybean, linseed, canola, rapeseed, and palm stearin. The G2 catalyst uses environmentally friendly calcium. After the batch reaction is complete, the catalyst is neutralized. It remains in the product, so there is no disposal of spent catalyst.

Biodiesel is a methyl ester of vegetable oil fatty acids. Its production has increased dramatically in the last few years to support America&#;s national strategic intent to diversify its fuels. This catalyst technology is positioned to capitalize on the megatrend toward biodiesel by using biodiesel to make high-value, high-performance, biodegradable, and safe surfactants. During , Huntsman began manufacturing fatty methyl ester ethoxylates at its plant in the United States; the product name is SURFONIC® ME530-PS surfactant.

GEL-COR®: A New, Environmentally Compatible, Bullet-Trapping Medium for Small-Arms Firing Ranges: In , there were approximately 12,000 small-arms firing ranges in the United States. In , the U.S. EPA estimated that approximately 6.4 million pounds of lead go onto these ranges each year. Containing and recovering lead and other heavy metals in a safe, environmentally acceptable manner is vital to controlling soil and groundwater pollution from ranges.

GEL-COR® is an engineered ballistic material designed to collect impacting bullets fired on small-arms training ranges in a safe, environmentally compatible way. It captures the spent bullets and contains the lead and other heavy metals that would otherwise escape into the environment. GEL-COR® is a mixture of recycled tire-tread rubber chunks, a hydrated superabsorbent polymer gel (a copolymer of acrylamide and potassium acrylate), and three salt additives (tricalcium phosphate, aluminum hydroxide, and calcium carbonate). This resilient mixture stops incoming bullets, captures them intact with few exceptions, and does not make any detectable metal dust.

The gel-rubber mixture contains approximately 40 percent water by mass, which prevents it from sustaining a fire. The salt additives immobilize the lead and copper in the trapped bullets and keep them from leaching into the environment. Exposed lead surfaces react with the salts to form insoluble lead aluminum phosphate (plumbogummite), one of the safest, most stable lead compounds. Copper reacts to form an insoluble copper phosphate. The mixture maintains an alkaline pH, stabilizing the gel and minimizing the dissolution of the heavy metal salts. GELCOR® is the first resilient medium that contains no toxic additives and will not burn, even if exposed to a source of ignition. GEL-COR® is an important step in ensuring that live-fire ranges are safer and more environmentally compatible.

Super Trap received two patents for this technology in ; it holds an exclusive license to the technology, developed under a Cooperative Research and Development Agreement with the U.S. Army.

Generally Recognized as Safe (GRAS) Coatings: Using materials that are generally recognized as safe (GRAS) for human consumption, Ecology Coatings has developed coatings that can be applied to food or used in food packaging. These GRAS coatings protect food from outside elements, are safe for human consumption, and use natural ingredients, not plastics or other chemicals derived from fossil fuels. GRAS coatings have barrier properties to air, water, and solvents that will allow them to replace coatings originating from fossil fuels, especially plastic coatings made using acrylates and methacrylates. GRAS coatings have the potential to make food packaging greener and more sustainable by eliminating toxic plastics. Their environmental friendliness could allow increased recycling of food packaging. The coating includes a polypeptide such as albumin, a denaturing agent, and water as the solvent.

It can also include a natural gum, a flavoring agent, a dye, a de-foaming agent, maltodextrin, and an oil. When the mixture is exposed to UV light, it cures and cross-links, but does not coagulate. Used on food, the nominated coating will inhibit oxygen exposure and increase shelf life. GRAS coatings on food packages will also resist grease and can substitute for polyethylene or other petroleum-based coatings. Ecology Coatings&#; GRAS coating can also be used as a photoinitiator with conventional UV-curable materials that are approved for direct contact with food. GRAS coating components in powdered form not only promote UV curing but can extend the coverage of pigments.

In this use, the nominated technology could replace silica fillers. Finally, the GRAS coating can be used as a matting agent, which cures into the finished film and enhances the UV-curing process. Combined with other biobased additives, the GRAS coating can produce a rough surface that resists water and grease migration. In , Ecology Coatings filed a patent application for this technology.

Genesis® BRIGL Wash: Genesis® BRIGL Wash is a biodegradable blanket and roller wash for offset printers. It has a volatile organic compound (VOC) content of 34.3 grams per liter and an ASTM D-92 flashpoint greater than 200 °F. It contains over 90 percent soy methyl ester (a U.S.- renewable resource), less than 8 percent VOC-exempt acetic acid methyl ester, proprietary antioxidants, and preservatives. It does not contain water or surfactants. Genesis® BRIGL Wash offers a safer, more productive alternative to petroleum-based washes. It does not contain raw materials classified as SARA 313 chemicals or Hazardous Air Pollutants (HAPs).

It offers a solution to printers who want to increase productivity without compromising the health and safety of their employees. BRIGL is the only wash on the market that effectively cleans conventional, heat-set, ultraviolet, electronic-beam, and co-cure inks, so that printers can use only one wash for an entire pressroom instead of the usual four to nine solvents. More important, unlike other "green" blanket and roller washes, BRIGL is easily implemented into the print production environment. Since BRIGL&#;s introduction in October , over 50 full-time users have switched to it, and the list keeps growing. Premier printers who took part in Amerikal&#;s trial phase of BRIGL reported prolonged roller life, reduced overall consumption, a reduction in pressroom odors, and essentially no hazardous waste streams from blanket and roller washes.

Printers also discovered that BRIGL could be used for manual and automatic wash-up procedures, reducing consumption by 50&#;70 percent compared with traditional washes and cutting overall costs. With over 1,200 customers, Amerikal has used its vision, innovation, and initiative to redefine the standard for pressroom chemistry. Amerikal is the first and only pressroom chemical manufacturer dedicated solely to developing products that offset petroleum use; preserve natural resources; eliminate hazardous waste streams; and reduce global warming, energy costs, and pollution.

Genetic Engineering of Saccharomyces Yeasts for Effective Production of Ethanol and Other Green Chemicals from Renewable Cellulosic Biomass: Ethanol is an effective, environmentally friendly, non-fossil transportation biofuel that produces far less pollutants than gasoline. Furthermore, ethanol can be produced from plentiful, domestically available, renewable cellulosic biomass. This reduces our nation&#;s dependency on imported oil, protects our energy security, and reduces our trade deficit. Furthermore, cellulosic biomass is renewable, available at low cost, and extant in great abundance all over the world, especially in the United States.

Cellulosic biomass is, therefore, an attractive feedstock for the production of ethanol-fuel and numerous other industrial products by fermentation. Although ethanol has been produced by the fermentation of glucose-based feedstocks with Saccharomyces yeasts since the pre-industrial age, the conversion of cellulosic biomass to ethanol presented a major challenge. This is because cellulosic biomass contains two major sugars (glucose and xylose), and the Saccharomyces yeasts cannot ferment xylose to ethanol.

Dr. Ho has developed genetically engineered Saccharomyces yeasts that not only ferment xylose but can also effectively coferment glucose and xylose to ethanol. The genetically engineered yeasts produce at least 30% more ethanol from cellulosic biomass than the non-engineered parent yeasts. Dr. Ho&#;s group has also recently found that their stable, metabolically engineered yeasts can repeatedly coferment glucose and xylose (using pure sugars or sugars from cellulosic biomass hydrolysates) to ethanol with high efficiencies for numerous cycles requiring very little nutrients. The technology outlined can easily be expanded to make yeast for the production of other important industrial products, such as lactic acid and citric acid, using glucose and xylose derived from cellulosic biomass as the feedstock.

Genetic Enhancement of an Anti-Freeze Protein: Traditional anti-icing/deicing agents are either propylene or ethylene glycol. These agents result in excessive biological oxygen demand (BOD) loading and are toxic to humans, mammals and aquatic species. The clean-up of sites contaminated with these deicers is expensive. For example, at Griffith AFB, NY, the use of glycols as a deicing fluid for aircraft has resulted in ground-water cleanup programs costing over $8.2 million. An Air Force policy has been issued banning future purchase of ethylene glycol. The Environmental Protection Agency (EPA) has recently passed regulations that require the construction of on-site collection and treatment facilities for spent deicing chemicals. Under these regulations, waste deicing fluid runoff will be classified as a non-storm water discharge which must have a low BOD and an individual permit if the BOD cannot be eliminated.

This project will develop deicing/anti-icing agents from antifreeze proteins characterized by a BOD substantially lower than the current agents. Initial research has indicated that Dendriodes canadensis, a protein found in insects, produces a freezing point depression that is 300 to 500 times the predicted value based on its molal concentration due to non-colligative properties. This project proposes to genetically alter the Dendriodes canadensis antifreeze protein (D. can. AFP) gene in order to enhance its freezing point depression capabilities and increase its ability to function as a deicing/anti-icing agent.

Development and use of a deicing/anti-icing agent that is non-toxic and characterized by a low BOD should reduce the costs of the management of deicing/anti-icing operations and minimize the potential environmental impacts from discharge of untreated deicing/anti-icing wastewater to aquatic systems.

Accomplishments to date include the amino acid sequence analysis and binding domain comparisons of the Dendriodes canadensis antifreeze protein with other published AFP sequences. The design, synthesis and conformational sequencing of the mutagenesis DNA oligonucleotides to be used to mutate the D. can. AFP gene. The cloning of the D. can. AFP gene DNA into the pALTER II mutagenesis cloning vector. The confirmation of the mutated sequences by DNA sequencing. The cloning of the mutant D. can. AFPs genes into the yeast, Pichia pastoris, and their insertion confirmed by PCR analysis. These clones have since been proven to be expressing an immunoreactive protein that is secreted into the media which confirms the presence of an AFP.

All Services and the commercial airline industry will be apprized of initial results. Successful candidates will be further tested by Service programs.

Gentle Power BleachTM: A Revolutionary Enzymatic Textile Bleaching System: Currently, the textile industry faces major challenges in managing its use of natural resources. Traditional textile processing has a substantial impact on natural resources and requires potentially hazardous materials. Textile wet processing (e.g., bleaching) is the most environmentally hazardous stage in the textile supply chain. Regulatory and consumer pressure support reducing the environmental impacts of textile production; the future of the textile industry depends on reduced impacts.

Huntsman Textile Effects and Genencor, a division of Danisco A/S, collaborated to introduce Gentle Power BleachTM (GPB), a first-to-market enzymatic textile pretreatment bleaching system. GPB uses Genencor&#;s PrimaGreenTM Eco White liquid enzyme formulation containing a bacterial arylesterase. This unique, proprietary enzyme catalyzes the perhydrolysis of propylene glycol diacetate (PGDA) to propylene glycol and peracetic acid at neutral pH over a wide range of temperatures. Genencor engineered the enzyme to favor the perhydrolysis reaction to peracetic acid over the hydrolysis reaction to propylene glycol. The generation of peracetic acid in situ sets the GPB system apart from other enzyme systems and traditional chemical bleaching systems.

Using Genencor&#;s enzyme formulation, Huntsman developed the GPB technology. Introduced in March , GPB perfectly prepares cotton and elastane blends for dying. GPB enables low-temperature, neutral pH bleaching of fabrics and replaces harmful chemicals such as caustic soda. Gentler processing yields softer, bulkier, higher-quality fabrics than traditional bleaching and also reduces cotton loss during processing by 50 percent. An environmental lifecycle assessment (LCA) shows that GPB has a marked advantage over traditional textile bleaching for cotton fabrics. Lower treatment and rinsing temperatures and fewer rinse baths can result in water and energy savings of up to 40 percent for GPB. The LCA results demonstrate at least a 20 percent benefit in most categories, including climate change, human health, ecosystem quality, and water use, relative to a traditional bleaching system.

Georgia-Pacific Mining Reagents That Improve Recovery, Reduce Wastes, and Conserve Water and Other Natural Resources: Froth flotation is a method of purifying mined ores from the waste minerals and clays inherent in the ore bodies. Froth flotation exploits the difference in the surface hydrophobicity of an ore and a waste mineral or clay to separate and purify the ore. During this process, air is dispersed in the slurry that contains the ore and wastes, forming bubbles to which the hydrophobic particles (ore) adhere. The hydrophobic particles are then carried with the bubbles into the froth layer whereas the hydrophilic particles (wastes) remain behind. Often termed slimes, the hydrophilic particles retain water. If they are carried along with the ore, they increase the energy required to dewater the product. In contrast, if too much of the ore remains in the slurry, it is disposed of with the waste or slimes.

Georgia-Pacific (GP) mining reagents improve the separation of ore from the associated waste, so less ore is wasted and less slime is recovered with the ore. The mining reagents act as depressors to help remove slimes and as coagulants to improve dewatering. As a result, significantly more water can be reused; the ore is easier to dry, and, therefore, resources, water, and energy are conserved.

Currently, in the United States, up to 30 percent of coal and 70 percent of potash are purified by flotation. Coal is a major source of energy, and approximately 53 percent of the electricity used in the United States is generated from the combustion of more than 1 billion tons of coal. Potash is commonly used as an agricultural fertilizer to supplement soluble potassium, which is one of the most essential elements required in large amounts for plants. This improved process helps to conserve natural resources including water, coal, potash, or other ores at the source as well as to reduce pollutants through increased energy efficiency at the mine site.

GEOSET NEO®: Low Emission Technology for the Metal Casting Industry: Foundries in the metal casting industry typically use organic polymers, known as binders, on sand to produce a variety of cores and molds. Although these organic binders allow high productivity, they also emit volatile organic compounds (VOCs) and hazardous air pollutants (HAPs). Because the binders cause problems with worker health and safety, foundries must use expensive abatement equipment such as odor control filters and scrubbers. Inorganic binders can address these problems, but previous inorganic binders performed poorly, produced more core and mold scrap, and reduced productivity. Most were limited to nonferrous applications.

Ashland has developed a low-emission, inorganic binder technology for both ferrous and nonferrous applications in the metal casting industry. Their GEOSET NEO® (Negligible Emissions and Odor) inorganic binders are aluminosilicate gels that are waterbased and heat-cured. They have excellent core and mold rigidity, good dimensional stability, and high hot strength. There is little concern for human exposure to VOCs or HAPs before, during, or after the casting process. GEOSET binders release virtually no nuisance odors during core or mold production. During the casting process, the decomposition products from GEOSET binders are water vapor and carbon dioxide (CO2). As a result, foundries can both reduce or eliminate their costly abatement equipment and provide a cleaner atmosphere for employees and the environment nearby.

Ashland expects GEOSET NEO® binders to have a profound impact not only on foundries, but also on the environment. Substituting organic binders with inorganic binders can reduce a foundry&#;s emissions by up to 90 percent and assist in compliance with environmental regulations. GEOSET can eliminate most nuisance odors and smoke that would otherwise drift into communities near a foundry. Due to the rising price of petroleum, inorganic binders are comparable in cost to organic binders. During and , Ashland implemented and cultivated joint development programs with customers.

GF-120TM NF NaturalyteTM Fruit Fly Bait: Tephritid fruit flies, including the Mediterranean fruit fly, are important quarantine pests that can devastate fruit and vegetable production and limit the transportation of produce. Previously, a wide range of insecticide baits had been used to control these fruit flies; the results were often inconsistent, however, due to a lack of understanding of fly attractiveness, feeding biology, and quality control. The active ingredients in these baits were organophosphates. The organophosphates were generally used at rates as high as 0.5&#;1.0 pounds per acre to overcome their inadequacy. The International Atomic Energy Association and others had developed irradiated sterile insect techniques (SIT), but this tool works best with low insect populations. An improved bait system using an environmentally sound active ingredient was needed (1) to reduce population levels so that sterile insect and other integrated pest management solutions could be used and (2) to protect fly-free regions such as the United States.

Dow AgroSciences had already developed spinosad, a new reduced-risk insecticide active ingredient that was successful in spray applications. Dow AgroSciences combined its project management, industrial manufacturing, quality control, and formulation science skills with USDA&#;s knowledge of fruit fly biology and behavior. Together, Dow AgroSciences and USDA developed a superior bait technology, GF-120 NFTM, to protect fruits and vegetables from the Mediterranean fruit fly and similar pests. This is the first bait plus active ingredient (spinosad) that contains only organically acceptable components; it is so attractive to flies that farmers need less than 0.003 pounds of spinosad per acre. Between and , farmers used GF-120 NFTM to treat over six million acres. GF-120 NFTM is now the fruit fly bait of choice in much of the world.

GlaxoSmithKline&#;s Eco-Design ToolkitTM: GlaxoSmithKline (GSK) developed the Eco-Design ToolkitTM to provide bench-level chemists and engineers with easy access to green chemistry information so they could design-out hazardous chemicals, identify alternative chemistries and technologies, and implement best practices. The Eco-Design ToolkitTM allows GSK to bring products to market more cost-effectively because it enables the company to produce medicines with fewer environmental, health, and safety (EHS) impacts throughout their lifecycle.

GSK developed its Eco-Design ToolkitTM following state-of-the-art scientific advancements and standards. It currently has five modules: a Green Chemistry and Technology Guide to applying green chemistry and engineering principles; Materials Guides on a wide range of solvents and bases with information and EHS rankings that include the lifecycle impacts of solvent manufacture; Fast Lifecycle Assessment for Synthetic Chemistry (FLASCTM) for streamlining evaluations of environmental lifecycle and measuring green metrics including mass efficiency; a Green Packaging Guide to evaluating and selecting packaging that includes an environmental assessment tool; and a Chemicals Legislation Guide that identifies legislation phasing out hazardous substances (chemicals of concern). Each module is designed to ensure that GSK considers all EHS impacts from the manufacture of raw materials through the ultimate fate of products and wastes. The toolkit is accessible through the GSK intranet.

Methodologies of most of the tools are published in peer-reviewed scientific journals. Tools such as the Solvent Guide, FLASCTM, or the Green Technology Guide are first in their class and are recognized by academic and industrial groups for their innovation as leading the green design of pharmaceuticals. GSK continues to update the toolkit to integrate new scientific advances and regulatory information.

GSK routinely uses the toolkit to develop new products. During , the mass percent of chemicals of concern across all products decreased nine-fold and the estimated average lifecycle impacts were reduced four-fold as compounds moved to the last stage of development.

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Glycerin to Epichlorohydrin Process: How Green is my Epichlorohydrin?: Epichlorohydrin is a large-volume, commodity chemical used mostly to manufacture liquid epoxy resins. Estimated worldwide capacity for epichlorohydrin was two billion pounds in . The predominant manufacturing process today is a multistep route using petrochemical-derived propylene and electrochemically generated chlorine as the primary feedstocks. This route has significant environmental issues including the formation of chlorinated byproducts and large amounts of wastewater. Further, the route incorporates only one of the four chlorine atoms it uses into the final product; the other three appear as aqueous chloride waste or hydrogen chloride.

The Dow Glycerin to Epichlorohydrin (GTE) process exploits the increasing availability of low-cost glycerin, which is a byproduct of biodiesel production from renewable seed oils. Likewise, it uses hydrogen chloride, a byproduct from several commodity-scale manufacturing processes such as the incumbent epichlorohydrin process, vinyl chloride, or isocyanate manufacture; hydrogen chloride is often neutralized and wasted. The GTE process uses a simple, two-step route with a carboxylic acid catalyst to synthesize epichlorohydrin. The key innovation is the use of hydrogen chloride at elevated pressure. The resulting elevated liquid-phase hydrogen chloride concentration drives the reaction to high conversions to the desired dichlorohydrins without removing the coproduct water from the reaction. Water in the reaction prevents the formation of chlorinated byproducts.

The GTE route has additional environmentally desirable attributes, including more efficient use of chlorine, formation of fewer chlorinated byproducts, and less production of aqueous chloride waste. The process will reduce wastewater by over 70 percent and reduce the formation of organic byproducts by over 75 percent. It is significantly more energy efficient: it uses 30-percent less steam and uses less energy to make chlorine and caustic. Commercialization of this economically and environmentally advantageous process is planned for , when it will produce up to 150,000 metric tons per year of highly pure epichlorohydrin.

Glycerol tert-Butyl Ether (GTBE): A Biofuel Additive for Today: Current petroleum-based additives for boosting octane in gasoline improve the miles-per-gallon (mpg) of vehicles, but not significantly. The traditional fuel additive, methyl tert-butyl ether (MTBE), has been phased out in many states due to its toxicity and has no obvious replacement. Glycerol tert-butyl ether (GTBE) is a high-value, biobased fuel additive that improves the combustion and efficiency of petroleum and biobased fuels. CPS Biofuels has developed a process to make GTBE from waste glycerol, a low-value, high-volume byproduct of biodiesel production. CPS makes GTBE by acid catalysis of glycerol and isobutylene or other appropriate olefins followed by fractional distillation. Sulfuric acid is the preferred acid catalyst. Although GTBE can have up to three ether linkages, it is preferable to have at least one or two free hydroxyl groups to hydrogen-bond with ethanol and help lower its vapor pressure. GTBE is a biobased, nontoxic, biodegradable alternative fuel oxygenate and octane booster that helps fuel combust more completely and improves fuel efficiency with cleaner resulting emissions.

It both improves gas mileage and reduces greenhouse gas (GHG) emissions; with petroleum diesel fuels, it reduces up to 35 percent of particulates. It is useful as a fuel system icing inhibitor (FSII) in military (JP-8) and commercial (Jet A) kerosene-type jet fuel. GTBE can replace PRIST®, the existing jet fuel FSII, which is severely detrimental to human health. CPS is focusing on improving the efficiency of the E10 and E15 blends of biofuels for the existing energy infrastructure. GTBE fuel additives are compatible with the U.S. energy infrastructure, providing tremendous advantages over alternatives that require new production facilities or new engines for vehicles. CPS recently completed manufacturing trials, and testing of GTBE showed extremely efficient, essentially emission-free combustion and an octane rating over 120. GTBE has been commercially available as CPS PowerShotTM since January .

Green Card: A Biopolymer-Based and Environmentally Conscious Printed Wiring Board Technology: Printed wiring boards (PWBs) have become ubiquitous in our society and are found in an ever-expanding range of industrial and consumer products including computers, VCRs, cameras, and automobiles. The demand for PWBs is increasing rapidly- the world market for PWBs has increased at an average rate of $2 billion per year since to a current value of over $25 billion. PWBs are composites that are generally formed from an epoxy or novolac resin coated on fiberglass or paper sheets that are laminated in multilayer stacks that are interleaved with suitably patterned copper sheets. PWBs provide both the substrate for physically attaching electrical components, as well as copper traces that provide electrical connectivity between the components. Due to the use of highly crosslinked thermosetting resins, the laminates form intractable composites that cannot be recycled by melting and reforming in the same manner as thermoplastic polymers.

Of increasing concern is the manufacture and disposal of the more than 150 million square meters of laminate that are produced globally each year. The resins currently in use for PWB manufacture are generated entirely from petroleum-based stocks. Natural products, especially if used in a form similar to that in which they occur in nature, generally take less energy to produce than their petroleum-based counterparts, hence replacement of part or all of the current raw materials could result in significant energy savings. Both energy and effluent (solid, liquid, or gaseous) reductions may be possible by choosing appropriate biobased raw materials.

New resin compositions that incorporate wood or plant resources (available in commercial quantities) were investigated. The technical objectives of this program culminated in the development and optimization of the use of lignin- a waste byproduct of paper manufacture- for the fabrication of several PWB demonstration vehicles to prove manufacturing feasibility. Resins that included as much as 50 to 60 wt% lignin were formulated to meet the primary requirements for printed circuit board physical and electrical properties. The utility of lignin in epoxy-based resins was demonstrated for a range of current and advanced applications. Pilot scale manufacture of resin and laminates using these formulations was accomplished on standard manufacturing equipment using current processing techniques and chemicals. In addition, the lignin/epoxy formulations have financial incentives that increase their desirability due to the inexpensive nature of lignin as a raw material.

A lifecycle analysis was performed, showing that the environmental benefits of a lignin-based resin system included reductions in energy usage, solid wastes, air and waterborne emissions, and "greenhouse gases" such as CO2from petroleum based sources, methane, and nitrogen oxides. Due to the lower energy requirements for production of natural raw materials, fuel usage for resin production can be cut by up to 40% by converting from standard epoxies to lignin-based resins. Lignin resins can be cast from ketone/alcohol or ketone/propylene glycol methyl ether acetate solvents, which would reduce the usage of methyl ethyl ketone (a SARA listed chemical) and acetone in PWB manufacture. Disposal concerns are also reduced, as incineration will produce reduced levels of greenhouse gases, and boards submitted to compost/landfill will have increased opportunity for biodegradation due to fungi potentially present in that environment that can break down lignin.

Green Chemistry for Energy Conservation and Indoor Environmental Quality: Ultraviolet photocatalytic oxidation (UVPCO) mimics naturally occurring atmospheric processes to improve indoor environmental quality (IEQ) by reducing levels of volatile, particulate, and biological contaminants. In UVPCO modules, UVC light activates nanoparticles of a titanium dioxide catalyst coated on a pleated flexible mesh support to initiate photocatalytic reactions. These reactions oxidize volatile organic compounds (VOCs), primarily to water and carbon dioxide (CO2); they also agglomerate fine particles and inactivate bioaerosols. UVPCO modules are integrated with air filters and instrumental controls into customized engineered systems that are more energy- and cost-efficient than conventional processes, such as carbon adsorption or particulate filtration. The scientific validity of UVPCO technology has been proven in environmental test chambers and at field test sites.

UVPCO technology is expected to replace carbon adsorption, which requires media derived from carbonization of petroleum feedstocks at high temperatures. UVPCO can destroy contaminants both in air circulated within buildings and in air exhausted to the atmosphere. Because UVPCO systems reuse indoor air for more cycles, they reduce the introduction of contaminants from outside air to indoor air. This broadly applicable technology offers benefits to human health and the environment by treating building environments to reduce air contaminants, thereby reducing ventilation demands and conserving energy.

Ingenuity IEQ, a small business in Midland, MI, incorporates UVPCO modules manufactured by Genesis Air into customized engineered systems that they design, install, and maintain in a variety of new and existing buildings. Genesis Air, Inc., a small business in Lubbock, TX, develops unique UVPCO modules that are generally applicable to healthcare, homeland security, LEEDTM green building systems, and ASHRAE High-Performance buildings in institutional, commercial, and governmental facilities within the United States. Ingenuity IEQ is positioning UVPCO, marketed as GAPTM technology, into new and existing systems to ensure proper residence time and effectiveness for optimized air purification.

Green Chemistry for Industrial Coatings: The conventional industrial coating process is pollution-, time-, space- and energy-intensive. In a departure from both solvent-based traditional coatings and newer powder coatings that require substantial heat to cure, Ecology Coatings&#;s LiquidNTM coatings are sprayable, 100 percent solids formulations that cross-link to form a durable barrier when exposed to ultraviolet light. They offer abrasion resistance, moisture resistance, and durability equal to or better than that of conventional waterborne, solvent-based, or powder coatings. The LiquidNTM coatings can be precision-sprayed at ambient temperatures, enabling them to integrate easily into existing finishing processes. Requiring only a few seconds of light exposure to cure, these pioneering coatings reduce time up to 99 percent, energy use up to 75 percent, and space on the manufacturing line up to 80 percent. These solvent-free coatings also virtually eliminate emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs), in turn reducing associated regulatory burdens.

In addition to presenting Ecology Coatings with clear economic and environmental advantages over conventional industrial coatings, LiquidNTM coatings have unique characteristics that enable them to serve an entirely new spectrum of applications. Because the coatings contain no liquid and do not require heat to cure, they are particularly well-suited for consumer electronics and other sensitive products. Unlike existing coatings that are generally limited to one or two applications, LiquidNTM coatings are suitable for plastics, metals, composites, paper, biodegradable materials, and more. Ecology Coatings&#;s innovative coatings technology is capable of propelling the coatings market, an integral piece of the U.S. manufacturing industry, into America&#;s greener future. Ecology Coatings has licensed its technology to DuPont Performance Coatings and Red Spot, which is a leader in the field of UV-curable coatings.

Green Chemistry in Action: A Remarkably Efficient and Sustainable Synthesis of the HIV Integrase Inhibitor, RaltegravirTM: ISENTRESS® (raltegravirTM) is the first medication to be approved in a new class of anti-retroviral therapies called integrase inhibitors. It represents a critical advance for the treatment of HIV/AIDS. Merck developed the initial route to raltegravirTM rapidly in response to a fast-paced clinical development program. This route produced enough of the drug for development and initial commercial launch. As Merck required quantities of this drug in the thousands-of-kilograms range, however, it became clear that the company needed a more efficient and sustainable route.

Merck&#;s process redesign resulted in a remarkably efficient, environmentally sustainable, eight-step process for raltegravirTM. The revised process combines a highly innovative, atom-economical Michael addition/cycloisomerization sequence used in the first-generation route with exceptional streamlining of the final steps. The improved process increases overall yield by 35 percent, reduces total waste by 70 percent, eliminates toxic reagents, and reduces the manufacturing cost. The process replaces methyl iodide, a well-known carcinogen, neurotoxin, and respiratory toxicant, with trimethylsulfoxonium iodide, an innovative, substantially less toxic substitute. The optimized process requires no special equipment.

Overall, Merck reduced the e-factor or process mass intensity (PMI) from 314 for the original process to 97 for the new process. This is a remarkable reduction of 12 PMI per step. The waste reduction is equal to 217 metric tons per metric ton of raltegravirTM manufactured. Given the required dose of 800 milligrams per person per day of ISENTRESS®, the waste reduction translates to 140 pounds per person per year compared to the original manufacturing route. Merck completely developed the revised process and introduced it into production at manufacturing scale in April . Because Merck converted to its new optimized route shortly after it launched ISENTRESS®, the benefits of the greener process will accrue throughout the lifecycle of this important medicine.

Green Chemistry in the Manufacture of Thioglycolic Acid: Arkema Inc. has manufactured thioglycolic acid (TGA or mercaptoacetic acid) at its plant in Axis, AL for over 20 years. TGA is used as an industrial intermediate, a component of cosmetics, and a component of products to treat hides and leather. Arkema&#;s traditional process included hydrogen sulfide (H2S) as a feedstock. H2S is a poisonous, flammable, colorless gas that is regulated as an air pollutant, a water pollutant, and a hazardous waste. Because of its requirements for high-purity H2S feedstock, Arkema was buying H2S from a source in Canada and transporting over 4 million pounds of pressurized, liquid H2S by railcar to Alabama each year.

Arkema developed and implemented a beneficial process change that replaced the H2S in its manufacturing process with sodium hydrosulfide (NaSH). NaSH is safer for workers, is subject to fewer air, water, and waste regulations, is comparable to H2S in price, and is readily available in consistently high purity. Further, changing to NaSH involved little or no change in facility air or wastewater permits or disposal methods for spent materials. The substitution of NaSH solution for H2S gas in the TGA process allowed the Alabama plant to eliminate the cross-country transportation of millions of pounds of an extremely hazardous and toxic chemical, reduce the risk of accidental release of a toxic chemical, and lessen risk management activities at the plant. The major advantages of this substitution were improved worker safety and a reduced risk of environmental releases. At the same time, Arkema realized higher production yields of 1 million pounds per year. In , Arkema finished switching over to NaSH and made engineering modifications to increase its production capacity.

Green Chemistry in the Redesign of the Celecoxib Process: Pfizer has redesigned its celecoxib manufacturing process with green chemistry objectives as some of the project&#;s primary goals. The results are dramatic environmental and worker safety improvements in the manufacture of the active ingredient in the medicine, Celebrex®. These improvements followed the elucidation of two unprecedented reaction mechanisms responsible for the formation of isomeric impurities whose presence required a subsequent recrystallization with its concomitant loss of yield and increased expense. Celecoxib made by Pfizer&#;s new process is pure enough to permit final isolation directly from the reaction mixture; such isolations are very rare in the pharmaceutical industry. Pfizer&#;s new mechanistic understanding increases the process efficiency significantly with respect to raw materials, solvents, energy, and waste.

The environmental and safety improvements are also significant. Compared to its initial process, Pfizer&#;s new process (based on production volume) reduced total waste (excluding water) from 8.9 million to 2.4 million kilograms per year (waste reduced from 23.4 to 6.3 kilograms per kilogram celecoxib). In total, Pfizer has eliminated 5,200 metric tons per year of organic solvents. Pfizer has also completely removed tetrahydrofuran and 35 percent hydrochloric acid (212 metric tons per year). Organic solvent washes during isolation have been partially replaced by water. In addition, raw materials have been reduced by over 150 metric tons per year. By eliminating the recrystallization and using the heats of reaction and other temperature parameters judiciously, Pfizer saves over 4 billion Btu per year. Pfizer has also improved worker safety by reducing the number of unit operations required per batch and improving the process payload (product produced/reactor volume), resulting in the need for fewer batches to fulfill demand.

The U.S. FDA has approved Pfizer&#;s improved manufacturing process for celecoxib; more than 50 similar agencies worldwide have also approved the new process. These regulatory authorities now require Pfizer&#;s new process for all commercial pharmaceutical manufacture of celecoxib.

Green Chemistry Process for the Large-Scale Manufacture of Polyamino Acids: Polyamino acids have properties that mimic proteins and make them ideal for targeted drug delivery. They are water-soluble, selective, biodegradable, low-toxicity molecules with a wide range of molecular weights. Their production, however, involves both unstable, intermediate amino acid N-carboxyanhydrides (NCAs) and polymer processing. Traditionally, these steps require large quantities of hazardous chemicals including phosgene, hydrogen bromide&#;acetic acid, acetone, and dioxane. Sigma-Aldrich has developed novel manufacturing processes for polyamino acids that minimize hazardous chemicals, improve efficiency, and increase product quality.

For NCA production, Sigma-Aldrich eliminated NCA recrystallizations and reduced manufacturing runs by over 30 percent. They reduced phosgene and tetrahydrofuran by 30 percent and ethyl acetate and hexane by 50 percent, which reduced hazardous waste. Finally, they increased consistency in quality and yield. Sigma-Aldrich also applied green chemistry to manufacturing poly-l-glutamic acid, a major drug-delivery polymer, which requires hazardous operations with hydrogen bromide&#;acetic acid or hydrogenation as well as highly flammable solvents.

Replacing a benzyl protecting group with an ethyl group allowed them to replace hazardous chemicals with water-based chemicals, decrease cycle time by over half, decrease energy use and greenhouse gas emissions, and improve the scaleup potential 10-fold. Sigma-Aldrich achieved similar savings with new processes for polylysine polymers and polyamino acid copolymers.

For polylysine polymers, Sigma-Aldrich used only half the previous amount of hazardous chemicals (dioxane, hydrogen bromide&#;acetic acid, and acetone), but increased the yield from 10&#;30 percent to 43&#;53 percent. Sigma-Aldrich halved production runs, which is saving hundreds of gallons of hazardous chemicals, generating less waste, and saving energy. They also switched polyamino acid copolymer production to water-based systems that eliminate benzyl bromide, a hazardous lachrymator byproduct. Sigma-Aldrich believes its contributions will lead to efficient chemotherapeutic treatments for diseases such as cancer, multiple sclerosis (MS), and diabetes and pave the way for greener chemical industry practices.

Green Chemistry through Function-Oriented Synthesis, Step Economy, and Ideal Synthesis: For decades, Professor Wender has pioneered the development of chemical methods for preparing biologically important molecules and has advanced the concepts of ideal synthesis and step economy. Recently, he has developed Functional Organic Synthesis (FOS), a multi-faceted, inclusive approach. FOS simplifies biologically active natural products to create new target structures that are amenable to preparative organic synthesis with greater efficiency and less waste while maintaining or improving their original activity. Professor Wender has revolutionized the preconceptions of other chemists by inventing new synthetic reactions that rapidly and efficiently raise the complexity of simpler starting materials to product-like intermediates in just a few steps. Professor Wender has impressed the chemistry community with his arene-olefin photocycloaddition, cyclopropane and other rearrangements, and numerous so-called "impossible" annelation reactions (e.g., [5+2], [2+2+2+2], [5+2+1], [4+4]).

FOS has not only guided the design of improved drug-like targets and their more efficient syntheses, but has also led to new reactions that achieve those goals better and with less waste. Recent examples of FOS from his laboratory include (1) simple arenes that modulate protein kinase C and mimic the more complex phorbols; (2) simplified enediyne compounds for cancer treatment; (3) simplified bryostatin analogs that contain only key pharmacophores, but have improved potency; (4) laulimalide analogs with simplified structures that remove the inherent functional instability of natural laulimalide, thus rendering them more desirable as drug candidates; (5) the design, synthesis, and optimization of polyarginine drug transporters to improve potency and circumvent multidrug resistance pathways in cancer cells; and (6) an efficient "reverse" process to transform a more plentiful natural product, phorbol, into prostratin, an important HIV drug adjuvant that activates the latent virus rendering it more available to conventional drug therapy. Professor Wender&#;s FOS concept has many facets, any of which can lead to greener chemistry in drug discovery.

Green Chemistry Through the Use of Supercritical Fluids and Free Radicals: Professor Tanko explored the use of supercritical carbon dioxide (SC-CO2) as a replacement for many of the toxic and/or environmentally-threatening solvents used in chemical synthesis. This research demonstrated that SC-CO2 is a viable, environmentally benign alternative to a variety of health or environmentally hazardous solvents and that there are also numerous advantages from a chemical perspective associated with the use of SC-CO2 . The research led to the development of a new, environmentally friendly chemical process for hydrocarbon functionalization and C-C bond formation. SC-CO2 is especially attractive because its critical parameters (temperature and pressure) are moderate, thereby permitting access to the supercritical state without a disproportionate expenditure of energy. The newly developed hydrocarbon functionalization accomplishes (in a single, high-yield step) a transformation which would normally require multiple steps and the use of toxic reagents or strong acids and bases. This reaction should scale up readily for large-scale (or industrial) applications.

Green Composites: Environment-Friendly and Fully Sustainable: Fiber-reinforced composites have many applications due to their favorable mechanical properties. Most composites on the market today, however, use nondegradable polymeric resins and fibers derived from petroleum. Professor Netravali uses plant-based, yearly renewable feedstocks to fabricate fully sustainable and environmentally friendly green composites. His chemically modified soy proteins have mechanical and thermal properties that make them suitable for use as resins. He reinforces these resins with plant-based fibers, yarns, or fabrics to make fully sustainable, environment-friendly, green composites. After use, his green resins and composites biodegrade fully during composting.

Soy protein is commercially available as isolate (SPI), concentrate (SPC), and flour (SF); it contains 18 amino acid residues, many of which have reactive amine, hydroxyl, or carboxyl groups. Soy protein can be processed into a lightly cross-linked resin, mainly through its cystine residues. Dehydroalanine residues formed from alanine can react with lysine and cystine to form additional cross-links. The resulting resin is too weak and brittle, however, for use in composites.

Professor Netravali has chemically modified SPC and SPI with Phytagel®, a linear D-glucose/D-glucuronic acid/L-rhamnose (2:1:1) tetrasaccharide, to form complex, interpenetrating network-like (IPN-like) structures that are also strongly hydrogen-bonded. Phytagel® forms a strong cross-linked gel with soy protein by ionic and hydrogen bonding in the presence of the mono- or divalent ions (ash and mineral) present naturally in soy protein. The resulting structure has excellent mechanical properties. Professor Netravali has obtained even better mechanical and thermal properties by dispersing exfoliated nanoclay particles in the IPN-like resin to form nanocomposite resins whose properties are better than those of common epoxy resins. He has used his modified soy resins with plant-based fibers such as flax and ramie to form green composites with excellent mechanical properties. Currently, Professor Netravali is working with Nissan, USA to mass manufacture green composite panels for automobile interiors.

Green LogicTM: Chitosan-Enhanced Paint Detackifier: GREEN LOGICTM is a liquid, chitosan-containing, paint denaturant technology that provides an alternative to traditional chemistries based on melamine&#;formaldehyde or acrylic acid. Paint denaturants, also referred to as "paint detackifiers", are added to the water curtain circulating in downdraft, water-washed paint spray booths to render oversprayed paint non-sticky. In traditional, wet paint spraying operations used in automotive original equipment manufacturing (OEM), only 50&#;80 percent of the paint is transferred to the vehicle; the residual 20&#;50 percent remains in the air until it is trapped in the circulating water curtain. The chemicals added to the water curtain detackify, coagulate, and flocculate this oversprayed paint, allowing it to be removed from the water later. The available melamine&#;formaldehyde-based detackifiers contain small amounts of free formaldehyde, a known carcinogen. The alternative acrylic acid based paint denaturants rely on two nonrenewable petroleum-based feedstocks: ethylene and propylene.

PPG derives its GREEN LOGICTM technology from the chitin of crab, lobster, and shrimp shells that are waste products of food production. Chitosan, the main component of GREEN LOGICTM technology, is poly(glucosamine), a glucosamine polysaccharide structurally similar to cellulose. PPG&#;s technology requires less overall tackification chemical and reduces the use of sodium hydroxide by 87 percent. Chitosan has been demonstrated to have antimicrobial properties and, therefore, it decreases the use of hazardous biocides. GREEN LOGICTM exhibits superior foam control, which reduces environmental stack emissions. The GREEN LOGICTM technology has performed as well as and in some cases better than traditional products used in this area while providing significant cost savings to customers and reducing their carbon footprints. Financial data from a number of customers show a 40-percent savings in wastewater treatment (approximately 5.5 million gallons per year per plant) and a 28-percent overall process savings. Seventeen automobile manufacturing plants in the United States are currently using this technology.

Green pH Electrodes: Glass tubing containing 20&#;30 percent lead is traditionally used to manufacture pH electrodes as it has the ideal workability and coefficient of expansion to easily fuse to the glass pH membrane tips. The solder used to join the electrodes&#; cables and connectors contains lead as well. Mercury&#;mercurous chloride reference systems are also currently used in some pH electrodes. Both lead and mercury create problems with electrode disposal; they are known to be detrimental to the environment and, thus, products containing these heavy metals must be disposed of as hazardous waste.

Thermo Fisher Scientific is now using a lead-free glass and lead-free solder to create completely lead-free pH electrodes. The replacement glass uses a nickel&#;iron alloy metal seal instead of lead to achieve the necessary properties. The cost of this lead-free glass decreased recently so that it became a feasible replacement for lead-containing glass without increasing the cost of the electrode. Eliminating lead from all pH electrodes in the world market would save more than 2,000 kilograms of lead annually.

Some pH electrodes contain a mercury&#;mercurous chloride reference junction that is known to be very stable, even in difficult sample matrices. Testing has shown that a silver&#;silver chloride reference held in a stable polymer-based electrolyte gives the same performance, thus eliminating the need for mercury in the electrode. Eliminating mercury from electrodes prevents them from requiring disposal as hazardous waste and also prevents the risk of exposing the user to mercury if the electrode breaks.

These new pH electrodes will have performance and cost comparable to current lead- and mercury-containing electrodes, but will be disposable as regular trash. Thermo Fisher Scientific manufactured and tested its first prototype pH electrodes using completely lead-free glass in .

The main raw materials for Green PolyurethaneTM are polyoxypropylene triols and epoxidized vegetable oils. NTI also uses primary aliphatic diamines prepared by biomimetic synthesis in its production of Green PolyurethaneTM. Green PolyurethaneTM is a potential replacement for current, isocyanate-based polyurethanes, especially those polyurethanes in foams and coatings that contain free isocyanates in aerosol form after polymerization. Green Polyurethane&#;sTM unique formulation combines the best mechanical properties of polyurethane with the chemical resistance properties of epoxy binders. Green PolyurethaneTM coatings contain no volatile organic compounds (VOCs).

They are solventless, 100 percent solids-based, 30&#;50 percent more resistant to chemical degradation, 10&#;30 percent more adhesive with some substrates, and 20 percent more wear-resistant. These coatings can also be applied on wet surfaces and will cure in cold conditions. Insulating foam made from Green PolyurethaneTM provides energy savings of more than 30 percent, has one of the highest R values per inch of all insulation materials, does not require a primer, and has greater adhesiveness. In EPA added Cycloate A, a key binder ingredient in Green PolyurethaneTM, to the Toxic Substances Control Act (TSCA) Inventory following Premanufacture Review. NTI submitted a Premanufacture Notice under TSCA for its proprietary hydroxyalkyl urethane modifier (HUM). Also in , Nanotech Industries began commercializing its hybrid non-isocyanate polyurethane UV-resistant coating technology.

Green Primaries: Environmentally Friendly, Sensitive Explosives: Initiating devices use primary explosives (i.e., primaries) to detonate main charge explosives. The synthetic chemistry "holy-grail" in energetic materials has been the search for environmentally benign alternatives to replace toxic mercury fulminate, lead azide, and lead styphnate in primaries. Detrimental effects on the environment and personnel safety from primaries based on toxic mercury and lead have made their replacement essential.

Dr. Huynh at Los Alamos has created green primaries based on 5-nitrotetrazolato-N2-metalates that contain iron or copper. These green primaries are coordination anions charge-compensated by environmentally benign cations. They combine superior explosive performance with greatly improved health and safety conditions during synthesis, manufacturing, and use. They have many national security and commercial applications.

The U.S. Department of Defense requires environmentally friendly primaries to meet six criteria. They must be insensitive to moisture and light, sensitive to initiation but not too sensitive to handle, thermally stable to at least 200 °C, chemically stable for extended periods, and devoid of toxic metals and perchlorate. Dr. Huynh&#;s green primaries are the only primaries known to fulfill all six criteria. Green primaries give quantitative yields without purification or recrystallization, so they can be manufactured quickly with lower expenses for waste disposal.

The benefits of green primaries include safe, inexpensive manufacture and transport; elimination of mercury and lead contamination; great versatility in, and control over, initiating sensitivities and explosive performance; elimination of toxic waste; and release of only innocuous byproducts upon detonation. The benign detonation byproducts prevent chronic lead exposure to civilians and military personnel. Green primaries are safely prepared in, and desensitized by, water or ethanol, so toxic fumes and solvents are eliminated during preparation. Green primaries eliminate the potential for accidental explosions, saving lives. Finally, they reduce costs for specialized safety equipment, transportation, and liability insurance.

Three patent applications have been filed; all three will be licensed exclusively so that commercialization can begin.

Green Process of Unfolding Soy Protein Polymers for Green Adhesives: About 20 billion pounds of adhesives are used annually in the United States for applications including wood products, foundries, packaging, and labeling. These adhesives are mainly petroleum-based. Industry is seeking biobased adhesives and coatings, but enabling technologies are lacking. On the other hand, the byproducts of the current annual production of soybean biodiesel and corn ethanol include about 90 billion pounds of low-cost, protein-based meals aside from food and feed uses.

Most proteins contain both hydrophobic and hydrophilic regions. Hydrophobic interactions are a dominating factor in protein folding, unfolding, aggregation, gelling, self-assembly, adhesion, and cohesion. Hydrophobic regions are often buried inside the complicated protein molecule, however.

Professor Sun&#;s technology unfolds protein molecules with 0.5&#;5 percent nonhazardous agents such as urea, detergents, organic&#;inorganic salts, and pH-adjustment agents such as sodium hydroxide (NaOH) and hyrdrochloric acid (HCl). As the proteins unfold, some of their covalent and hydrogen bonds break and form individual polypeptides. Because hydrophobic groups are now exposed on their surfaces, the resulting polypeptides become surface-active and interact with other hydrophobic polymers, cross-linking agents, and chemicals. Potential applications include adhesives; surfactants; coatings; medical materials such as tissue engineering, drug delivery, and pharmaceuticals; thickeners and binders for food and animal feed; and cosmetic products. This technology makes high-value products from the coproducts of biofuel production and, thus, can have great impacts on bioenergy and the environment. It will replace at least 6 billion pounds of hazardous materials including adhesives based on formaldehyde, vinyl acetate, isocyanine, and acrylic acid. The performance of Professor Sun&#;s adhesives is superior or similar to urea&#;formaldehyde, phenol&#;formaldehyde, and many other synthetic, latex-based adhesives.

Dr. Sun&#;s adhesive technologies are in the pipeline for commercialization. Biodegradable, edible feed containers for livestock were commercialized in . One company has licensed the technology for pet food binders; others are evaluating samples for a variety of uses.

Green Product and Munitions Compliance Analytical Systems: Until recently, manufacturers and regulatory agencies were restricted to qualitative, generic, and intuitive considerations of green chemicals and products (e.g., less harmful to human health and the environment) because no one had defined quantitative criteria for them. Chemical Compliance Systems has overcome this deficiency by compiling more than 75,000,000 data elements for over 210,000 chemicals and 250,000 products over the past 20 years.

They have synthesized these data into quantitative green chemical and product ratings with their Green Products Compliance Analytical System (GP-CAS) and their Green Munitions Analytical Compliance System (G-MACS). G-MACS also uses the MIDAS munitions characterization database from the U.S. Army Defense Ammunition Center. Both GP-CAS and G-MACS are based upon 46 green chemical criteria, each normalized on a scale of 0% (least green) to 100% (most green). These criteria encompass a broad spectrum of ecological, health, and safety hazards.

Both of these systems also identify which of 475 state, federal, and international regulatory lists include each chemical constituent of a product. Both systems can complete green analyses in 10-30 seconds. Any industry, facility, or location can utilize these systems, which have been available on the Internet since November . GP-CAS and G-MACS can reap economic benefits throughout the product lifecycle. Chemical Compliance Systems can readily customize either system for special requirements and maintain confidentiality. Incorporation of these green analyses into complementary analytical systems is underway (e.g., their MSDS retrieval and manufacturing&#;import&#;export systems). No other capabilities of this type currently exist.

Green Sense? Concrete: Concrete is the most widely used, versatile building material in the world. It uses raw materials such as Portland cement and water (cement paste) as glue to hold fine and coarse aggregates together, creating a solid material for constructing buildings, houses, and roadways. Portland cement manufacturing requires so much energy that it produces a reported 5 percent of the world&#;s carbon dioxide (CO2) emissions according to the Portland Cement Association. Although the CO2-equivalent emissions, or carbon footprint, of products like concrete are often used as the only measure of environmental impacts, this information alone may produce misleading conclusions because the mining of aggregates also depletes natural resources. Considering several environmental impacts and rigorously measuring the comprehensive environmental impact and lifecycle costs of products allow more informed and science-based decisions on the most sustainable solutions.

BASF has developed a series of Glenium® chemical admixtures for use in concrete for multiple applications. The Glenium® chemical admixtures are engineered and carefully formulated products containing an aqueous solution of dispersants based on polycarboxylate ether chemistry. The aqueous Glenium® admixtures are nontoxic, nonhazardous, and nonflammable. These admixtures, when combined with alternative raw materials in concrete mixes, make up Green Sense? Concrete. Glenium® admixtures allow BASF to replace CO2-intensive Portland cement with traditional waste materials such as fly ash, slag, and cement kiln dust.

BASF also developed its Eco-Efficiency Analysis (EEA) tool for concrete. EEA is a third-party validated, award-winning holistic and strategic environmental lifecycle assessment methodology that focuses on multiple environmental parameters, not only CO2 emissions. With this tool, BASF can analyze each concrete mix to achieve new levels of economy and sustainability.

In , BASF introduced Glenium® admixtures, Green Sense? concrete, and its EEA tool. In , BASF Construction Chemicals worked with hundreds of concrete producers in the United States to optimize their concrete mixes with Glenium® admixtures and Green Sense? concrete.

Green Separation Science and Technology: Using Environmentally Benign Polymers to Replace VOCs in Industrial Scale Liquid/Liquid or Chromatographic Separations: One area of opportunity for new chemical science and engineering technology which will help meet the goals of Technology Vision is the development of new separations technologies that eliminate the use of flammable, toxic VOCs as industrial solvents. Used in conjunction with, or instead of, appropriate current manufacturing processes, such technologies would help to prevent pollution and increase safety. The nominated technologies are based on the use of water soluble polyethylene glycol polymers in either liquid/liquid (aqueous biphasic systems - ABS) or chromatographic (aqueous biphasic extraction chromatographic resins - ABEC) separations.

Two patented technologies are highlighted: a) applications in radiopharmacy to allow the use of cleaner neutron-irradiated isotopes rather than fission-produced isotopes, and b) applications in remediation where reduction of secondary waste streams or conventional technologies are anticipated. The separations approach followed in developing these technologies suggest a wider industrial application for VOC-free separations. Within a paradigm of pollution prevention and with industry participation, a tool-box approach to Green Separation Science & Technology can be developed based on the use of environmentally-benign polymers.

Green Synthesis of Nanometal Catalysts and Plant Surfactant-Based, In Situ Chemical Oxidation for Sustainable Treatment and Remediation: According to EPA&#;s publication, "Cleaning up the Nation&#;s Waste Sites", an estimated 294,000 sites will need to be cleaned up at an estimated cost of approximately $209 billion. Many of these sites contain Non-Aqueous-Phase Liquids (NAPLs). EPA also estimates that there are as many as 15,000 contaminated sites of former manufactured gas plants and coal-burning factories nationwide. Beyond digging up these sites and hauling large quantities of contaminated soils to landfills, there are extremely limited options currently available to treat NAPLs.

VeruTEK Technologies has developed a novel green reaction process called Surfactant-Enhanced In-Situ Chemical Oxidation (S-ISCOTM) to reduce the amount of NAPLs in soils. Its patent-pending S-ISCOTM technology uses VeruSOLTM (e.g., coconut oil, castor oil, citrus extracts: biodegradable, U.S. FDA Generally Recognized as Safe (GRAS) surfactants) to solubilize immiscible phase organic contaminants into groundwater where oxidation reactions readily destroy them.

Under a Cooperative Research and Development Agreement (CRADA) with EPA, VeruTEK has also produced nanometals made from simple plant extracts such as tea or other high-antioxidant plant polyphenols and dissolved metals at ambient temperature and pressure. VeruTEK has used these nanometals to catalyze advanced oxidation reactions; they have no hazardous materials in their synthesis and produce no hazardous wastes. In , VeruTEK and EPA submitted a patent application for the green synthesis of these nanometals. VeruTEK has also developed green chemical reactions using plant-based co-solvents and surfactants to simultaneously solubilize and oxidize toxic, organic-phase contaminants in situ. These two processes will (1) reduce the use of toxic chemicals associated with the individual chemical reactions; (2) eliminate hazardous chemicals and wastes in the synthesis of many useful nanometals; (3) profoundly reduce the quantities of hazardous, regulated waste generated by excavating contaminated sites; and (4) eliminate the wasteful use of clean sand and gravel to backfill contaminated sites after excavation.

Green Technology for the 21st Century: Microporous Ceramics: The Green Technology for the 21st Century: Microporous Ceramics program is dedicated to both the fundamental understanding and practical environmental applications of microporous ceramic materials. These materials are typically used as thin porous films on a variety of supports for numerous applications. Such films are composed of nano particulate oxides (i.e., 0.5 to 10 nm in diameter) that are either randomly close-packed to form membranes (i.e., 30 percent porosity) or more loosely packed to form catalysts, photocatalysts, and thin film energy storage devices. Because the particle size, surface chemistry, and particle packing of these oxides can be controlled, so can the pore size, pore size distribution, and the physical-chemical properties of these materials.

As a result, the properties of these materials can be tailored for given applications which include reverse osmosis and gas separation membranes; high temperature membrane reactors; size and shape selective photolysis membranes; low temperature deep-oxidation catalysts; room temperature photocatalysts; and energy storage devices such as thin film batteries, ultracapacitors, and fuel cells. The Green Technology for the 21st Century: Microporous Ceramics program is illustrated using three examples: an indoor air cleaner for the complete oxidation of volatile organic compounds; an inorganic photoreactor for the size and shape selective synthesis of desired compounds with a minimum of waste; and, finally, an inexpensive, thin film ultra-capacitor which exceeds the U.S. Department of Energy"s near-term goal for this type of energy storage device.

GreenEarth® Cleaning, Dry Cleaning with Silicone Solvent: Historically, solvents used for dry cleaning fabrics have been hazardous to soil, groundwater, air, and industry employees. GreenEarth Cleaning (GEC) has developed and patented a process using cyclic siloxane (decamethylcyclopentasiloxane) that is a safe and viable alternative. Commercial drycleaners license the use of this process in their independent operations. Prior to commercializing this process, GEC conducted beta testing at 27 retail dry cleaning sites in the United States over a 10-month period.

During this period, two million pounds of clothing were processed, and independent, certified testing laboratories performed more than 26,000 test measurements on air and waste streams, proving the process is safe for the environment and employees. Beta-test sites also reduced the volume of their solid waste by 40&#;65 percent. The GEC silicone does not influence air quality because it is not volatile. Tests confirm that it will not impact soil or groundwater, as it degrades to SiO2, CO2, and H2O within 28 days. GEC has licensed this process at 481 locations in the United States and over 500 locations in ten other countries, with growing acceptance based on its health, safety, and environmental profile, as well as its operational advantages.

Greener by Design: An Efficient, Multiobjective Framework Under Uncertainty: Professor Diwekar and her group have developed an efficient, integrated framework for computer-aided green process design that combines chemical synthesis with process synthesis, design, and operation. Even in the presence of multiple, conflicting objectives, her framework uses new, efficient, optimization algorithms to provide cost-effective, environment-friendly designs that also explicitly identify trade-offs. The framework quantifies and characterizes uncertainties inherent in group contribution methods for chemical synthesis and in environmental impact assessments and includes them in the design process.

Because the property data needed to assess environmental impacts are not available for many molecules, scientists have turned to computational chemistry and molecular simulations to predict these properties. Previous simulations have, however, been computationally intensive and have produced large errors in predicted properties. Professor Diwekar&#;s new framework reduces computational intensity and predictive errors for environmental property prediction by an order of magnitude compared to other molecular simulations. Her framework has wide applicability ranging from molecular simulations to designing profitable greener chemicals, chemical processes, environmental control technologies, and energy systems. It can also be used for effective environmental management and operations including nuclear waste disposal and renewable energy systems.

In the last five years, Professor Diwekar&#;s work has resulted in 25 research papers in peerreviewed journals (including five invited papers), three invited chapters (one in The Encyclopedia of Chemical Technology), two American Institute of Chemical Engineers (AIChE) graduate research awards (a Separations Division Award and a Environmental Division Award), a patent application, industrial implementation, and several conference and invited presentations. Results of Dr. Diwekar&#;s work are currently being used in both continuous and batch chemical production and in energy systems. This is the first framework that considers chemical synthesis, process synthesis, and design under uncertainty together when confronted with multiple and conflicting objectives encountered in the selection of environment-friendly chemicals and technology designs for large-scale systems.

Greener Chemistry for Nitrate Analysis: Enzymatic Reduction Method: The Nitrate Elimination Company, Inc. (NECi) is pioneering the migration of enzyme-based analytical methods from research and biomedical labs into the mainstream analytical chemistry community. Biotechnology enables the engineering of enzymes into dependable analytical reagents. NECi has adapted a plant enzyme, nitrate reductase, for use in nitrate analysis. NECi&#;s recombinant nitrate reductase has made the company&#;s enzymatic reduction method for nitrate analysis robust and practical. The enzyme is produced in commercial quantities with consistent performance properties at affordable cost.

Nitrate is a primary analyte under the Safe Drinking Water and Clean Water Acts. The U.S. EPA-certified method for nitrate analysis in drinking water and wastewater is based on cadmium metal reduction of nitrate to nitrite and conversion of the nitrite to a colored compound using Greiss reagents. Cadmium is hazardous to handle and ends up as toxic, persistent waste after use of this method.

In the new technology, NECi&#;s recombinant nitrate reductase (NaR) and the natural reducing agent beta-nicotinamide adenine dinucleotide in its reduced form (NADH) replace the first step of the cadmium reduction method. The enzymatic method is sustainable, greener, and safe to handle; it generates only minimal amounts of biodegradable waste. The enzymatic method has been validated by comparison to the cadmium method. It is ideally suited for the newer robotic analyzers, called discrete analyzers, which are beginning to be used for water analysis in the United States and the rest of the world. Between and , NECi commercialized two Superior Stock Nitrate Reductases (YNaR1 and AtNaR2) for automated nitrate analysis using continuous flow analysis and discrete analyzers. Currently, NECi is submitting its NaR-based nitrate analysis methods to Standard Methods and the U.S. EPA for certification as alternatives for nitrate analysis in drinking water and wastewater.

Greener Production of Functionalized Nanoparticles: Professor Hutchison has applied the principles of green chemistry to the production of functionalized metal nanoparticles. Functionalized nanoparticles bring together the functionality of a molecular ligand shell and the novel properties of a nanoparticle core, resulting in a high degree of functionality in a nanoscale object. The unique properties of functionalized nanoparticles promise to enhance or revolutionize applications in a wide array of technological sectors including medical diagnostics and therapeutics, catalysis, electronic/optic materials, and environmental remediation.

Methods of producing functionalized nanoparticles are typically inefficient; they often require hazardous reagents. Professor Hutchison&#;s team developed a novel synthesis of triphenylphosphine-stabilized gold nanoparticles that eliminates the need for hazardous reagents including diborane and benzene, reduces or eliminates organic solvents in both production and purification, and improves the overall safety of the process. At the same time, the synthesis is more efficient and economical. By addressing each of three steps involved in producing functionalized nanoparticles (core synthesis, functionalization, and purification), Professor Hutchison has demonstrated that human health, environmental, and economic benefits can be realized. Further, his approach is general and can be readily extended to the production of other nanoparticle compositions.

The production of metal nanoparticles alone is forecast to reach 2 million metric tons by . Given this anticipated growth, Professor Hutchison expects his approach to have a significant impact in realizing greener nanotechnology. Because his methods reduce the cost to produce functionalized nanomaterials, there is now commercial interest in them. In , Dune Sciences LLC was formed to commercialize applications of nanoparticles in medical diagnostics and catalysis.

Greenhouse Gases: From Waste to Product: About 5 billion pounds of adipic acid are manufactured worldwide each year. In the United States alone, approximately 3 billion pounds of adipic acid are produced every year. Adipic acid is used in the manufacture of a large number of consumer products, including nylon for carpets, apparel, industrial fabrics, and also for urethanes, plasticizers, and food additives. Essentially all adipic acid is manufactured today by a three step process starting with benzene: the benzene is hydrogenated to cyclohexane, the cyclohexane is oxidized with air to a mixture of cyclohexanol and cyclohexanone (KA oil), and the KA oil is oxidized to adipic acid using nitric acid as the oxidant.

Waste generation is a serious environmental issue with the traditional processes used to make adipic acid: the oxidation processes produce large amounts of nitrous oxide and organic wastes that must be disposed of or destroyed. For example, with the current technology, the production of 5 billion pounds of adipic acid also results in the production of 2 billion pounds of nitrous oxide. Nitrous oxide is a known greenhouse gas with a global warming potential 300 times greater than carbon dioxide and is also a suspected ozone depleter. It has been estimated that release of nitrous oxide from adipic acid manufacture accounts for 10% of the annual releases of manmade nitrous oxide into the atmosphere worldwide.

As part of Solutia"s program to search worldwide for new technologies to reduce or eliminate waste from its operations, the company initiated a partnership with Boreskov Institute of Catalysis in Novosibirsk, Siberia, to develop an alternative method for manufacturing adipic acid. This new process recycles the nitrous oxide waste gas and uses it as a raw material in the production of phenol. This eliminates either the direct release of this greenhouse gas into the atmosphere or the use of expensive, energy intensive CO2 greenhouse gas producing abatement processes. At the same time, the yield of phenol from Solutia"s new technology is very high. Furthermore, since the cost of this alternative method of producing adipic acid is lower than the commercial method traditionally used by the chemical industry, the process is both environmentally and economically sustainable.

A pilot plant demonstrating the process on a continuous basis was started at Solutia"s Pensacola Technology Center in May . The unit has operated successfully since startup and provided the data currently being used in design of the full scale commercial plant. The new plant will utilize all of Solutia"s nitrous oxide (250 million pounds per year) to produce more than 300 million pounds per year of phenol. This revolutionary process represents the first major breakthrough in the production of phenol in more than 50 years. The new efficient process saves energy and eliminates the emission of massive amounts of greenhouse gases, while greatly reducing the production of organic wastes.

Greening Atorvastatin Manufacture: Replacing a Wasteful, Cryogenic Borohydride Reduction with a Green-by-Design, More Economical Biocatalytic Reduction for a Higher Quality Product: Atorvastatin calcium is the active ingredient in Pfizer&#;s cholesterol-lowering drug Lipitor®. The key advanced chiral intermediate in the manufacture of atorvastatin is t-butyl (4R,6R)-6-cyanomethyl-2,2-dimethyl-1,3-dioxane-4-acetate (i.e., ATS-8, also known as TBIN). It is the control point for stereopurity and the first isolated intermediate comprising both of atorvastatin&#;s chiral alcohol centers. Pfizer&#;s traditional ATS-8 process used a NaBH4 reduction of the corresponding (5R)-hydroxy-3-ketoester (ATS-6, HK) enantiomer under cryogenic conditions to give, after quenching, the (3R,5R)-dihydroxyester (ATS-7, diol). The ATS-6 was first converted with hazardous triethylborane in situ to a diastereo-directing boron chelate, which was then reacted with NaBH4 at or below -85 °C to promote diastereoinduction. After this reaction, the boronic wastes were removed by repeated methanol quenches and vacuum distillations. The diastereoinduction was inadequate, however, and several percent of the wrong (3S) diastereomer was formed. Subsequently, the ATS-7 diol, an oil, was protected as its acetonide, ATS-8, whose diastereopurity required upgrading by crystallization, with concomitant product loss.

Codexis developed a greener, more economical process for reducing ATS-6 to diastereopure ATS-7. This process uses a ketoreductase biocatalyst specifically evolved to reduce ATS-6 with perfect diastereoselectivity under greener, aqueous, ambient reaction conditions in conjunction with a previously evolved, process-tolerant glucose dehydrogenase biocatalyst. It obviates the use of hazardous boron reagents, reduces solvent use by 85 percent, reduces waste by 60 percent, lowers energy use dramatically, and provides a higher yield of more stereopure ATS-7. The ATS-7 from this reaction is already more diastereopure than was the atorva-statin in Pfizer&#;s Lipitor® pills as of . Codexis&#;s biocatalytic process is now supplying tens of metric tons per year, and growing, of high-quality ATS-8 to manufacturers of atorva-statin for geographic generic markets. During , Pfizer announced the conversion of its ATS-8 manufacture to a biocatalytic reduction using a ketoreductase in-licensed from a third party.

Greening Insecticides and Parasiticides: Synthetic chemicals are the current primary means of abating and controlling invertebrate pests, but these products are flawed due to the development of insect resistance, environmental concerns, and adverse health and environmental effects. Natural plant oils are safer and have various degrees of pesticidal activity, but historically have not been as effective as nor offered as broad a spectrum of control as products based on synthetic chemicals.

TyraTech is developing proprietary insecticide and parasiticide products that incorporate unique blends of natural active ingredients. TyraTech&#;s proprietary development platform enables them to identify potent mixtures of plant oils that are active as insecticides and parasiticides. Their screening platform currently includes three chemoreceptors that they cloned into Drosophila cell lines: the tyramine neurotransmitter receptor (expressed solely in invertebrates) and two insect olfactory receptors. Compounds that bind to and activate these receptors have been shown to be powerful insecticides. With this platform, TyraTech can rapidly select blends of individual oils that have synergistic ability to activate multiple insect neurological and olfactory receptors.

TyraTech&#;s products use natural, volatile oils as the main active ingredients, ensuring that toxic chemicals do not persist in the environment and also drastically limiting the potential for unintended adverse health effects for humans and other animals. By targeting multiple chemical receptors simultaneously with natural ingredients, TyraTech&#;s products decrease the incidence of insect resistance that is characteristic of the synthetic chemical pesticides currently in use. Their products are highly effective and inherently safer than other current products.

TyraTech is targeting diverse pesticide markets including agricultural and horticultural applications, consumer and institutional markets, professional pest control, vector control, and human and animal healthcare applications. During , TyraTech commercialized its first product, a ready-to-use broad spectrum Crawling Insect Spray for the institutional market.

Greening Montelukast Manufacture: Replacing a Stoichiometric Chiral Boron Reagent with a Green-by-Design, Economical Biocatalytic Reduction Enabled by Directed Evolution: Methyl (S,E)-2-(3-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-hydroxypropyl)-benzoate (MLK-III) is the key chiral intermediate in the manufacture of montelukast sodium, the active pharmaceutical ingredient in Merck&#;s bronchodilator, Singulair®. The innovator&#;s ketone reduction to this chiral alcohol requires at least 1.8 equivalents of the expensive, hazardous reductant (&#;)-ß-chlorodiisopinocampheylborane ((&#;)-DIP-Cl) in tetrahydrofuran (THF) at -20 to -25 °C. After quenching, an extraction is required to remove spent borate salt waste. The reduction produces the S-alcohol in 97 percent enantiomeric excess (e.e.) and requires crystallization to give 99.5 percent e.e. in 87 percent isolated yield.

Codexis developed a green, more economical biocatalytic reduction to manufacture MLK-III with a ketoreductase biocatalyst evolved to reduce MLK-II, its ketone precursor. No naturally occurring or commercially available ketoreductase shows activity toward MLK-II. Codexis used a minimally active ketoreductase it had evolved previously and evolved it further to increase its activity and stability by over 2,000-fold, replacing one-third of the amino acids in its active site in the process.

The evolved ketoreductase produces MLK-III with essentially perfect enantioselectivity under greener reaction conditions: 100 g/L in isopropanol&#;water&#;toluene and 45 °C. Isopropanol is the reductant, which the ketoreductase uses to regenerate its catalytic cofactor NADPH, producing acetone as the coproduct. The process runs as a slurry-to-slurry conversion with product precipitation driving the reaction to completion. The precipitated chiral alcohol is of high chemical purity and exquisite stereopurity. (The distomer is undetectable.) Filtration and washing then recover MLK-III. The process replaces the hazardous boron reagent, greatly reduces organic solvent use, essentially eliminates inorganic salt waste, uses less energy, and provides a higher yield of MLK-III in higher stereopurity.

With its commercial manufacturing partner, Arch Pharmalabs, Codexis has scaled up the manufacture of MLK-III using this biocatalytic reduction and has provided samples of MLK-IV to manufacturers of generic montelukast. Codexis has scheduled commercial manufacture on the multi-ton scale in .

Greening the Design of Chemical Production with Microbes: Currently, chemical synthesis using energy-intensive processes and fossil-based materials produces the majority of fine chemicals. In contrast, the biosynthesis of fine chemicals from biobased feedstocks has demonstrated feasibility and promise, however, over the past few years. Blue Marble Biomaterials is developing microbial systems to lower the carbon intensity and improve the lifecycle sustainability of fine chemical production. Blue Marble has developed a proprietary combination of microbes that produce a wide variety of fine chemicals and chemical intermediates including carboxylic acids, esters, thiols, and other organosulfur compounds in a single batch.

Blue Marble&#;s unique polyculture fermentation uses no genetically modified organisms and resists environmental stress. This fermentation can process low-cost, nonsterile lignin, cellulose, and protein-based waste byproducts from food, forestry, and algae companies without chemical or thermal preprocessing. Using these feedstocks for fermentation prevents landfilling or burning them and abates approximately 15.28 tons of carbon dioxide equivalents (CO2 eq.) per ton of feedstock. Compared to microbial systems that use carbon- and energy-intensive virgin or preprocessed plant materials, Blue Marble&#;s system recycles waste biomass, capturing the carbon it contains. In , the company scaled up production to a commercial facility in Missoula, MT.

This facility is currently undergoing food-grade and kosher certification. It will operate at 100 percent capacity in the first quarter of . Each year, it will use 860 wet tons of feedstock to produce 414,900 kg of carboxylic acids, esters, thiols, and other organosulfur compounds. An on-site water recycling system will reuse 75 percent of the water required for fermentation, saving 574,000 gallons of water per month. Finally, all biogas from the fermentation system will run through an algae remediation system to reduce facility emissions by scrubbing CO2 and methane. Blue Marble is working with several major manufacturers in the flavoring, food, and personal care industries and with Sigma-Aldrich Fine Chemicals toward global distribution of seven compounds.

GreensKeeper® Polymer Slurries for Oil and Gas Well Stimulation: In December , the major oil and gas pumping service companies (Benchmark&#;s customers) entered into an agreement with the U.S. EPA to eliminate diesel fuel from hydraulic fracturing fluids injected into coalbed methane production wells. This agreement arose from U.S. EPA&#;s concern that diesel-based slurries used for oil and gas well stimulation pose a risk to underground sources of drinking water. To respond to its customers, Benchmark evaluated many potential carriers as diesel substitutes, considering slurry quality, cost, performance, safety and regulatory concerns, toxicity, flammability, and environmental impacts. Benchmark used these nondiesel carriers to evaluate more than a thousand different suspension slurries.

In , Benchmark introduced its GreensKeeper® line of environmentally friendly polymer slurries to replace diesel-based slurries. GreensKeeper® slurry products are the first ones available to the industry that are completely compliant with the requirements of the Safe Drinking Water Act. GreensKeeper® not only eliminates diesel but also contains no benzene, toluene, ethylbenzene, or xylene (BTEX), or any of the 126 Priority Pollutants identified by the U.S. EPA.

In addition to superior environmental performance, GreensKeeper® products offer exceptional slurry characteristics including stability for extended periods at temperatures of over 100 °F, pumpability under subzero (less than °F) conditions, and compatibility with all commonly used boron, titanium, and zirconium cross-linkers. Unlike diesel-based slurries, GreensKeeper® slurry products are nonflammable, thus reducing fire and explosion risk during production, transport, storage, and use. Unlike diesel, they are not DOT-regulated, thus eliminating the risks associated with transporting hazardous chemicals. Widespread acceptance of GreensKeeper® slurries was directly attributable to Benchmark&#;s national distribution network and transportation capabilities. By December , Benchmark had produced and sold over 10 million gallons of GreensKeeper® slurry to the oil and gas industry. After only 20 months, GreensKeeper® already represents 70 percent of Benchmark&#;s monthly slurry sales volumes.

GreenWorksTM Natural Cleaners from the Makers of Clorox: Home Cleaning Products: GreenWorksTM Natural Cleaners set a new standard for natural cleaning. These products perform as well as conventional cleaners and are composed of over 99-percent natural, plant-based ingredients from renewable sources and minerals. The formulas optimally blend natural ingredients and naturally derived surfactants to achieve excellent cleaning performance.

One key to the GreenWorksTM technology was Clorox&#;s development of a novel nanoemulsion that dissolves ingredients such as essential oils in the formulation as well as dirt or soil. The reduced particle sizes provide optimized surface interactions and increase the one-phase stability region. This technology enables GreenWorksTM products to be isotropic clear upon infinite dilution, reducing the ingredients by ten-fold compared to normal all-purpose or glass cleaners. The products are biodegradable and non-allergenic, are not tested on animals, and come in recyclable containers. The manufacturing facilities used to produce GreenWorksTM have zero emissions discharge. All GreenWorksTM products perform as well as or better than leading conventional cleaners in laboratory and in blind, in-home consumer tests. This level of cleaning is important to convincing consumers to switch from traditional cleaning products. The EPA Design for the Environment (DfE) initiative has recognized the safe ingredients and cleaning performance of GreenWorksTM products, which proudly display the DfE logo.

Fossil fuels contribute significantly to greenhouse gas emissions. By switching from petrochemicals to natural ingredients in its GreenWorksTM line, Clorox achieved a savings of approximately 450,000 gallons of petroleum in the United States during . In addition, plant-based renewable sources reduce emissions of carbon dioxide (CO2), a greenhouse gas, during photosynthesis.

Clorox launched GreenWorksTM Natural Cleaners in January . GreenWorksTM products sell at only a modest premium over conventional cleaners, despite their use of costlier plant-based renewable ingredients, an environmentally friendly manufacturing process, and innovative science, which together offer the consumer the most natural, powerful cleaning products on the market.

Grignards Going Greener by Continuous Processing: The synthetic pathways of numerous intermediates for food additives, industrial chemicals, and pharmaceuticals have included the Grignard reaction since the start of the 20th century. Despite these successes, the acute hazards of the Grignard reaction make it one of the more challenging reactions to bring to commercial scale. These hazards include: (1) strongly exothermic activation and reaction steps; (2) heterogeneous reactions with potential problems suspending and mixing the reaction mixture; and (3) extreme operational hazards posed by ethereal solvents such as diethyl ether. Eli Lilly and Company has developed inherently safer Grignard chemistry using a continuous stirred tank reactor (CSTR) that allows continuous formation of Grignard reagents with continuous coupling and quenching operations.

This strategy minimizes hazards by operating at a small reaction volume, performing metal activation only once for each campaign, and using 2-methyltetrahydrofuran (2-MeTHF) as a Grignard reagent and reaction solvent that may be derived from renewable resources. Grignard reactions using 2-MeTHF also result in products with enhanced chemo- and stereoselectivity. Relative to batch processing, the continuous approach allows rapid, steady-state control and overall reductions up to 43 percent in magnesium, 10 percent in Grignard reagent stoichiometry, and 30 percent in process mass intensity (PMI). The continuous approach reduces reaction impurities substantially. In addition, small-scale operation at end-of-reaction dilution allows all ambient processing conditions.

Lilly is using its CSTR Grignard approach to produce three pharmaceutical intermediates. One of these is the penultimate intermediate of LY.HCl, a norepinephrine reuptake inhibitor that is under phase 3 clinical investigation for treatment of depression. Lilly uses a similar approach to synthesize an intermediate for LY, an investigational new drug candidate under clinical evaluation to treat benign prostatic hyperplasia. Lilly anticipates commercial production on 22 liter scales that will replace the 2,000 liter reactors used in batch processes.

Guar-Based Chemistry Advances Targeted Performance of Crop Sprays by Reducing Drift and Improving Retention: It is estimated that less than 10 percent of all sprayed pesticides reach their intended targets. A major reason for the off-target movement of pesticides is the drift of the droplets and the inability of the droplets to stick to a leaf or plant surface.

Rhodia uses derivatives of guar, a naturally occurring polysaccharide, to solve this problem. Hydroxypropoxylation (HP) of guar improves its hydration, making it amenable to uses in a wide range of temperatures. Rhodia&#;s technology uses HP-guar to mitigate the effect of drift and improve the retention of pesticide droplets on target surfaces. Guar-based polymers can reduce drift by increasing droplet size and can improve the retention of droplets by providing a "shock absorber" effect. The results of field trials using pesticides corroborate Rhodia&#;s fundamental studies: when guar-based polymers are added to a fungicide against the pathogen Asian soybean rust, both the efficacy and the crop yield increase. Also, results of field tests using an herbicide show that guar-based polymers increase weed kill across the board. More importantly, a very small amount of HP-guar (0.07 percent) can increase efficacy considerably, irrespective of the active ingredient.

Rhodia sells HP-guar for agricultural applications as AgRHOTMDR . Farmers currently apply AgRHOTMDR on more than 16 million acres of soybeans in the United States, which represents 15 percent of the total sprayable soybean acreage. Within the next five years, Rhodia expects to apply its technology to other crops covering more than triple the current sprayable acreage.

HCR-188C1: A.S. Trust & Holdings, Inc.'s All-New, High-Efficiency Hydrocarbon Refrigerant With No Impact on Global Warming or the Ozone Layer: Chlorofluorocarbons (CFCs) have been used as refrigerants in air conditioners and refrigerators since the s, when they were hailed as a safer alternative to dangerous coolants. Yet while CFCs have the advantages of safe incombustibility, high stability, and low toxicity, they also contribute heavily to ozone layer depletion, languishing as dangerous chlorine atoms in the stratosphere for up to a century. As a result, the production and use of CFCs have been virtually abolished over the past decade, and they&#;ve been systematically replaced by various hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). Yet while HCFCs and HFCs are less destructive to the ozone layer, they&#;re also powerful greenhouse gases that present their own set of unfortunate environmental risks.

A.S. Trust & Holdings has developed a new substitute hydrocarbon (HC) formulation, HCR-188C1, that has been independently shown to have zero ozone depletion potential (ODP) and zero global warming potential (GWP). HCR-188C1 is a proprietary blend made strictly from naturally occurring substances approved for common use and available at any gas manufacturer: propane, butane, isobutene, and ethane. This substance can be used independently of CFCs and HFCs/HCFCs, and cools so effectively that only one-quarter the mass of HCR-188C1 is needed in a refrigerator or automotive air-conditioning system that would have required a full charge of the CFC R-12 or the high-GWP formula HFC R-134a. HCR-188C1 is the only approved alternative refrigerant that can act as a substitute in both system types. HCR-188C1 also features major safety improvements over other HCs, including reduced charge rates, and solves the problem of decomposition upon leakage that causes HFCs to become less efficient and require more frequent replacement. HCR-188C1&#;s higher molecular weight makes it less apt to leak through joints or o-rings, and it also retains its cooling properties, thus extending the lifetime of any unit that runs on it. A.S. Trust has been successfully using the original HCR-188C formulation for automotive and refrigerator cooling for more than ten years.

Heavy Metals Free, Non-Formaldehyde Fixing Agent for Direct and Fiber Reactive Dyes: Generally, a textile fixing agent is a cationic polymer, which forms a resin film covering the surface of the fiber and adheres to it. This action causes the many cationic groups in the molecule of the polymer to bond with the dye anions in the fabric to block the hydrophilic groups of the dye, thereby forming insoluble salts. Once completed, this process allows the dye to be retained in the fabric, preserving the intended color shade through the normal washing processes. The cationic charges in these types of polymers is often supplied by the positive charge of heavy metal ions such as zinc. It was NICCA&#;s strong commitment to the environment and recognition of the value of such green chemistry that led to the development of NEOFIX® E-117. NEOFIX® E-117 is a heavy metals free, nonformaldehyde based fixing agent for direct and fiber reactive dyes. It significantly improves wash fastness of cellulosic fabrics and their blends. Unlike many fixing agents of this nature, NEOFIX® E-117 adds the extra benefit of helping its users comply with environmental and safety regulations by removing occupational and environmentally hazardous compounds.

High CO Tolerant Polymer Electrolyte Membrane Fuel Cell Technology: Polymer electrolyte membrane (PEM) fuel cells are a paradigm shift technology in power generation because they use an electrochemical process to convert hydrogen and oxygen into electricity without combustion and combustion associated pollution. A fuel cell operating on natural gas produces less than 1 ounce of air pollutants as compared to 25 lbs. of pollution produced by conventional combustion generation. Existing PEM fuel cells, however, are very sensitive to carbon monoxide (CO) poisoning and membrane hydration. Trace amounts of CO in the fuel can reduce fuel cell performance, and a reduction in the hydration of today&#;s membranes can shorten the membrane life. With such a high sensitivity to CO and hydration, current PEM fuel cells are expensive to maintain, and have limited lifetime and reliability.

Under the NIST Advanced Technology Program, Plug Power, Inc. has demonstrated a high CO tolerant fuel cell technology using a novel polymer electrolyte membrane. This new membrane does not require external humidification and because it operates at high temperature (160C), this new version of a PEM fuel cell can operate with over 1% (10,000 ppm) of CO without performance degradation. The significant increase in CO tolerance and the elimination of membrane hydration have substantially improved fuel cell operational performance and greatly simplified the overall system; thereby reducing system related cost and increasing system life. A reliable and low cost PEM fuel cell system with commercial viability is now being developed based on this new technology.

High Energy Efficiency, Environmentally Friendly Refrigerants: For several decades chlorofluorocarbons (CFCs) were the most widely used refrigerant fluids because of their nonflammability, low toxicity, low cost, and reasonably high performance. Because CFCs have been implicated in stratospheric ozone depletion, their production worldwide was stopped at the end of under the provisions of the Montreal Protocol as amended in Copenhagen in . The phaseout of CFCs and HCFCs and increasing concern about greenhouse gases create the urgent need for nontoxic, nonflammable, environmentally safe refrigerants with high capacity and energy efficiency. Dr. Jonathan Nimitz and his co-inventor, Lance Lankford, have discovered and patented a family of improved refrigerants based on blends containing trifluoromethyl iodide (CF3I).

CF3I has attractive physical properties, zero ozone depletion potential (ODP), low global warming potential (GWP), relatively low toxicity, and is a combustion inhibitor. CF3I can be combined with high-capacity, energy-efficient, environmentally friendly, but flammable refrigerant compounds to obtain excellent refrigerant blends that remain nonflammable. The result is an energy-efficient, environmentally friendly, safe refrigerant. The inventors and Dole Food Company have formed a new company, Ikon, Inc., to support testing and commercialization of the refrigerants.

The first formulation developed, Ikon® A, has extremely low GWP and can be used in R-12 or R-134a systems. Ikon® A has been demonstrated for over 3 years in Dole Food Company refrigerated transports, with excellent results. Ikon® A was also tested in a new R-134a domestic refrigerator, with results of 19% higher energy efficiency and 15% greater volumetric cooling capacity versus R-134a. Ikon® B was developed as a less expensive version of Ikon® A; it has been tested and demonstrated in refrigerated transport units, a 5-ton water chiller (sponsored by NASA Kennedy Space Center), and a new R-134a domestic refrigerator (sponsored by EPA). A 20% market penetration of Ikon® B by will result in a decrease in carbon dioxide emissions of approximately 4 million tons per year.

There would also be annual reductions of approximately 12 thousand tons particulate, 16 thousand tons nitrogen oxides, and 24 thousand tons sulfur oxides. The installation cost for Ikon refrigerants will be repaid within 3 years in most applications. At 20% market penetration by , $0.08 per kWhr and 15% lower energy use, estimated energy cost savings by are $400 million per year. The human health and environmental benefits of the Ikon refrigerants will be significant. Their use will result in improvements in human health, improvements in air and water quality, and reductions in skin cancer and ecological and crop damage from UV radiation.

High Performance Macromolecular Antioxidants for Materials: A Green Chemistry Approach: Industrial antioxidants are an increasingly important and fast-growing market. The antioxidant market generates annual sales of approximately $2.1 billion, based mainly on low-molecular weight products with limited thermal stability, relatively low material protection, and higher material diffusion rates.

Polnox Corporation is in the process of introducing seven high-performance macromolecular antioxidants that it synthesizes from FDA-approved phenol antioxidants in a one-step process using biocatalysts and biomimetic catalysts. Polnox invented a new biotechnology-based methodology for synthesizing its macromolecular antioxidants. The starting materials for the Polnox macromolecular antioxidants include butylated hydroxyanisole, tert-butylhydroquinone, and propyl gallate. The Polnox antioxidants have shown superior oxidative resistance (1- to 30 fold) and higher thermal stability compared with current low-molecular-weight antioxidants. The antioxidants demonstrate superior performance in a wide range of materials and applications including but not limited to plastics and elastomers, lubricants, fuels, oil, cooking oil, food and food packaging, and beverage and other industries. They are cost-effective, safe to use, and have a superior price-to-performance ratio. Acute oral toxicity (LD50) tests for these materials are at the same level as other FDA-approved antioxidants already used in food.

Dr. Cholli and his team at the University of Massachusetts Lowell originally discovered the technology. In January , Dr. Cholli formed Polnox Corporation to commercialize his antioxidants. Polnox has filed for 40 patents and has also demonstrated production feasibility by scale-up to the multi-kilogram (mini-pilot plant) scale batches for two of its seven core antioxidants. Polnox completed beta site tests in and is planning to commercializeone or more of its antioxidants during .

High Performance Soy-Based Metalworking Fluid: Metalworking fluids used in operations requiring high lubricity are typically formulated with petroleum oil and chlorinated paraffins, which are neither environmentally friendly nor readily biodegradable. In fact, EPA has placed chlorinated paraffins under regulatory scrutiny because they exhibit aquatic toxicity and certain chain lengths are considered to be carcinogens. Current annual sales of chlorinated paraffins for metalworking fluids are approximately 75 million pounds.

Desilube Technology has developed an environmentally friendly metalworking fluid that contains the methyl ester of soybean oil plus the organic amine salt of a phosphoric acid and a fatty acid. This fluid does not contain any chlorinated or sulfurized compounds and is not prepared with petroleum oil. It has been used successfully in commercial applications that require high lubricity. Desilube&#;s soybean oil based metalworking fluid outperforms conventional petroleum oil formulated with 35 percent chlorinated paraffin in two heavy-duty machining operations: deep drawing and fine blanking. The performance of Desilube&#;s metalworking fluid is due to synergism between the methyl ester of soybean oil and the amine salt of phosphoric acid with a fatty acid. This synergism also applies to water-dilutable metalworking fluid designed for metal removal applications.

Most, if not all, metalworking fluids currently used in these and other heavy-duty applications contain chlorinated paraffins. Desilube&#;s soy-based metalworking fluid has the potential to help replace chlorinated paraffins. In addition, the soybean oil base stock also has the potential to replace petroleum oil, reduce the dependency of the United States on crude oil, and take advantage of the large domestic supply of soybean oil provided in good part by farmers supporting the United Soybean Board.

The most recent patents for these soy-based technologies were published in and assigned to the United Soybean Board. Commercial sales of the environmentally friendly metalworking fluid over the past two years have averaged $45,000 per year.

High-Efficiency Olefin to Polyolefin Process with Toxic Solvent Elimination: ZIVATECH has developed novel catalytic processes to dehydrogenate aliphatic (paraffin) hydrocarbons into olefins and, subsequently, to polymerize them into polyolefins. These processes use catalytic dehydrogenation reactors in conjunction with polymerization reactors and coordination-type metal catalysts, such as titanium trichloride. This technology replaces the conventional cracking and refining of paraffins, which require more energy. In developing these processes, ZIVATECH considered materials and energy conservation coupled with environmentally benign modifications (e.g., eliminating toxic or hazardous solvents, catalysts, and other media). Process improvements include increased polymer and olefin product yields, recycling of both reactants and intermediate products within the process, reduction of toxic solvent generation, reduction of process steps, and reduction of capital and operational costs (including materials and energy costs). In , this technology received a U.S. patent. ZIVATECH is currently in the process of licensing and scaling up this technology.

Highly Water-Dispersed Oilfield Corrosion Inhibitors Eliminate over One Million Pounds of Nonrenewable Solvents Annually: Corrosion-induced leaks in hydrocarbon-producing equipment threaten safety, health, and the environment. Only recently, however, has anyone focused on safer corrosion inhibitors with reduced environmental impacts. Extensive product development by Baker Hughes has led to an innovative line of corrosion management chemicals that is free of hydrocarbon solvents, but contains active inhibitors that historically could only be formulated with these flammable solvents. The new, highly water-dispersed products exhibit better dispersibility and water partitioning in use than traditional products and, therefore, deliver the active inhibitors to metal surfaces more efficiently. The net result is significantly reduced field-level chemical use rates that do not compromise corrosion inhibitor performance.

This innovative technology entails much more than simply making water-soluble formulations. What truly distinguishes the new technology is its use of the inhibitors themselves as dispersing agents, both eliminating the need for hydrocarbon solvents and limiting or eliminating the need for additional additives or surfactants. The chemistry is based on formulated fatty acid amide&#;imidazoline technology. Careful adjustments of pH, hydrophilic-lipophilic balance, and levels of active ingredients produce stable dispersions of the inhibitors with no or only minimal added surfactants. As a result, oilfield operators can reap the benefits of the powerful chemicals commonly found in hydrocarbon-based, corrosion-inhibiting products in safer, water-based formulas that have less impact on the environment. The water-based products contain no naphthalene; they have higher flash-points than traditional, solvent-based products, so they are safer to store and handle.

Since , Baker Hughes has commercialized five of these products. Based on sales, the net direct environmental impact of this technology is the elimination of at least 1 million pounds of hydrocarbon solvents annually. With continuing development and as oilfield deployment of this technology grows, the direct and indirect positive impacts of the technology are expected to increase several-fold in the very near term.

High-Performance Polyols from CO2 at Low Cost: The vast majority of polyols currently used in coatings, foams, adhesives, elastomers, and thermoplastic polyurethanes are derived exclusively from petrochemicals. Novomer has developed a proprietary technology platform that transforms waste carbon dioxide (CO2) into very precise, high-performance polyols at lower cost than polyols from either petroleum or natural oils. Novomer&#;s polyol technology platform combines several innovations. Novomer has developed a breakthrough cobalt-based CO2&#;epoxide catalyst that is over 500-fold more active and far more precise than past zinc-based catalysts. I

n , Novomer modified its catalyst system with resin bed technology to recover and recycle the catalyst without losing activity or selectivity. Novomer was also the first to develop low-molecular-weight CO2-based polyols using chain-transfer agents. The manufacturing process for Novomer&#;s CO2-based polyols is a proven, low-cost, synthetic technology based on chemistry. It can be completed in existing chemical industry infrastructure under mild reaction conditions with conversions of over 90 percent in short timeframes. Using CO2 cuts raw material costs nearly in half, yielding a significant cost advantage. The environmental and human health benefits of Novomer&#;s CO2-based polyol technology platform are considerable. Because these polyols contain 40&#;50 percent CO2 by weight, they can potentially sequester 10 billion pounds of CO2 per year in targeted polyol markets.

More important, they enable the chemical industry to eliminate 10 billion pounds per year of petroleum-based raw materials, a source reduction that impacts the entire petrochemical value chain. In addition, because Novomer polycarbonate polyols contain no bisphenol A (BPA), they can potentially eliminate the use of BPA-containing resins in food-contact coatings. Novomer is commercializing its polyols in several markets. Jointly with the Dutch company, DSM, Novomer will introduce its first large-scale commercial polyol product for coil coating applications in . In partnership with industry-leading polyol producers, formulators, and end users, Novomer is developing additional polyol products for footwear foams, rigid insulating foams, and polyurethane adhesives.

High-Solids Hybrid Sucrose Ester Polymer Technology: In , the U.S. paint market included approximately 500 million gallons of solventborne paints and coatings. In general, these were solvent-rich, oil-based products containing over 350 grams per liter of volatile organic compounds (VOCs). Upcoming regulations in the United States, however, are tightening the limits for VOCs in coatings, especially architectural and industrial coatings. As one example, EPA&#;s VOC targets for are less than 100 grams per liter for non-flat architectural coatings. These and other regulations have necessitated a search for alternate, VOC-compliant products that feel and apply by brush, roller, and spray like high-VOC coatings.

Sherwin-Williams developed its innovative, high-solids, hybrid sucrose ester polymer technology to address this urgent need. Sherwin-Williams&#;s novel, high-solids, oxidative crosslinking hybrid sucrose ester technology uses a modified sucrose ester technology from the Procter and Gamble Company (P&G). At the request of Sherwin-Williams, P&G converted its Sucrose Ester 7.75 (Sefose® 7.75, which has no reactive groups) into a reactive Sucrose Ester 6.0 (Sefose® 6.0) with two reactive hydroxyls available for further modification.

Sherwin-Williams then acrylated Sucrose Ester 6.0 with methacrylic anhydride in a solventless process to obtain a 100-percent-solids acrylated sucrose ester polymer. This ester polymer was formulated, scaled-up, and commercialized into pigmented, oil-based coatings with excellent performance and application features for architectural and industrial maintenance applications. A single coat of the higher-solids product gives the opacification desired by customers. Subsequently, Sherwin-Williams replaced methacrylic anhydride with glycidyl methacrylate for industrial applications; this second-generation technology was acrylated and urethanated without generating waste byproducts via ring-opening of the epoxide.

This technology is enabling Sherwin-Williams to market the only compliant, oil-based, pigmented coating in the United States with VOCs less than half of the current oil-based coatings. In and , Sherwin-Williams filed a patent application and commercialized three products using this technology.

Hydrofluoroethers (HFEs)&#;The Right Balance of Properties: Research on hydrofluoroethers (HFEs) started in , and the first commercial compound came to the marketplace in . The design of the hydrofluoroethers provides a balance of properties that make them excellent substitutes for ozone-depleting compounds. 3M formed a technical team in the early s to find a substitute for ozone-depleting substances (ODSs, i.e., CFCs and HCFCs). In addition to addressing the issue of ozone depletion, the team also set criteria for candidate molecules on the basis of flammability, toxicity, photochemical reactivity (potential for smog formation), and global warming potential.

The 3M team investigated the performance, health, and environmental attributes of more than 100 compounds before the invention of HFEs. HFEs did not require the team to compromise on any of its desired qualities for an ODS replacement. HFEs do not deplete the ozone layer, do not contribute to photochemical smog, are very low in toxicity, are nonflammable, and have very low global warming potentials. The first commercial product for the HFE program was HFE-. HFE- (C4F9OCH3) was brought to the market in and was followed by HFE- (C4F9OCH2CH3) in . Both of these compounds are approved for use under EPA&#;s Significant New Alternatives Policy Program (SNAP) for solvent cleaning, aerosol, and heat transfer applications. E

PA also declared these materials as VOC exempt on August 25, . The acute and subchronic toxicity of HFE- has been thoroughly investigated. An evaluation of these data by the American Industrial Hygiene Association Workplace Environment Exposure Limit Committee yielded an exposure guideline of 750 ppm. The exceptional low toxicity of HFEs make them unique in a marketplace that has traditionally had to compromise on the toxicity of available alternatives.

Hydrogen Sulfide Elimination: Mallinckrodt Baker has developed a method that eliminates hydrogen sulfide from the substances not precipitated by H2S test. The existing method uses hazardous hydrogen sulfide, takes about 5 hours to perform, and is precise only for combined alkali results. The new method is safer (does not use hazardous reagents), takes only 30 minutes to perform, and is accurate for individual element determinations.

Imation No Process Plates: Although the principles of lithography were first applied to printing in , aluminum plates precoated with photoactive polymers did not enter volume production until the s. Availability of these presensitized plates fueled rapid growth in the lithographic printing industry due to superior print performance and economy. When a conventional presensitized plate is exposed to ultraviolet radiation through a contact masking film, formation of ink receptive image areas is initiated. These plates then require wet development to activate the printing surface, most often using a mechanical processor that also rinses the plates.

Many developers contain hazardous solvents. Developer solutions saturate with dissolved coating compounds, including toxins and heavy metals. Total U.S. printing plate consumption in the year is expected to reach 68 million square yards. Wet processing of this total volume will consume over one million gallons of aqueous developer, based upon typical depletion rates. Depleted solutions containing coating solids require disposal at hazardous waste sites in many regions of the United States. In addition, more than 1.2 billion gallons of rinse water would become part of the waste stream.

Recognizing the environmental costs of the total waste stream, Imation launched an intensive Research and Development effort to commercialize plates requiring no wet chemical processing of any kind. Today, this no process technology provides a superior printing plate, without wet processing, under the trademark name "ImationTM No Process Plates." Demand for the technology is growing rapidly across the printing industry. ImationTM No Process Plates employ photoactive polymers that form printing surfaces without wet chemical processing. When the plate is exposed to ultraviolet radiation through a masking film, formation of ink receptive areas is initiated, but activation takes place on press under action of the ink/water emulsion during the normal plate roll up process.

This technology is applicable across the printing industry, from general commercial lithographic printing to forms, packaging, and newsprint operations. Environmental benefits available to the industry are truly significant and valuable because pollution is prevented through source reduction. When ImationTM No Process Plates are used along with Imation&#;s DryViewTM imagesetting films, even greater waste reductions are possible. If 68 million square yards of DryViewTM film were used to image plates, an additional 2.4 million gallons of film developer, 4.1 million gallons of fixer, and 675 million gallons of rinse waste could be eliminated from the waste stream.

IMPACT Technology: A Greener Polyether Polyol Process: The Bayer MaterialScience (BMS) IMPACT technology for polyether polyol (PET) production couples a breakthrough catalyst invention with an equally innovative process design. The IMPACT process includes modifying the double metal cyanide (DMC) catalyst to increase its reactivity more than 10-fold and exploiting an unusual kinetic property: the modified DMC selectively adds alkylene oxides to the lower-molecular-weight molecules in a mixture of molecular weights. Combining these two inventions gives a continuous process that requires less equipment. The new process generates less waste, eliminates process steps, and is inherently safer.

A gate-to-gate life cycle assessment (LCA) of the continuous process in comparison with conventional technology shows reductions of 76&#;80 percent in energy consumption, carbon dioxide (CO2) generation, acidification, eutrophication potential, and smog. Moreover, the BMS Channelview, TX plant eliminates over 34 kilotons of wastewater annually at typical run rates and reduces over 32 kilotons of CO2 equivalents at full capacity. Recently, total production in the United States using the continuous process reached a billion pounds, and BMS completed licensing its technology to major competitors.

These milestones have established IMPACT as the industry standard in environmental savings and productivity. Worldwide, plants will be converted or constructed for IMPACT technology, increasing the positive effects on the environment. Polyethers for use in polyurethanes have a multi-billionpound worldwide market with applications spanning nearly every market segment including insulation, coatings, elastomers, and flexible foams such as bedding, furniture, and automotive seating. BMS has a 23-percent market share with a global capacity of over 1,100 kilotons. Around 50 percent of BMS&#;s PET production can be manufactured using the IMPACT technology. BMS has converted about half of this volume to the new processes. BMS has used this technology to double PET production at the Channelview plant within four years to 200 kilotons and has lowered its variable production costs by 40 percent.

Implementation and Verification of Aqueous Alkaline Cleaners: Lockheed Martin Tactical Aircraft Systems (LMTAS) was the first aerospace company to implement innovative aqueous cleaning technology for cleaning tubing and honeycomb core. Tubing is used in the aerospace industry for transferring pressurized oxygen within an aerospace vehicle. Honeycomb core is used in the aerospace industry for producing bonded structural parts. Both applications require that the parts meet stringent cleanliness requirements. These requirements were previously met by using cold cleaning or vapor degreasing with chlorinated solvents.

These solvents included 1,1,1-trichloethane [sic] (TCA) and trichloroethylene (TCE). These chlorinated solvents are toxic, and TCA is an ozone depleting compound. The use of chlorinated solvents posed a threat to the environment because the solvents were commonly released into the air during cleaning operations and because the likelihood of a spill during their use was significant. These solvents were successfully replaced with aqueous cleaning technology. As of November , 100 percent of tubing manufactured at LMTAS (including oxygen tubing) is being cleaned in an aqueous cleaning system. As of May , 100 percent of all honeycomb core used at LMTAS is also being cleaned in an aqueous cleaning system.

Implementation of aqueous cleaning technology at LMTAS eliminated approximately 360 tons of air emissions per year and resulted in a cost savings of $490,000 per year. In addition to replacing chlorinated solvents with the innovative aqueous cleaning technology, LMTAS also explored the use of environmentally safe methods for quantifying surface contaminants on parts cleaned by various cleaning technologies. Traditionally, extraction with CFC-113 followed by gravimetric or FTIR analysis has been used for quantifying surface contaminants. The use of CFC-113 is undesirable due to its ozone depleting potential. LMTAS has demonstrated the usefulness of carbon dioxide coulometry for determining the amount of residue remaining on a surface after cleaning and has used this technique for comparing the cleaning effectiveness of various cleaning technologies.

Improved Resource Use in Carbon Nanotube Synthesis via Mechanistic Understanding: Carbon nanotube (CNT) production by catalytic chemical vapor deposition (CVD) currently exceeds 300 tons per year and is growing. The current CVD process has very low yields (3 percent or less) and high energy requirements. Emissions from ethene- and H2-fed CVD reactors contain over 45 distinct chemicals including: the potent greenhouse gas, methane; toxic and smog-forming compounds, such as benzene and 1,3-butadiene; and trace quantities of polycyclic aromatic hydrocarbons.

Eliminating thermal treatment of the feedstock gases may prevent the formation of unwanted byproducts, reduce energy demands, and improve overall control of the synthesis, but heating the feedstock gas is necessary to generate the critical, previously unidentified, CNT precursor molecules required for rapid CNT growth. Using in situ CNT height measurements and gas analysis, Professor Plata and her group identified the heat-generated compounds correlated with rapid CNT formation (e.g., propyne and but-1-en-3-yne). She then mixed each of these chemicals with typical feedstock gases (C2H4 and H2) without preheating and tested them with a heated metal catalyst. She found that several alkynes (e.g., ethyne, propyne, and but-1-en-3-yne) accelerate CNT formation.

This new mechanism for CNT formation features C&#;C bond formation between intact chemical precursors, similar to polymerizations. It challenges the accepted hypothesis that precursors must completely dissociate into C or C2 units before "precipitating" from the metal. Using these mechanistic insights, Professor Plata can form high-purity CNTs rapidly.

Her technology improves yields by 15-fold, reduces energy costs by 50 percent, and reduces the ethene and H2 starting materials by 20 and 40 percent, respectively. It also reduces unwanted byproducts by over 10-fold (translating to ton-sized reductions in toxic and smog-forming chemicals and greenhouse gases). The reduced starting materials and energy requirements also lower the cost of CNTs without sacrificing product quality. A commercial CNT manufacturer has licensed this patent-pending work.

In Vivo Synthesis of Lepidopteran Pheromone Precursors in Saccharomyces Cereviseae: An Economical Process for the Production of Effective, Nontoxic, Environmentally Safe Insect Control Products: Since the advent of DDT more than 50 years ago, broad spectrum neurotoxic insecticides have provided the principle means for the control of economically important insects in agriculture and public health programs. Whereas the use of synthetic insecticides initially resulted in spectacular increases in crop yields and the suppression of some important human and animal disease vectors, the development of insecticide resistance in insect pest populations and the environmental damage caused by insecticides were quickly recognized as serious drawbacks to their use.

Today, the environmental and human health effects associated with the manufacture and use of insecticides for pest control are widely recognized, including their acute toxicity to nontarget organisms (including human applicators), their persistence in the biosphere, and major point-source pollution associated with their manufacture. Despite these effects, the scale of release of active ingredients in insecticide formulations into the global environment is enormous; in the United States alone it is more than 400 million kg/year.

Pheromones have been used on a worldwide basis for the control of insect pests for more than 15 years. Unlike conventional broad-spectrum insecticides, pheromones are nontoxic and highly specific for the species they are intended to control. Unfortunately, their effectiveness and selectivity depend upon high chemical and stereospecific purity, making them expensive to synthesize. The latter factor has limited their commercial success versus conventional insecticides. The major market for pheromone-based disruption products is in the United States and amounts to less than $50 million/year. In contrast, the worldwide insecticide market is greater than $6 billion/year.

The goal of the work of Dr. Knipple at Cornell University is to develop a cheaper process for pheromone synthesis. Toward this goal, he has proposed to use genetic and molecular technology to clone and functionally express in vivo genes encoding desaturase enzymes present in the pheromone glands of adult female moths, which catalyze the formation of key unsaturated pheromone intermediates. Accomplishment of the technical objectives of this work will contribute materially and methodologically to development of an alternative biosynthetic process for commercial pheromone production. Achievement of the latter goal will significantly improve the economic competitiveness of existing pheromone products and could provide the basis for the expansion of this promising insect control technology into other markets.

Increased Utilization of Raw Materials in the Production of Vinyl Chloride Monomer: Commercial catalytic oxidation processes have been adapted for disposal of organic solvents, ground-water pollutants, synthetic co-products, incinerator flue exhaust, and automotive exhausts. In the large-scale catalytic oxidation of chlorinated hydrocarbons, fuel value is typically recovered as steam and chlorine is recovered as HCl and/or Cl2. Various approaches are disclosed in the patent and scientific literature. Studies of the deactivation of commercial catalysts over long-term exposure of streams of chlorinated and nonchlorinated hydrocarbons found that during long-term use the reaction temperature needed to be increased in order to maintain high conversion rates and reduce catalyst deactivation.

In commercial scale catalytic oxidation of chlorinated materials, the maximum operating temperatures are limited by the optimal temperature range for the chosen catalyst as well as the corrosion resistance inherent in the metals used for the equipment. For example, certain economical nickel alloy steels undergo catastrophic corrosion in the presence of HCl at or above 530 ºC. Increasing the operating temperature of the reaction approaching 530 ºC will lead to higher corrosion rates. It would therefore be desirable from an economic standpoint to maintain very high conversion of 99% or higher of feedstocks over long periods of time without risking increased rates of corrosion.

Geon developed CatoxidTM as a catalytic process for the recovery of chlorine and energy from chlorinated organic materials. Typically, such materials are co-products of the production of useful chemicals such as vinyl chloride monomer (VCM), or other chlorinated and nonchlorinated products. The recovery is accomplished by catalytically reacting the organochlorines and an oxygen containing gas such as air to produce hydrogen chloride (HCl), carbon dioxide (CO2), and water in a fluidized bed reactor. No additional fuel is required to sustain the exothermic reaction, and the chemical energy of the materials is recovered as steam.

The HCl produced is fed directly to an oxychlorination reactor and recovered as 1,2-dichloroethane (EDC). The EDC is subsequently converted to VCM and ultimately PVC. The CatoxidTM process thus reduces the amount of chlorine required to produce a specific amount of the desired product VCM, and also reduces the fuel requirements of the production facility. Unlike incineration, which is the only acceptable alternative, the CatoxidTM process has no vents to the atmosphere. In addition, since no aqueous hydrochloric acid is generated (as is usually the case for incinerators), there is no need to utilize caustic or limestone to neutralize the acid. The CatoxidTM process was developed for the EDC/VCM/PVC industry and is directly applicable to many technologies used to produce VCM.

Industry-University-Government Partnership for Converting Regional Wastes into Chemical Products: A unique partnership in Maryland is demonstrating innovative approaches to simultaneously solve environmental problems and facilitate economic development. This partnership includes two companies (a composting company and a specialty chemical company), a chemical engineering professor, and a technology development specialist from a state economic development office. The goal of this partnership is to convert food and agricultural wastes into chemical products - thereby reducing nutrient addition to the Chesapeake Bay while creating manufacturing industries based on the state&#;s renewable natural resources.

Beginning with wastes from Maryland&#;s crab-packing industry, the partners guided research and development, leveraged state and federal resources, and obtained private sector funding to establish a manufacturing operation. The culmination of this partnership is ChitinWorks America, a private company that is converting wastes from Maryland&#;s crab-packing industry into the specialty biopolymer, chitosan. This manufacturing operation meets the state&#;s need to cost-effectively manage nutrient-rich wastes, while sparing the state&#;s crab packing industry the financial burdens associated with landfilling. Additionally, the product of this manufacturing operation is an environmentally-friendly biopolymer for various specialty applications (e.g. oil drilling).

Inert Filler TB-1: The U.S. Army has a requirement for projectiles and mortars to be loaded with inert (non-explosive) filler for training exercises and demonstration purposes. The primary inert filler used for many years at the Iowa Army Ammunition Plant (IAAAP) was Inert Filler E (Type II Filler; Spec: MIL-I-). This inert filler required ergonomically inferior methods to drill a 5" fuze well for a typical inert build (M549). The previous methods required either (1) drilling a 5" deep by 2" wide fuze well with drill bits that quickly became gummed up with filler so that the drilling required to install a fuze could take several hours per round, or (2) inserting a 5"-long shaft funnel into the poured inert filler before the filler set up to limit the drilling required.

Removing the funnel required striking it with a rubber mallet to break it loose; frequently the suction created made the funnel difficult to pull out and more drilling was still required to finish the fuze well. IAAAP achieved its goal by replacing Inert Filler E with inert filler TB-1, which meets all filler requirements. Inert filler TB-1 is easy to machine and drill: it takes only 20 seconds to drill a 5" long by 2" wide fuze well. Inert Filler TB-1 contains no hazardous materials and costs 40-percent less than the former Inert Filler E. Funnel scrap from pouring the Inert Filler TB-1 into projectiles should be 100-percent recyclable without separation, which allows the scrap to be saved for later use and minimizes waste generation.

Excess Inert Filler TB-1 easily flakes off from projectiles and equipment, so cleanup is very easy. Cleaning previous inert fillers required solvent and paper wipes; the solvent-contaminated paper wipes were hazardous waste. The U.S. Army has approved the loading of 2,000 inert 760 ammunition rounds with Inert Filler TB-1.

InfiGreenTM Polyols : Polyurethane manufacturers are seeking to pursue sustainability by reducing their carbon footprint, improving their green image, and cutting costs. The growing market for the polyols used to make polyurethane is currently about 11 billion pounds, but has few green options. Biobased polyols (primarily soy-based polyols) reduce polyurethane&#;s carbon footprint, but have significant consequences including higher prices for food and agricultural land. In addition, polyurethane manufacturing generates significant amounts of scrap, and virtually all post-consumer polyurethane scrap goes into landfills. With InfiGreenTM polyols and recycling technology, InfiChem Polymers is providing sustainable, green, economical raw materials that are not biobased and do not divert land from food production. This technology transforms polyurethane foams into InfiGreenTM polyols with over 60 percent recycled content for reuse in polyurethanes.

The process liquefies scrap foam in a reaction with glycol, and then transposes it into various InfiGreenTM polyols by propoxylation or patent-pending chemical steps; it typically generates less than one percent waste. InfiChem Polymers demonstrated its process on a pilot scale with both flexible and rigid foam scrap. Substituting one pound of conventional petroleum-based polyols with InfiGreenTM polyols reduces the carbon footprint by approximately two pounds of carbon dioxide (CO2). Polyurethane manufacturers can benefit from closed-loop recycling of their polyurethane production scrap, which can significantly reduce their landfill costs and provide them with InfiGreenTM polyols at prices typically below those for conventional petroleum-based and biobased polyols.

InfiGreenTM polyols are currently used in automotive seat cushions and in the construction industry. InfiChem Polymers expects to reach its current capacity of one million pounds of InfiGreenTM polyols in late ; within 5 years, it expects sales of 50 million pounds in NAFTA countries. With projected worldwide production of 180 million pounds of InfiGreenTM polyols, the company will consume approximately 106 million pounds of polyurethane scrap or approximately 0.03 percent of all polyurethane produced.

Innovative Green Chemistry for Sustainable Manufacture of Caprolactam: Evergreen Nylon Recycling LLC (ENR) has developed an innovative green chemistry pathway for producing nylon 6 using sustainable, renewable feedstock. The process chemically renews nylon 6 by manufacturing caprolactam (the base monomer of nylon 6) from post-consumer nylon 6 carpet and other nylon 6 waste articles. This is the world"s first, large-scale, sustainable (closed-loop) nylon recycling process, and it eliminates the annual use of 700,000 barrels of crude oil, 83 million pounds of benzene, 120 million pounds of cumene, and 86 million pounds of phenol as the source feedstock for caprolactam.

Additionally, numerous direct environmental benefits are gained. Over 200 million pounds of nylon wastes (post-consumer & post-industrial) are diverted from landfills each year. There is zero use or generation or emissions of toxic materials in the Evergreen process. Air emissions are significantly lower as compared to traditional caprolactam manufacturing, and the feedstock for the process is indefinitely renewable because nylon 6 can be recycled by Evergreen over and over again without ever degrading product quality.

The technology has been implemented through a $100 million investment in the ENR plant in Augusta, GA. Start-up occurred in December and full-rate production is expected by mid-.

Innovative Process for Treatment of Hog Waste and Production of Saleable Products from This Waste: Industrial hog production creates a large amount of liquid and solid waste, which is typically flushed into an open lagoon or sprayed onto fields, causing a number of environmental and human health problems. Recovery Systems has developed a process to treat the waste and recover valuable products from it. A standard 5,000-head farm is expected to generate about $170,000 per year in products; there are about 2,000 hog farms in North Carolina alone.

In the Recovery Systems process, the waste is flushed out of the barn to a surge tank and pumped to mix tanks, where lime slurry is added to raise the pH. At this higher pH, the colloidal bonds of the solids and urea break down to release ammonia. The lime treatment kills over 99 percent of all pathogens. The slurry is then pumped through an ammonia stripper; the ammonia-laden air is exhausted through a phosphoric acid reactor and the resulting ammonium phosphate is pumped to a storage tank. Next, the slurry is pumped to a solids separation tank, where coagulant and flocculent are added to separate the solids from the liquid. The solids are pumped to a vibrating screen washer, where the undigested feed is separated from the digested fecal solids.

The liquid from the solids separation tank is pumped to a storage tank to be used in the flushing process. The digested solids are processed in a methane generator, which also concentrates the nutrients to produce organic fertilizer. Tests by North Carolina State University show that the undigested feed is suitable as cattle feed and poultry litter. Well water is used to dilute the supersaturated salts in the flushing liquid. Recovery Systems will be testing its process on a one-of-a-kind U.S. EPA test hog farm in Lizzie, NC. In , U.S. EPA issued a contract to Recovery Systems to fund the necessary construction permit.

Innovative Techniques for Chemical and Waste Reductions in the Printed Wire Board Circuitize Process: IBM produces 1.7 million square feet of multilayer circuit boards per year in a manufacturing plant in north Austin, Texas. Aqueous chemical baths and rinse water are processed at a pretreatment plant where acidity is neutralized and dissolved copper is removed prior to discharge to a sanitary sewer for further treatment in a POTW. In , the treatment process produced 1,417 tons of metal hydroxide sludge, a RCRA F006 hazardous waste. In , a team of environmental engineers, manufacturing engineers, and laboratory personnel was formed to reduce hazardous waste sludge generation at the water treatment plant by minimizing waste generation in the imaging line.

Areas of key importance to sludge reduction were identified as acid used in cleaning operations and developing solutions used prior to etching operations. Minimizing acid in the waste water reduces the amount of lime needed to neutralize the waste water. Reducing the developing solution reduces the carbonates in the waste water that precipitate as calcium carbonate in the presence of lime. By , the team accomplished a 90 percent reduction in hydrochloric acid used in cleaning for an annual savings of approximately $340,000 in chemical cost.

Additional work allowed for a 40 percent reduction of developing and stripping solutions used in the imaging area, for an annual savings of approximately $75,000. These changes resulted in an approximately 75 percent decrease in use of lime at the pretreatment plant. This decrease, in combination with reduced carbonate usage in developing solutions, resulted in a decrease in sludge production of over 670 tons per year (based on first half results) and a 47 percent reduction from sludge generation, for an additional savings of $250,000 in sludge disposal costs. This project has shown that waste minimization through chemical source reduction can reduce expenses as well as reduce waste.

In-Situ Generation of H2O2 in CO2 for Green Oxidations: We have demonstrated the use of CO2 as the sole solvent for the generation of propylene oxide (PO) from hydrogen, oxygen, and propylene via the in-situ generation of H2O2. CO2 can solubilize large quantities of gases, is immune to oxidative degradation and provides a non-flammable environment in which to mix H2 and O2. Our results to date show that the use of CO2 as the sole solvent in the reaction produces 90%+ selectivity to PO. We subsequently used the in-situ generation of H2O2 to oxidize benzene to phenol.

This technology could result in highly intensified processes for the synthesis of H2O2, PO, phenol, and other commodities. The chlorohydrin process for PO creates approximately 500 million gallons of salt-contaminated wastewater from US production alone, while the DOE has estimated that a one-step phenol synthesis could save 65 trillion BTU/year and eliminate 50 billion pounds of waste. H2O2 could be used to reduce the waste generated by these processes, yet H2O2 production using the anthraquinone route absorbs trillions of BTU needlessly and creates numerous waste streams. Demonstration that in-situ generation of H2O2 in CO2 supports subsequent oxidations with reasonable conversion and selectivity opens the door for more intensified, greener oxidation processes.

Integrated Methods for the Control of Aquatic Plants (IMCAPTM): Innovative Chemical and Precision Technologies: Integrated Methods for the Control of Aquatic Plants (IMCAP) is a set of newly developed and existing chemical and non-chemical technologies that successfully overcomes many challenges to "precision" use of pesticides. IMCAP makes possible planning for and the application of SePRO"s top herbicide product, SonarTM (chemical name fluridone), to aquatic environments within a few parts per billion of target concentration levels. SePRO developed or adapted five major components to create IMCAP: an immunoassay (FasTEST TM), two plant bioassays (PlanTEST TM and EffecTEST TM), and bathymetric/volumetric and hydroacoustic/remote sensing assessment techniques.

All five of these components are supported within a Geographic Information System (GIS)/Global Positioning Satellite (GPS) framework. IMCAP allows Sonar herbicide to be used at concentrations as low as 4% of its maximum approved FIFRA label use rate (e.g., 6 parts per billion (ppb) compared to the label rate of 150 ppb). At these lower application rates, Sonar provides control of some of the most noxious submerged aquatic invasive plant species while minimizing or eliminating harm to desirable native species. IMCAP, therefore, makes possible far more selective use of Sonar against target plant species, while taking advantage of Sonar"s other unique environmental properties that make it an attractive aquatic herbicide (e.g., it is nontoxic to animals and algae at its maximum application rates, and it induces the slow death of target vegetation, avoiding hypoxic or anoxic conditions).

IMCAP&#;s precision technologies allows up to a 70% reduction in chemical loading under certain treatment conditions. It also permits the wider scale use of Sonar with the resulting protections for animals, algae, native plant populations, drinking water, and recreational water uses, as well as reductions in herbicide costs. IMCAP is a successful system of "precision" technologies. No other manufacturer or user of aquatic herbicides or pesticides in general has developed or applied in a commercial setting a system comparable in scope or scale to IMCAP.

IntegRex Technology: In conventional manufacturing processes, poly(ethylene terephthalate) (PET) is produced in the melt phase at high temperature, formed into pellets and cooled, reheated for solid-state polymerization, and cooled again. Eliminating the slow, costly, solid-state phase had not been feasible because problems arose during polymerization entirely in the melt phase.

Eastman&#;s innovative reactor design and integrated process chemistry have solved the problems of making polymers entirely in the melt phase, enabling the production of meltphase polymers that are superior to those made in conventional processes. In the IntegRex process, the polymer is heated to a lower maximum temperature, cooled only once, and, thanks to intensified reactor technology, made with less equipment. Other advances include the innovative use of pipe reactors in polyester processes and novel catalyst systems. The viscosity of the in-process polymer is about three times higher than that encountered in conventional PET processes, in which much of the viscosity of the final product is achieved in the solid-state operation. The higher melt-viscosity makes it more difficult to move polymer through the process and also significantly impedes the mass transfer necessary to remove the ethylene glycol and water released during polymerization.

Eastman&#;s IntegRex Technology produces recyclable PET resin in a way that reduces energy consumption by 54 percent, reduces associated greenhouse gas emissions by more than 47 percent, occupies a smaller environmental footprint, and eliminates the need for wastewater treatment. Eastman uses the IntegRex process to manufacture its ParaStar resins. These resins are a drop-in replacement for standard PET in bottle-manufacturing equipment; they can be recycled along with traditional PET resins.

In late , Eastman opened a new 350,000-metric-ton PET plant at its Columbia, SC site. The facility is now home to the world&#;s first PET plant that uses IntegRex Technology: Eastman&#;s proprietary breakthrough process for producing PET resin that completely eliminates the solid-state process.

Invention and Commercialization of Environmentally Smart Thermosetting Binders: Thermosetting binders give shape and strength to nonwoven fibrous materials, including fiberglass insulation. The most common thermosetting binders are formaldehyde based, but concern with formaldehyde&#;s potential as a carcinogen and as an indoor air pollutant has sparked research for safer alternatives. Manufacturing operations and products that rely on formaldehyde-based technologies also require expensive emissions abatement equipment, employee protection measures, special handling, and transport.

In response, Rohm and Haas Company (ROH) has developed and patented AquasetTM acrylic thermosetting binders, a family of formaldehyde-free, curable, aqueous solutions of poly(acrylic acid), triethanolamine, and sodium hypophosphite (NaHP). Hypophosphite catalysis had been used earlier for esterification in permanent press fabric applications; ROH adapted it to fiberglass insulation to achieve greater network formation and robust physical properties. ROH enhanced reactivity and cross-linking by using NaHP as both an esterification catalyst and a chain-transfer agent. Ultimately, they enhanced the mobility of the polyol within the curing resin, increased the reactivity of primary alcohols such as triethanolamine, and optimized the cure temperatures.

Combining these steps, ROH created a class of acrylic thermosets that is an ideal green chemistry alternative to phenol-formaldehyde resins. The byproduct of cure is water; the technology eliminates formaldehyde wastes, emissions, and exposures. AquasetTM technology is nonreactive, nonflammable, recyclable, and benign at ambient conditions to ease handling, transport, storage, application, and cleanup.

Johns Manville (JM) has been refining the AquasetTM technology along with ROH. Since , when it began manufacturing formaldehyde-free fiberglass insulation, JM has converted all of its building insulation products to the AquasetTM technology, eliminating the emission of more than 200,000 pounds of formaldehyde and one million pounds of ammonia each year. JM has also eliminated more than 180,000 pounds of phenol and 280,000 pounds of methanol emissions per year. JM is now the only manufacturer exempted from the U.S. EPA National Emission Standards for Hazardous Air Pollutants (NESHAP) for Wool Fiberglass Manufacturing.

INVERTTM Solvents in Aircraft Paint Stripping: Recent changes in regulations affecting the aircraft stripping industry have resulted in increased research into new, more environmentally and toxicologically friendly formulations. The Dow Chemical Company has developed a new line of solvent continuous microemulsions, which have merit in aircraft paint stripping, to aid in the reduction of regulated chemicals as well as lower flammability and volatile organic compound (VOC) levels.

These solvent products are marketed under the INVERT trademark. Formulating with INVERT solvents allows for the inclusion of greater than 40 percent water in aircraft paint strippers so that worker exposure to chemicals, flammability, and VOC levels can be reduced. INVERT solvents are solvent continuous microemulsions that contain approximately 50 percent water, low surfactant levels (i.e., less than 5 percent), and approximately 45 percent solvents and cosolvents.

Paint stripping formulations can easily be prepared, using INVERT as a base, through the addition of active stripping solvents along with performance enhancing ingredients such as thickeners, activators, and evaporation retardants. Hydrocarbon-based stripper formulations often have low flash points and high VOC levels. The incorporation of water significantly increases fire point, and water addition reduces VOC levels. INVERT solvents offer an economical and effective way to incorporate water into hydrocarbon-based strippers to reduce flammability and VOC concerns without sacrificing performance. When methylene chloride is used as a stripping solvent, exposure and regulatory issues may call for a reduction in use level.

The use of INVERT solvent technology allows preparation of solvent continuous microemulsions with low methylene chloride content (i.e., less than 20 percent), while maintaining an excellent level of performance. The use of INVERT solvents in the aircraft stripping industry allows users to reduce worker exposure to regulated chemicals and to reduce emissions of volatile chemicals, while maintaining a high standard of performance and economic benefit.

Ionic Liquid/CO2 Biphasic Systems: New Media for Green Processing: Room-temperature ionic liquids are considered to be environmentally benign reaction media because they are low-viscosity liquids with no measurable vapor pressure. However, the lack of sustainable techniques for the removal of products from the room-temperature ionic liquids has limited their application. Professors Brennecke and Beckman have shown that environmentally benign carbon dioxide, which has been used extensively, both commercially and in research for the extraction of heavy organic solutes, can be used to extract nonvolatile organic compounds from room temperature ionic liquids (Blanchard et al., Nature, , 399, 28).

They found that extraction of a material into carbon dioxide represents an attractive means for recovery of products from ionic liquids because (a) CO2 dissolves in the ionic liquid to facilitate extraction, and (b) the ionic liquid does not dissolve appreciably in the CO2, so the product can be recovered in pure form. The research groups of Professors Brennecke and Beckman have shown that ionic liquids (using 1-butyl-3-methylimidazolium hexafluorophosphate as a prototype) and CO2 exhibit extremely unusual, and very attractive, phase behavior.

The solubility of CO2 in ionic liquids is substantial, reaching mole fractions as high as 0.6 at just 8 MPa. Yet the two phases do not become completely miscible, so CO2 can be used to extract compounds from the ionic liquids. Most importantly, the composition of the CO2-rich phase is essentially pure CO2; that is, there is no measurable cross-contamination of the CO2 by the ionic liquid. Moreover, nonvolatile organic solutes (using naphthalene as a prototype) may be quantitatively extracted from the ionic liquid with CO2, demonstrating the tremendous potential of ionic liquid/CO2 biphasic systems as environmentally benign solvents for combined reaction and separation schemes.

Irbesartan (Avapro®) Greenness Project: Irbesartan, which is chemically synthesized, is an angiotensin II receptor antagonist used to treat hypertension and renal disease in type 2 diabetic patients. Although clinical trials had demonstrated the medical benefits of Irbesartan, the original synthetic process was difficult to manage from an environmental, health, and safety (EHS) perspective. The primary concerns included a potential runaway bromination reaction, severe skin and eye irritation from an intermediate product, and negative environmental effects of several organic solvents. Previously, Bristol-Myers Squibb (BMS) had mitigated some of the negative EHS impacts of the original synthesis, but the bromination in the first synthetic step remained a concern. This bromination created a nonbiodegradable byproduct that required incineration and, thereby, created a significant waste disposal problem.

To address that problem and further minimize EHS impacts, BMS modified the bromination and crystallization processes it uses in the synthesis and modified the recrystallization process for the active pharmaceutical ingredient. These modifications have increased yield, saved energy, reduced the use of hazardous materials, reduced waste, and improved workplace health and safety. Based on a projected 5-year production of Irbesartan, BMS expects to save over 680 metric tons of solid chemicals, over 40 million liters of solvents, and 4.4 million liters of water. Other projected benefits include a 325-ton reduction in solid waste requiring incineration and a savings of 24,400 megawatts of energy from recycling the two remaining process solvents.

Iron Oxide for Arsenic Removal from Drinking Water: The U.S. EPA&#;s best available technologies for removing arsenic from drinking water include aluminum adsorption, ion exchange, reverse osmosis, and coagulation filtration. Adsorption technology is among the simplest approaches for removing metals, such as arsenic, from drinking water, but conventional adsorbents such as activated carbon or activated alumina have a limited capacity for arsenic.

Severn Trent Services worked with LANXESS Corporation to develop the proprietary Bayoxide® E33 media for efficient, effective adsorption of arsenic. Bayoxide® E33 consists of iron oxide hydroxide in the alpha-FeOOH form; it has a very high specific surface area and a high adsorption capacity for arsenic. Bayoxide® E33 is mechanically robust, is stable with a uniform grain size, has a low leaching potential, has good water distribution across the media minimizing pressure buildup, and is immediately effective in a start-stop process. Bayoxide® E33 can remove arsenic from groundwater to well below 4 micrograms per liter. In an adsorption system, SORB 33®, the Bayoxide® E33 media life expectancy depends on site-specific water quality and operating levels. The exhausted media is nonhazardous, passing the U.S. EPA&#;s Toxicity Characteristic Leaching Procedure (TCLP) threshold requirements.

Bayoxide® E33 media achieves a three-fold reduction in waste. First, Bayoxide® E33 media is manufactured from iron sulfate, a waste product of the steel industry. Second, service wash water from routine backwashing of the Bayoxide® E33 media can be reclaimed and returned to the plant inlet. Third, exhausted Bayoxide® E33 serves as a source of iron oxide for steel manufacturing processes, namely direct reduction iron (DRI) process and sintering plants, eliminating the disposal of Bayoxide® E33 into landfills.

The U.S. market for adsorptive arsenic removal media is estimated at over 6,000 metric tons per year, excluding residential applications. As of November , Severn Trent Services had sold Bayoxide® E33 to municipalities in 35 States in the United States.

ISOMET: Development of an Alternative Solvent: The U.S. Bureau of Engraving and Printing, the world"s largest security manufacturing establishment, produces currency, postage stamps, revenue stamps, naturalization certificates, U.S. savings bonds, and other government securities and documents. Until , Typewash, a solvent mixture, was used by the Bureau for cleaning typographic seals and serial numbers of the COPE Pack (overprinting presses) and for cleaning of sleeves of postage stamp presses. Typewash is a solvent mixture composed of methylene chloride (55%), toluene (25%), and acetone (20%). The use of Typewash was no longer in compliance with the District of Columbia environmental law and the federal air toxics law.

An alternative solvent, Isomet, was designed and developed to replace Typewash. Isomet is a mixture of isoparaffinic hydrocarbon (55%), propylene glycol monomethyl ether (10%), and isopropyl alcohol (35%). Isomet is less toxic, less polluting, and environmentally friendly. Isomet was found to be acceptable in the areas of (1) cleaning ability, (2) solvent evaporation rate, (3) solvent odor, (4) environmental and safety compliance, and (5) cost. Thus, a solvent discharged at the rate of 7,500 gallons per year was made environmentally friendly. The performance of Isomet is excellent and it has been used for cleaning all postage stamp and overprinting presses in the Bureau.

iSUSTAIN® Green Chemistry Index Tool for Sustainable Development: Cytec Industries Inc., in collaboration with Dr. John Warner, has developed the iSUSTAIN® Green Chemistry Index scoring tool. This is the first such tool to be based on the 12 Principles of Green Chemistry. The tool includes a metric for each of the twelve principles, which range from atom economy to reduced energy use and process hazard. The tool makes assessments using a novel algorithm and a database of safety, health, environmental impact, and regulatory status scores for the raw materials used to prepare the products being assessed. Information for assessments comes from several sources including EPA&#;s Sustainable FuturesTM modeling, qualitative structure-activity analysis (QSAR), literature searches, and testing.

iSUSTAIN® measures the sustainability of Cytec&#;s products and processes, allowing the company to develop both initial sustainability baselines and improvements. The index allows Cytec&#;s technical community to identify those factors within their control that can affect the overall sustainability of their processes. Cytec has been using the tool internally since to score both new product ideas and existing commercial products. Cytec has also incorporated the tool as part of its Stage-Gate New Product Introduction (NPI) system.

Starting in March , Cytec, in partnership with Sopheon Corporation and Beyond Benign Foundation, made the iSUSTAIN® Green Chemistry Index available to the public without charge. An enhanced version is available for a fee, but Cytec provides it free to academic users. iSUSTAIN® will foster learning and change the mindset of university scientists so future researchers will have the principles of sustainability ingrained in their thinking. By the end of , over 771 users including industry, government, and academia had logged onto the tool. Users signed up from 114 unique domains and 30 different domain types, creating over 1,000 scenarios using 442 substances from the materials database of 5,494 substances.

JONCRYL® FLX : A High-Performance, Water-Based Polymer to Facilitate the Conversion from Solvent- to Water-Based Inks in Surface Film Flexible Packaging Printing: The inks used in the flexible packaging industry must meet extensive performance requirements. They are expected to print well on a variety of flexible substrates and provide good print quality, excellent water and chemical resistance, adhesion, crinkle resistance, and heat resistance. Traditionally, such requirements have demanded that printing inks be solvent-based. Typical solvents are alcohols and acetates. An estimated 135&#;150 million pounds of solvent-based inks are used each year in the United States for applications on film and laminated flexible packaging. This high-volume use is, however, associated with environmental and handling concerns.

Johnson Polymer has developed a unique, water-based, self-cross-linking polymer system that has enhanced the performance of water-based inks significantly. Specific improvements include water-resistance, crinkle-resistance, and adhesion. At the same time, the new inks maintain the on-press resolubility that is critical for high-quality printed images.

This nomination compares the performance of JONCRYL® FLX , a new self-cross-linking, water-based polymer, to that of traditional water-based polymers; it also compares print trials using water-based inks based on JONCRYL® FLX to a traditional solvent-based ink.

Johnson Polymer formally introduced JONCRYL® FLX to the U.S. printing ink manufacturing market in October , culminating a research and development effort in the United States and Europe spanning the previous three to four years. Johnson Polymer has conducted multiple press trials, resulting in ongoing commercial sales in Europe and initial trial sales in the United States.

Kemiko and Sta-Crete Low VOC Architectural Coating: All of Epmar&#;s Kemiko and Sta-Crete low VOC architectural coating products referred to in this paper are water-based and significantly reduce the emission of ozone-producing VOCs. These products promote the EPA&#;s goal of reducing negative health effects from commonly used products, especially in cases such as architectural coatings to which humans will have long-term exposure.

In order to maintain the low VOC emission characteristics of the Kemiko and Sta-Crete product lines, Epmar and their raw material suppliers maintain strict manufacturing and quality specifications of the raw materials and finished product.

Epmar&#;s formulating technology minimizes the use of VOC-emitting materials. These unique products utilize commercially available raw materials and are commercially competitive in terms of performance, handling and pricing.

Kiehl&#;s "Aloe Vera" Biodegradable Liquid Body Cleanser: By developing and commercializing Kiehl&#;s "Aloe Vera" Biodegradable Liquid Body Cleanser, L&#;Oreal launched the first ever Cradle to Cradle® certified biodegradable product within the cosmetic industry. Inspired by the Cradle to Cradle® philosophy and in collaboration with the Make It Right Foundation, L&#;Oreal formulated this product with green chemistry in mind. Cradle to Cradle® certification is a multi-attribute eco-label of McDonough Braungart Design Chemistry (MBDC). It assesses a product&#;s safety to humans and the environment as well as its design for future lifecycles. Kiehl&#;s "Aloe Vera" Biodegradable Liquid Body Cleanser received the Cradle to Cradle® silver certification. This product received a gold score in material reutilization and silver scores in the other four categories: material health, renewable energy use, water stewardship, and social responsibility.

The ingredients in the Kiehl&#;s "Aloe Vera" formulation are water, sodium coco-sulfate, cocoglucoside, sodium benzoate, potassium sorbate, glycerin, Aloe barbadensis leaf juice, citric acid, sodium chloride, and fragrance. L&#;Oreal minimized the amount of ingredients to simplify and optimize the use of each ingredient and avoid unnecessary ingredients. In formulating this product, the company used ingredients in three main categories: coconut-derived surfactants for cleansing, preservatives commonly found in food, and fundamental moisturizing ingredients with known benefits. L&#;Oreal selected each ingredient not only to ensure biodegradability but also to ensure that the product was not ecotoxic.

The product is packaged in 100 percent post-consumer recycled poly(ethylene terephthalate) (PET) to minimize the production of plastic bottles from new materials. L&#;Oreal launched this product in . It donates all of the net profits from sales of this product to the Make It Right Foundation.

Kilogram-Scale Purification of Pharmaceutical Candidates and Intermediates Using Preparative Supercritical Fluid Chromatography: Preparative chromatography is increasingly used in the pharmaceutical industry to purify kilogram quantities of developmental compounds for preclinical evaluation. Historically, the industry has carried out these separations by high-performance liquid chromatography (HPLC) using large amounts of petrochemical-derived organic solvents. Merck has recently demonstrated the possibility of performing these separations at the kilogram scale using subcritical or supercritical fluid chromatography (SFC), in which pressurized carbon dioxide (CO2) replaces the hydrocarbon solvents often used in HPLC.

Using custom-designed preparative SFC equipment prepared in collaboration with several vendors, Merck has recently carried out the first kilogram-scale SFC enantioseparations of pharmaceutical intermediates in the pharmaceutical industry. Merck has reported its results in a recent publication (Welsh, C.J. et al., LC-GC, , 16&#;29). In one example, enantioseparation of 2.5 kilograms of an intermediate was projected to require 36,000 liters of solvent by HPLC, but used only 900 liters by SFC. Although this example is extreme, a 10-fold decrease in solvent consumption is typical. Equally important, SFC also produces a corresponding decrease in solvent evaporation, leading to considerable savings in equipment, time, and energy. Further, preparative SFC is generally more productive than HPLC, especially for chiral separations. The SFC advantage can be extreme, as in the case where there was no suitable HPLC purification for a single stereoisomer of a drug candidate intermediate, yet SFC (5 cm i.d. column, 350 g/min, 830 L organic solvent) purified 1.7 kilograms easily in only 72 hours. During , Merck demonstrated preparative SFC using a 15-ton CO2 bulk tank and custom-built, 3-kilogram-per-minute CO2 delivery system.

Merck has demonstrated that preparative SFC is not only a more environmentally friendly method for purifying developmental drugs and intermediates, it is simply better, with greater productivity and cost-effectiveness, both of which are important considerations for large-scale separations to support pharmaceutical manufacturing.

KILZ MAXTM PRIMER-SEALER-STAINBLOCKER: Oil-Based Performance in a Water-Based Formula with Less Environmental Impact: Solvent- and shellac-based stain-blocking primers typically include resins that require petroleum-based solvents such as mineral spirits or ethanol. These solvents are not only combustible (and in some cases flammable); they also release significant amounts of volatile organic compounds (VOCs) during application and drying. Water-based primers made with a variety of acrylic and styrene&#;acrylic resins are available, but they have extended dry times and cannot approach the stain-blocking properties of solvent-based primers.

Masterchem Brands has developed KILZ MAXTM primer, using specialized epoxy-based resin technology to provide heavy stain-blocking and odor blocking in a more eco-friendly, water-based formula. This product has the benefits of solvent- or shellac-based primers including the ability to block severe stains and odors, resist tannin stains, and more. It does not have the associated drawbacks of high odor, high VOCs, or clean up that requires mineral spirits. Independent testing confirms that KILZ MAXTM performs as well or better than oil- and shellac-based primers on virtually all problem stains, odors, and other surface imperfections.

It also meets or exceeds the performance of many products marketed as having similar technology. KILZ MAXTM primer has a VOC level near 75 grams per liter; this is over seven-fold lower than competitive shellac-based primers and six-fold lower than typical competitive specialty primers.

Replacing the solvent with water in KILZ MAXTM primer eliminates approximately 3 pounds of VOCs per gallon compared to KILZ® Original solvent-based primer. In , Masterchem Brands sold over 3.3 million gallons of KILZ® Original primer. Replacing the higher-VOC version with KILZ MAXTM primer would reduce airborne VOCs by as much as 9 million pounds annually. Another benefit is the ability to sell high-performance stain-blockers in areas regulated by the South Coast Air Quality Management District (SCAQMD), the California Air Resources Board (CARB), and others. KILZ MAXTM primer was first produced and launched in retail markets in .

Klean-Strip® GreenTM Safer Paint Thinner: Petroleum distillates present risks to human health and the environment, such as air pollution from volatile organic compounds (VOCs), health hazards from inhalation and skin contact, and fire hazards during manufacture, use, storage, and transport. Although consumers can foresee these hazards and government regulators, industry, and the marketplace deem them to be acceptable and reasonable, Barr sought to develop a safer, more environmentally friendly alternative.

Klean-Strip® GreenTM Safer Paint Thinner is a formulation of Type IIC mineral spirits suspended in water with a small amount of oleic acid emulsifier. It contains 67 percent lower VOCs than regular paint thinner. The mineral spirits are a safer petroleum distillate without any hazardous air pollutants (HAPs). Consumers of Klean-Strip® GreenTM Safer Paint Thinner report lower odors and less skin irritation than with regular paint thinner. Klean-Strip® GreenTM Safer Paint Thinner is nonflammable and noncombustible; therefore, it poses no fire hazards.

Its lower VOC content means that it is less volatile than regular paint thinner, so indoor air pollution is less of a problem for consumers. Unlike regular paint thinner, Klean-Strip® GreenTM Safer Paint Thinner is not a hazardous waste under the Resource Conservation and Recovery Act (RCRA), not a hazardous substance under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) and the Superfund Amendments and Reauthorization Act (SARA), and not a hazardous material under Department of Transportation regulations.

Other environmental benefits include less dependence on nonrenewable resources such as petroleum because 67 percent of the product is water, a renewable resource. Because water is readily available at Barr&#;s manufacturing site, there are fewer transportation risks and environmental impacts (i.e., air pollution) associated with raw material supply. Since its introduction in , this product has had average annual sales of 8 million pounds, eliminating the use and VOC emissions of 5 million pounds of petroleum distillate.

Liquid but Nonvolatile Sulfonic Acids and Amines: Greener Chemicals for Greening Processes: Chemistry impacts most aspects of the global economy. Acids and bases, many of the former as sulfonic acids and the latter as amines, impact chemistry. Pure or in solution, these acids and amines are commonly volatile, noxious, and malodorous, are frequently flammable, and often pose substantial risks to health and the environment. Professor Davis has effectively eliminated these problems by covalently anchoring acid and amine functionalities to nonvolatile liquid salt matrices (ionic liquids; ILs). These ILs function as nonvolatile reagents and catalysts. Their application to important problems such as carbon dioxide (CO2) capture and catalysis can lead to process efficiencies that are greener because they consume less energy.

Professor Davis and his group covalently tether reactive functional groups to ions that they then use to formulate ILs. Their term "task-specific ionic liquids" (TSILs) describes these materials. Their successes include developing nonvolatile liquid amine TSILs that reversibly scavenge CO2. These TSILs can replace aqueous monoethanolamine and diethanolamine that scavenge CO2 impurities from natural gas. First-generation TSILs have a CO2-uptake capacity equal to that of the free amines and require only about one-third the energy to extrude the captured CO2. Second-generation amine TSILs are even more effective, contain no fluorine or other exotic elements, have an atom-efficient synthesis, and are far less expensive. Three large U.S. companies are investigating amine TSILs for bulk CO2 capture and membrane-based CO2 separation. During , Professor Davis licensed the rights for small-scale manufacturing and sales of second-generation amine TSILs to Frontier Scientific, Inc.

Professor Davis has also developed acid TSILs that are nonvolatile liquid Brønsted acids for catalyzing important industrial organic reactions. An industrial collaborator is investigating these TSILs. Professor Davis has licensed first-generation amine and acid TSILs to Merck KGaA. He is negotiating agreements with several large international firms for second-generation TSILs.

Liquid Oxidation Reactor (LOR): Praxair, Inc. has developed a unique process that allows the safe oxidation of organic chemicals with pure or nearly pure oxygen. This technology, known as the Liquid Oxidation Reactor, (LOR), provides significant environmental advantages compared to conventional, air-based oxidation processes. The use of oxygen in place of air reduces the total gas throughput to the reactor, thereby reducing the compression energy and the amount of vent gas that must be treated prior to atmospheric release. In addition, the oxygen use can positively affect the chemistry of the reaction, allowing the operation of the process at lower temperatures or pressures, thereby improving selectivity without sacrificing production rate. T

he use of the Praxair LOR increases the overall rate of reaction and volumetric productivity of hydrocarbon oxidations while increasing selectivity and reducing the loss of solvent and reactant to carbon oxides. The increased chemical efficiency with oxygen results in substantial raw materials cost saving, and a 96 percent reduction in the quantity of waste gases. The cost of product purification and waste disposal is reduced substantially.

In addition, the lower temperature operations afforded by the LOR process reduces the loss of reactant or solvent to byproducts and to waste streams that also can contribute to environmental problems and must be treated prior to release. The LOR will enable a large and important segment of the U.S. chemical industry to realize more efficient use of raw materials, reduced environmental emissions, and energy saving. Because the LOR also allows for higher productivity, lover [sic] capital costs, and, consequently, improves competitiveness, there are significant incentives for the implementation of the technology. Average operating-cost [sic] savings and productivity gains worth $5 to $20 million per plant per year have been projected.

Liquid Seal and Nonhazardous Cleaner Eliminate Odor, Health, and Maintenance Problems Stifling the Acceptance and Implementation of Waterless Urinals: The Kohler Company approached Environmentally Sensitive Solutions, Inc. (ESS) to develop the chemistry for a new waterless urinal in a joint project. Waterless urinals have existed for years, but their high maintenance requirements and lack of effective odor and exposure controls have limited their large-scale adoption. ESS was to develop a superior liquid seal and nonhazardous cleaner that would be an environmentally friendly combination, both more effective than current waterless urinal designs and safer than traditional, caustic urinal cleaners.

The ESS unique liquid seal eliminates the odor that is problematic in traditional waterless urinals. The patent-pending liquid seal is a formulated vegetable-oil-based, biodegradable product that floats on the urine in the trap. This liquid seal is formulated to prevent sewer gases and urine odors from emanating from the waterless urinal while allowing urine through. Even when subjected to turbulence, the liquid seal repairs itself quickly, preventing hazardous gases and undesirable odors from escaping. The liquid seal chemistry also eliminates the need for the hazardous urinal pucks used as supplemental odor control in an estimated 90 percent of flush urinals. These p-dichlorobenzene-based pucks have been proven harmful to human health and the environment.

The ESS waterless urinal cleaner is neutral, noncorrosive, and surfactant-based; it eliminates the hazards of traditional cleaners. For daily cleaning, the ESS cleaner is compatible with the liquid seal and does not adversely affect the performance of the liquid seal.

The keys to waterless urinal acceptance and implementation are the complete odor control and low maintenance that only these green chemistries can provide. Each waterless urinal has the potential to save up to 40,000 gallons of water per year. Kohler has implemented the ESS liquid seal and cleaner in the global launch of its StewardTM collection of waterless urinals.

Low Temperature, Hydrocarbon Hydroxylation: The Key to Greener, Lower Cost Chemistry for Chemicals, Fuel and Power for the 21st Century: As we enter the 21st century we should pause to consider that our foundational technologies are inherently inefficient. Thus, power production is only 20&#;30% efficient while fuel and basic chemicals are primarily produced from limited petroleum reserves rather than from the vast reserves of underutilized remote natural gas. The development of new, lower-temperature, hydrocarbon processing chemistry could lead to a paradigm shift toward greener technologies. The key to this next generation green chemistry is the development of catalysts that allow the direct conversion of CH bonds to COH bonds at temperatures below 250°C in high yields. With this green chemistry power production could ultimately be carried out with >300% reduction in emissions and remote natural gas and other hydrocarbon feedstocks could be more efficiently converted to fuel and basic chemicals. Such catalysts have been long considered a "Holy Grail" in chemistry. However, the recent work of the PI has provided the first demonstration of the only known catalyst that allows the direct conversion of methane to methanol in >70% yield at 220°C. With this precedent in hand, the paradigm shift to greener, petrochemical processes is well underway.

Low VOC Chemical Agent Resistance Coatings: This project developed a low volatile organic compound (VOC) Chemical Agent Resistant Coating (CARC) system suitable for use on military equipment in which the materials and processes for the reformulation/application, stripping, and disposal are optimized and in compliance with current and anticipated regulatory requirements. The primary focus was to reduce the VOC of the polyurethane topcoat from 3.5 lb/gal to 1.8 lb/gal. Additionally, this CARC will eliminate the hazardous air pollutants (HAP) and toxic solvents used in the current topcoat formulation.

At current annual usage, a CARC targeted to a 1.8 lb/gal VOC limit would save at least 5 million pounds of VOC per year, proportionately reduce photochemical smog generation and avert Notices of Violation (NOV) at user facilities including depots, air logistic centers (ALC), bases, and original equipment manufacturers. VOCs which would be reduced or eliminated include: methyl isobutyl ketone, methyl isoamyl ketone, toluene, xylene, and butyl acetate, all of which are HAPs. The technology developed by this project will also eliminate the need to install emission control devices for approximately twelve facilities for a total cost avoidance of $60 million for equipment installation and $3 million in annual operating costs. By developing one CARC topcoat for use by all the Services, substantial savings will result in procurement and logistics operations. While this formulation was developed specifically for military applications, its demonstrated durability and enhanced performance properties will make it ideal for hard use civilian applications.

After successful development of the new CARC formulation, the FY99 efforts focused on stripping tests using chemicals which have been used recently at various depots. The most recent data acquired in the wheat starch, laser and chemical stripper tests yielded results similar to those obtained from stripping with steel shot, flash jet, plastic media, and garnet. The recent data indicate that the new CARC strips at a rate similar to that of the current CARC topcoat.

Low-Temperature Cleaning In Place: Most industrial processes for cleaning in place (CIP) combine chemistry, temperature, time, and mechanical energy. Traditional CIP systems require high-strength chlorinated caustic soda and temperatures of 150 °F. In an average fluid milk plant, these CIP processes account for approximately half of the plant&#;s total fossil fuel use and carbon dioxide (CO2) emissions.

Ecolab has developed the Advantis LT two-product program for CIP in the dairy and food industries. The first product is an alkaline detergent including water conditioners and a transition metal catalyst (MnSO4 or Fe2(SO4)3). The second product is a detergent containing hydrogen peroxide (H2O2). Injecting the two products sequentially into the CIP balance or supply tank during circulation generates microbubbles of oxygen on soiled structures, enabling fluid in the system to flush away the loosened soil. The Advantis LT program results in successful cleaning at lower temperatures: steam heat exchangers bring the temperature up to 110 °F instead of 150 °F, saving 50 percent in energy. A typical cheese plant could save steam equal to 5,000 decatherms of natural gas annually; the 350 large dairy plants in North America could save a total of 2.0 million decatherms.

Lower-temperature cleaning cycles reduce the length of heat-up steps by as much as 10&#;15 minutes per object being cleaned. In many plants, this can translate to increased output. Reduced cleaning temperatures also extend equipment life by avoiding temperature stress on stainless steel structures and elastomeric gaskets and seals. Finally, Ecolab&#;s technology reduces caustic soda consumption by 35 percent without using any chlorine bleach, resulting in less wastewater.

Calculations for the International Dairy Foods Association estimate that the Advantis LT program can reduce the overall carbon footprint of a fluid milk plant by up to 10 percent. Following further refinements, Ecolab plans to commercialize this technology during the latter half of .

Lysine-Based Phosphonate Scale Inhibitor with Improved Biodegradation and Maintained Performance: Offshore oil production is increasing the demand for scale inhibitors as reservoirs age and production more frequently requires secondary recovery techniques, such as saltwater injection. Offshore oil wells are susceptible to accumulating scale when ions in injected seawater mix with ions in oil-bearing formations. The precipitation of calcium carbonate, barium sulfate, and other scales from the water that comes up with the oil can reduce production rates, increase maintenance costs, or block pipelines completely.

The annual worldwide market for oilfield scale inhibitors is $200 million. Organic phosphonates inhibit scale formation as low-dose additives (sometimes at levels below parts-per-million, far below the dosage required for comparable carboxylate chelants). They have high efficacy, low toxicity, and a low tendency to bioaccumulate. They typically exhibit low rates of biodegradation, however, and legislation in the United States and North Sea countries has driven research into biodegradable scale inhibitors.

Although polymeric scale inhibitors can substitute for phosphonates because they have greater biodegradation rates and a low tendency to bioaccumulate, they cost more and require higher dosages to be effective. Champion Technologies has developed new phosphonate scale inhibitors that biodegrade more readily and offer a competitive price yet preserve the inherently high performance, low toxicity, and low bioaccumulation of phosphonates.

Champion replaced diethylenetriamine (DETA) and other synthetic polyamine starting materials for traditional phosphonates with lysine, a naturally occurring amino acid that is also a renewable polyamine. Champion optimized the extent of phosphonomethylation to maximize both performance and biodegradation. Lysine phosphonate exhibits the desired scale inhibition and is inherently biodegradable, demonstrating 20&#;60-percent biodegradation in 28 days by OECD 306 (the seawater biodegradation test of the Organisation for Economic Co-operation and Development). By comparison, traditional phosphonates are nonbiodegradable, with less than 20 percent biodegradation in 28 days by OECD 306. In , Champion submitted a patent application for this technology.

Manufactured Firelogs Based on Whole Timber: The market for conventional manufactured firelogs is 110 million logs per year. Conventional manufactured firelogs offer lower emissions than cordwood. They are typically made of recycled materials such as sawdust bound together with petroleum wax from fossil fuel, which is a solid fuel additive.

Torch Technologies has developed an alternative to conventional manufactured firelogs using cleaner-burning, inexpensive, bioderived materials that are waste streams from various industries. Torch firelogs are made from whole timber and crude glycerol by a simple timber treatment process. The timber is cutoff parts of plantation-grown trees that have only minimal commercial value as a feedstock for the paper industry. Because the timber is whole, Torch can use a liquid fuel additive, glycerol, which is a low-value byproduct of biodiesel production. Torch firelogs contain no fossil fuel components.

Torch firelogs are a sustainable fuel option. They are 20&#;40 percent less expensive to produce than conventional manufactured firelogs, depending on the raw materials. They burn with emissions that are 50 percent lower than conventional manufactured firelogs. Torch firelogs are structurally stronger than conventional manufactured firelogs, which makes them safer to burn and easier to package and transport (saving cost and energy). Their structure also allows consumers to burn multiple logs at one time, similar to a conventional cordwood fire, but with an extended burn time.

Torch Technologies LLC is a joint business venture between Torch Innovations and Chemco Inc., established to market the new Torch firelog for use in domestic fireplaces, stoves, and outdoors. During , the company continued development and raw material sourcing. It validated the combination of a wide range of waste streams from the logging, sawmilling, biodiesel, papermaking, and other industries.

Manufacturing More Efficient Fuel Cells to Reduce Carbon Dioxide Emissions: Huntsman Advanced Materials and GrafTech have collaborated to develop two new grades of high-performance, resin-impregnated, expanded graphite composites for GRAFCELL® bipolar plates targeted at high-temperature fuel cell applications. The Huntsman resins that enable the new composites were developed to offer improved properties yet remain compatible with GrafTech&#;s continuous manufacturing process.

Composites incorporating benzoxazine resins allow continuous operation at 120 °C and will meet the aggressive targets for performance and cost set by the U.S. Department of Energy for automobiles in . Composites incorporating bismaleimide resins allow operation at temperatures up to 180 °C in concentrated acid environments, enabling these composites to be used in phosphoric acid fuel cells and polymer electrolyte membrane (PEM) fuel cells incorporating polybenzimidazole (PBI) membranes. These new systems are superior to existing commercially available systems in mechanical testing, gas permeability, dimensional stability, and single cell fuel testing. Compared to the metal bipolar plate, the graphite composite bipolar plate with new Huntsman resins has the following advantages: (1) superior corrosion resistance, (2) lighter weight for greater efficiencies, (3) a long operating life because there is no poisoning of the PEM membrane, and (4) consistent electrical performance because no insulating surface forms. These benefits have a direct impact on the reduction of carbon dioxide (CO2) emissions during the lifecycle of the fuel cell.

These resin systems also enable the use of cost-effective, high-volume manufacturing techniques that will lower plate costs per kilowatt and ultimately accelerate the widespread commercial adoption of hydrogen-based energy systems. Huntsman anticipates the commercialization of fuel cells with its benzoxazine resins for stationary power applications in ; it anticipates the commercialization of fuel cells with its bismaleimide resins for automobiles during late or early .

Melt Processing for Solvent-Less Manufacture of High Performance Dry Powder Coatings: The innovation presented in this nomination, developed at the Polymer Processing Institute at New Jersey Institute of Technology, provides a process to manufacture dry powder coating products without the use of solvent. The necessary performance characteristics for the dry powders are achieved by the use of crosslinkable acrylics or crosslinkable unsaturated polyesters prepared in solventless systems by melt processing. The resulting formulations can be shown to have superior performance characteristics, and have been applied within the last five years to automotive coating operations. The technology extends the benefit of dry powder coating in reduction of solvent use by eliminating the use of solvent in the manufacture of the dry powder in addition to the use of the dry powder. The basic concept of chemical reaction in melts with careful selection and handling of reactants and of careful control of reaction conditions is widely applicable to chemical manufacturing.

Membrane Separation in Solvent Lube Dewaxing: Mobil Oil Corporation and W. R. Grace have developed a pioneering technology that significantly reduces the impact of solvent refining of lubricants on the environment. The membrane-based process provides greater lubricant selectivity and reduces waste generation, while simultaneously decreasing emissions of volatile organic compounds and greenhouse gases. The use of membranes to facilitate the solvent dewaxing of lubricants represents the first significant, environmentally focused improvement in this technology in over 40 years. In conventional lube dewaxing, a lube oil/solvent mixture is generated as part of the process. The solvent is removed from this mixture by distillation to isolate the lube oil product. The solvents are then cooled and refrigerated to the desired process temperature before being recycled to the process.

The improved process uses a proprietary polymeric membrane material developed by W. R. Grace to separate up to 50% of the dewaxing solvents from the lube oil/solvent mixture. Consequently, the spirally wound membranes significantly reduce energy consumption by minimizing the need for energy-intensive distillation, cooling, and refrigeration. As a result, a single commercial facility could reduce fuel oil consumption by 36,000 bbl/yr. This equates to a reduction in greenhouse gas emissions of about 20,000 tons/yr for each plant in which the technology is installed. The same plant would reduce cooling water use by nearly 4 million gal/day, or about 15 billion gal/yr.

The use of membranes allows more solvent to be recirculated in the dewaxing operation, which in turn leads to higher lubricant yields and a reduction in the amount of undesirable byproducts generated in the process. The higher process yields reduce by about 5% the volume of crude oil required to produce a given volume of lube oil. For a world-scale plant, this equates to a savings of about 2 million barrels of crude oil per year. Finally, the loss of dewaxing solvents, which are volatile organic materials, into the environment could be decreased by 50 to 200 tons/yr per plant depending on the age and mechanical condition of the dewaxing equipment.

This results from a reflection in the number of pieces of equipment required to refine a given volume of lube oil. This technology was first implemented commercially at Mobil&#;s Beaumont, Texas, refinery. It can easily be retrofitted into existing plants or incorporated into new plant designs and is currently available for license.

Mesotrione and Callisto® Plant Technology: The mesotrione story began when a U.S. Syngenta scientist noticed that few weeds were growing under a Callistemon citrinus (bottle brush) plant. Upon analyzing a soil sample, he discovered that the Callistemon plant secretes an herbicidal compound through its roots, an ability known as allelopathy. Using a combination of infrared spectroscopy, mass spectroscopy, and nuclear magnetic resonance, he identified the structure of the allelopathic compound produced by the bottle brush plant as leptospermone. This allelochemical, leptospermone, presented interesting properties including good foliar activity, soil activity, being tolerated well by corn, and control of a wide range of weeds.

Scientists at Syngenta discovered mesotrione (C14H13O7NS; MW 339.32) by modifying and optimizing the backbone of leptospermone. Mesotrione has the same mode of action as leptospermone, but is 20 times more potent and, thus, more commercially viable. Mesotrione is a member of the triketone group of selective herbicides that act by inhibiting the enzyme p-hydoxyphenylpyruvate dioxygenase (HPPD). HPPD is part of the biosynthetic pathway for carotenoid, a precursor of chlorophyll. Thus, inhibition of HPPD causes bleaching followed by necrosis in sensitive plants (i.e., target weeds).

In , U.S. EPA approved mesotrione as a reduced-risk herbicide. Shortly thereafter, Syngenta introduced Callisto®, a mesotrione-containing herbicide for post-emergent weeds. Callisto® challenged all competitive broadleaf herbicides for use in corn crops: during its first full-season year in , it achieved almost a 25 percent share of the post-emergent, broadleaf weed control market, treating more than four million acres. Syngenta&#;s introductions of two mesotrione formulations for pre-emergent weeds, LUMAX® in and Lexar® in , added strength to the Callisto Plant Technology family. Today, farmers worldwide recognize mesotrione and Callisto Plant Technology as unique herbicide products that provide important benefits including exceptional crop safety, unprecedented broadleaf weed control, application flexibility, and a 21st-century environmental profile.

Metabolic Engineering of Crops for Commercial Production of Biodegradable Plastics: Poly(hydroxyalkanoates) (PHAs) are a class of polymers accumulated by numerous bacterial species as carbon and energy reserves. These polymers have thermoplastic properties that make them attractive as biodegradable alternatives to petrochemical plastics. One polymer of this class, poly(ß-hydroxybutyrate-co-ß-hydroxyvalerate) (PHBV) is currently produced by fermentation of the bacterium Ralstonia eutropha; however, the process is not economically competitive with polymer production from petrochemicals. PHA production in green plants promises much lower costs, but producing polymer with the appropriate monomer composition is problematic.

The goal of Monsanto is to produce PHBV by transferring the R. eutropha biosynthesis pathway to plants and modifying the plant&#;s intermediary metabolism to generate the appropriate metabolic precursors for copolymer synthesis. Metabolic engineering of Arabidopsis and Brassica to redirect intracellular pools of both short-chain fatty acids and amino acids resulted in the production of PHBV. This process required transformation of plants with four separate transgenes, and a novel application of one endogenous plant enzyme.

This technology provides a novel biosynthetic route to plastic using atmospheric CO2 as the carbon source and sunlight as energy. The project is intended to utilize green technology from cradle to grave. The energy for polymer extraction and processing will ultimately be provided by the residual biomass derived from the polymer production crop. Key environmental benefits include utilization of atmospheric CO2 (rather than petroleum) as a chemical feedstock, reduced combustion of fossil fuels for polymer production, and reduced consumption of landfill space because the polymer is biodegradable (compostable). Additionally, economic benefits to the agricultural sector will be associated with production of the new or modified crop.

This project is one of the first and most complex attempts to metabolically engineer green plants to produce novel chemicals. Agriculture already provides a large number of chemical raw materials for industry, including sugars, oils, fibers, and many small molecules. The power of this new technology lies in the ability to manipulate plant metabolism, thereby creating new pathways leading to new products. Therefore, this project serves both the specific aim of PHBV production in plants, and opens the use of green plants as factories for the commercial, environmentally sustainable production of biodegradable plastics.

Metal Adhesive Polymers from Cu(I)-Catalyzed Azide-Alkyne Cycloaddition: a New Approach to Solder Replacements: Lead&#;tin solder is typically used to assemble printed circuit boards for personal microelectronic devices such as cell phones. The global proliferation of these devices results in unacceptable exposures of workers to lead, tin, and other toxic chemicals during device fabrication and, eventually, disassembly for recycling. International and state laws are beginning to limit these toxic substances in electronics, expanding the market for lead-free solder replacements.

In his research on finding lead-free solder, Professor Finn at The Scripps Research Institute has pioneered the discovery and application of Cu (I)-catalyzed azide&#;alkyne cycloaddition (CuAAC) reactions. The Sharpless and Finn labs were first to use this reaction to produce metal-adhesive materials from multivalent azide and alkyne monomers. Metallic copper at surfaces of metal substrates exposed to air provides enough Cu (I) ions to catalyze the formation of triazole cross-links, which bind the metal tightly. Triazole cross-links are also nontoxic and resistant to oxidation, reduction, irradiation, and heat. The highly efficient CuAAC process provides high conversions of azide and alkyne groups to triazoles. This process maximizes the cross-link density of the adhesive and thereby its strength, but at the expense of increasing the brittleness of the material. The incorporation of flexibility-inducing components and additional amine ligands in the adhesive mixtures enhances strength as determined by measuring maximum load before failure in a modified peel test on a custom-built, high-throughput instrument.

Current research is examining the conductivity, surface composition, and thickness of mixtures of the adhesive with conjugated molecular wires, silver nanoparticles, and carbon black using conductive probe atomic force microscopy (CP-AFM), X-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, and ellipsometry. This work provides exciting prospects for replacing resource-intensive solder composites with low-cost, nontoxic, conductive organic mixtures. In , Professors Finn and Sharpless submitted a patent application for this technology and had a second patent published.

Metal Extraction and Recovery Using Carbon Dioxide: Recovery of metals from dilute solution, whether the matrix is solid or liquid, remains a considerable technical and financial challenge. Methods currently exist whereby metals can be extracted from either type of matrix, yet these methods consume significant quantities of reagents and can also generate multiple waste streams in the process. Technology developed in the lab of Eric J. Beckman, University of Pittsburgh, over the past three years allows efficient application of environmentally-benign CO2 to a number of separation problems involving metals.

For example, biphasic mixtures of CO2 and water have been employed as a green acid leach medium. Metals have been extracted from a steelmaking process residue and then recovered as metal carbonates through depressurization. In this process, metals are extracted and recovered without the use of reagents other than CO2 and water, and CO2 is sequestered as a solid. In addition, through synthesis of CO2-miscible phase transfer agents, CO2 can replace the organic solvent currently used in refining of precious metals. The sensitivity to pressure of phase behavior in a CO2-mixture may allow significant streamlining of the process as well. Finally, CO2-soluble chelating agents have been used to extract toxic metals from acidic effluent such as that found in plating facilities.

Metal, Phenol and Ash-Free Antiwear Hydraulic Additive Providing Performance Previously Only Achieved by Use of Zinc Containing Additives: The use of heavy metals in lubricants presents environmental concerns primarily due to zinc contamination coming from hydraulic oils. The global antiwear hydraulic lubricant market consists of approximately 980 million gallons, roughly 95% of which is based on lubricants containing Zinc Dialkyl Dithiophosphate (ZDDP) as the antiwear additive and only approximately 5%, based on lubricants containing the less toxic, environmentally friendly, ashless antiwear additive technology. Of the lubricants using the ashless additive technology, the majority of the fluids are based on conventional mineral oils with globally, only approximately 3% based on biodegradable fluids.

The slow growth in the use of antiwear hydraulic fluids based on ashless technology is due, in part, to problems in the field, where performance equivalent to fluids based on ZDDPs has not been achieved. This is especially true for biodegradable hydraulic fluids. In this work we have identified an additive technology that is not only ashless, but also phenol free which when used in mineral oils gives performance equivalent if not better than that of ZDDP based fluids. This is the first ashless mineral oil based technology to be tested and approved against new, more severe requirements from original equipment manufacturers (OEMs). Also this ashless additive technology, along with boosters in biodegradable oils, is the first to be approved against new specifications, designed specifically for environmentally friendly fluids.

Metal-, Phenol-, and Ash-Free Antiwear Hydraulic Additive: Providing Performance Previously Only Achieved by Use of Zinc-Containing Additives: The use of heavy metals in lubricants presents environmental concerns, due primarily to zinc contamination coming from hydraulic oils. The global antiwear hydraulic lubricant market is approximately 980 million gallons. Roughly 95% of this global market is based on lubricants containing zinc dialkyl dithiophosphate (ZDDP) as the antiwear additive.

Only approximately 5% of this market is based on lubricants containing the less toxic, environmentally friendly, ashless, antiwear additive technology. Of the lubricants using ashless additive technology, the majority are based on conventional mineral oils with, globally, only approximately 3% based on biodegradable fluids. The slow growth in the use of antiwear hydraulic fluids based on ashless technology is due, in part, to problems in the field, where performance equivalent to fluids based on ZDDPs had not been achieved previously. This is especially true for biodegradable hydraulic fluids.

Afton has identified an additive technology that is not only ashless, but also phenol-free. When used in mineral oils, Afton&#;s product performs as well as, if not better than, ZDDP-based fluids. This is the first ashless, mineral oil-based technology to be tested against new, more severe requirements and approved by original equipment manufacturers (OEMs). Also, this ashless additive technology, along with boosters in biodegradable oils, is the first to be approved against new specifications designed for environmentally friendly fluids. Afton&#;s HiTEC 543 contains an amine salt of a sulfurized phosphite that provides antiwear protection over a wide temperature range in dry and wet conditions, a thiadiazole corrosion inhibitor that provides compatability with yellow metals, a three-way phenol-free antioxidant system, and a dispersant. Afton received its first commercial order for this new product in April .

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Meta-TecTM Low-VOC, One-Component, Cross-Linking Adhesive: Innovative Science&#;Applied Technology: Traditional flooring adhesives are one- or two-part reactive systems that are urethane-, epoxy-, solvent-, or water-based; they include various industrial solvents and consume nonrenewable resources. The manufacturing and application processes for these adhesives can also create large amounts of hazardous waste byproducts and emissions. These products are estimated to release over 23 million pounds of volatile organic compounds (VOCs) to the environment annually. Meta-TecTM technology is a unique class of adhesives that are low-VOC, reactive, one-part, and self-cross-linking.

The Meta-TecTM adhesives consist of a viscous mixture of drying oils such as soybean oil, linseed oil, and sunflower oil, inorganic fillers, renewable tackifiers such as rosins, polymers with carboxyl functionalities, metal catalysts, and a nontoxic cross-linking agent. Although these adhesives have performance characteristics previously exhibited only by reactive systems such as urethanes and epoxies, they contain very low VOCs and use more renewable resources.

With the high volume of adhesives used throughout the flooring industry, the ability of Taylor&#;s Meta-TecTM technology to eliminate the risks associated with volatile hazardous chemicals by reducing VOCs promises to have a significant positive impact upon the environment and on human health. The use of just one product, Meta-TecTM Wood Flooring Adhesive, would potentially prevent over 9 million pounds of solvents from entering the atmosphere. Between and (latest available data), this product was used to install over 60 million square feet of wood flooring products. The company expects this product to capture over 25 percent (25 million pounds) of the market by the end of .

Method Smarty Dish for Fish: An Environmentally Responsible and Effective Cleaning Solution: No Phosphates, Acrylates, or Ethylenediaminetetraacetic Acid: In the United States, the market for automatic dishwashing products is approximately $525 million. These products release roughly two million pounds of environmentally persistent polyacrylates into U.S. waterways annually, placing a burden on wastewater treatment. The polyphosphates in these products are of even greater concern; they release phosphates, which are potent fertilizers that lead to algal eutrophication and fish kills.

Method has developed a product without phosphate or acrylate. An early challenge was to optimize green chelants, dispersants, and complexation agents to deliver functionality equal to or better than that of blends of polyacrylate, polyphosphate, and ethylenediaminetetraacetic acid (EDTA). Not all green materials can directly replace these stalwart ingredients. Critical performance functions include: (1) Water hardness and metal ion control over the wide pH and temperature ranges encountered during automatic dishwashing. This affects spotting, filming, and soil breakdown. (2) Stabilization of biodegradable components.

Method developed a synergistic green chelant dispersant system. It found that polyaspartate could replace acrylate-copolymer dispersant backbones because polyaspartate delivers both anticorrosive properties and crystal inhibition. Iminodisuccinate (IDS) provides the chelant backbone; IDS works with the critical cleaning agent, Fe(III), which has a stability constant high enough to be useful, but not high enough to persist in the environment. Method&#;s formulation includes gluconate and other organic acids to buttress water control above the favorable pH range for IDS. Method selected the raw materials in Smarty Dish to be ultra-low in phosphate, totaling less than 10 ppm in the final product.

Method invented a novel, cellulose-coated tablet, which required a custom manufacturing process. Method gave thorough attention to health, safety, sustainability, environmental considerations, and performance, each undergoing rigorous, third-party reviews. The result is Smarty Dish, an exceptionally well-considered green chemical development with top-level industry performance. Method launched its Smarty Dish Tablets nationally in .

MicroProTM Technology in Wood Preservation: For over 75 years, water-borne preservatives have relied on solubilized ingredients to penetrate the wood being treated. Currently, approximately 85 percent of the pressure-treated wood in the United States is treated with amine&#;copper preservatives. The two most commonly used amine&#;copper preservatives require a solvent, monoethanolamine (MEA), to solubilize the copper component. MEA is a corrosive compound and a known kidney and liver toxin; it poses potential health and environmental hazards. It also facilitates the growth of mold on treated wood, reducing commercial acceptability.

Osmose, Inc. of Buffalo, NY developed MicroProTM, which uses micronized copper to penetrate wood, eliminating the use of any solvent. The copper particles in MicroProTM are between 250 and 500 nm, allowing the preservative to penetrate the wood&#;s cell structure uniformly. The particle size is small enough that the copper can be forced into the cellular structure areas of wood by pressure treatment, but large enough that it cannot readily move back out under normal pressure conditions. MicroProTM has the potential to eliminate the use of 200 million pounds of MEA annually, equal to about half of the current MEA production. MicroProTM-treated wood leaches substantially less copper in service than does wood treated with current amine&#;copper systems. This reduces the environmental impact of copper from structures in aquatic and terrestrial environments by approximately 75 percent compared with the current systems.

MicroProTM can be shipped at almost four-fold greater concentration than other current preservatives. The higher concentration of ingredients in MicroProTM reduces the fuel energy required to deliver preservative to wood-treating plants by almost 75 percent, which reduces costs and overall environmental impact. In , the U.S. EPA registered Smart SenseTM MicroProTM as a pesticide. By November , this product was being used by 18 wood-treatment plants in 9 states.

Microwave Heating as an Enabling Tool for Greener Synthesis: Dr. Leadbeater and his research group are using microwave heating to develop cleaner, greener synthetic routes to commodity chemicals, pharmaceuticals, and biofuels. Microwave heating can enhance the rate of reactions and, in many cases, improve product yields. He and his group have developed fast, easy, metal-catalyzed reactions that form C&#;C bonds; many of these reactions use water as a solvent. They can perform Suzuki and Heck couplings using sub-ppm quantities of simple palladium salts as catalysts and can also perform hydroxy- and alkoxycarbonylation reactions using near-stoichiometric quantities of carbon monoxide.

They have been working to scale up microwave-promoted chemistries and have investigated both batch and continuous-flow methods. They have developed a fast, easy route for preparing biodiesel with a commercially available microwave unit that works with both new and used oil and is energy-efficient. Their continuous-flow apparatus makes approximately two gallons of biodiesel per minute.

It is difficult to optimize reactions using microwave heating because monitoring the reaction progress generally requires stopping the microwave, allowing the reaction mixture to cool, and then analyzing it. Dr. Leadbeater&#;s group has been using Raman spectroscopy to monitor microwave promoted reactions in real time. They developed a prototype Raman unit in conjunction with CEM Microwave Technology and EnWave Optronics. With real-time monitoring, they can optimize reaction conditions and stop a reaction when it is complete, avoiding decomposition or byproduct formation. By using only the minimum energy required for a reaction, they save considerable energy over other microwave technologies. With the Raman apparatus, they are probing the kinetics of reactions and comparing microwave and conventional heating in much more detail than was possible previously.

Dr. Leadbeater and Professor Cynthia McGowan from Merrimack College have written a manual, "Clean, Fast Organic Chemistry: Microwave-Assisted Laboratory Experiments", for use in undergraduate chemistry laboratories.

Mill Designed Biobleaching Technologies: The research studies undertaken in this program are directed at utilizing the catalytic oxidative properties of laccase, an oxoreductase enzyme found in several natural systems, to improve the physical properties of lignocellulosic pulps in an enhanced environmentally green manner. As such, our research studies have defined the fundamental chemical pathways involved when laccase and/or laccase-mediator systems (LMS) are employed with lignocellulosic materials. In addition, during these studies we have discovered several novel reactions, including the unique chemical reactivity of LMS with lignin, its ability to be used as an oxidative bleaching system for recycled fiber, a previously unrecognized benefit as a pretreatment for kraft pulping technologies, and as a surface activation technology yielding pulp fibers with substantially improved physical properties. The benefits of these discoveries are anticipated to yield novel methods of eliminating hazardous chlorinated chemical wastes, enhanced usage of recycled paper, improved pulping/bleaching efficiencies thereby reducing the need for virgin wood resources, and improved physical paper properties thereby reducing the power consumption associated with the production of high-value paper.

Minimizing Environmental Emissions by Using Different Solvents in Manufacturing Processes: Solvent selection is an important aspect of chemical process development. Two well-known effects of solvents are their influence on the desired reaction kinetics and their potential to minimize the effects of hazardous undesired reactions through dilution and heat absorption as solvent is vaporized. Recent testing of energetic chemicals has demonstrated that the chemistry and kinetics of their undesired decomposition reactions are also significantly altered by solvents.

Eastman Kodak has successfully applied this knowledge to the process safety element of process development by systematically evaluating potential solvents for their effectiveness in minimizing the potential environmental impacts of accidental process upsets. For example, the batch size of an existing process had been very restricted because of the potential severity of a thermal runaway. Research on chemistry/solvent-specific decomposition data was utilized to select candidate replacement solvents that would minimize environmental hazards. A cooperative effort by safety engineers and development chemists ensued, resulting in a final process that entirely eliminated the possibility of loss of containment due to a thermal runaway.

The end result of this work is that a new tool is available to help chemists and chemical engineers develop inherently safer chemical processes. Historically, changing a process to mitigate a potential hazard has been accomplished through drastic changes in process conditions, process chemistry, or through equipment modifications, all of which require significant capital and resources. It is demonstrated by example that the application of recent investigations into the effects of solvents on the decomposition kinetics of energetic chemicals can be leveraged to substantially decrease the potential environmental impact of thermal runaways in production-scale equipment. The technology described has the potential for broad application in chemical manufacturing processes that make or use thermally unstable materials.

Mold Prevention through the Novel Use of In Situ Electrochemistry to Eliminate Water Seepage in Concrete Structures: Electro-Osmotic Pulse (EOP) technology eliminates water seepage through concrete by the novel use of in situ electrochemistry. It prevents mold growth and eliminates the use of harmful volatile organic compounds (VOCs), such as from petroleum-based coatings used for waterproofing. EOP has led to a revolution in waterproofing technology through the application of electro-osmosis (forced movement of an aqueous solution containing a net electric charge due to an external electric field) to control water transport through belowgrade concrete structures such as foundations, basements, and tunnels. Unlike many conventional waterproofing methods, EOP reaction chemistry is inherently nontoxic and releases no VOCs. EOP improves air quality in below-grade spaces by reducing the interior concrete surface moisture below 55% relative humidity, such that mold cannot grow. Further, it costs about 40% less to install than traditional waterproofing methods.

EOP combines the novel application of an asymmetric, dual-polarity pulse with long-life ceramic-coated electrode materials. The anodes are inserted into the concrete wall on the interior of the structure; cathodes are placed either in the soil directly outside the structure or in the structure itself, near the exterior. A direct current (DC) power supply produces a low-voltage, dual-polarity pulse. This sets up an electric field between the electrodes, creating an electro-osmotic pressure sufficient to overcome the external hydraulic pressure and to reverse the flow of water seepage, actually causing moisture to move toward the outside of the basement walls. During and , the Army has installed EOP systems in the basements of 382 family houses on military bases.

Molyphos: A Chromate-Free Alternative for Corrosion Protection of Metal Parts: Nortel (Northern Telecom) developed an alternative to the use of hexavalent chromium, a known carcinogen, for the corrosion protection of metal parts. The new technology a molybdenum phosphate (Molyphos) based conversion coating replaces the chromate conversion technology (yellow chromate), an industry standard for over 40 years. In , Nortel successfully applied the Molyphos technology in tests and commercial production of several of its telecommunications products. Molyphos technology achieves multiple environmental benefits.

First, and most importantly, hexavalent chromium is eliminated as a raw material in the metal coating process, resulting in a safer work environment and the reduction in hazardous emissions and wastes. Second, Molyphos alleviates the internal stresses of zinc plating, which allow Nortel to replace cyanide based zinc electroplating with an alkaline process. Third, the superior electrical conductivity of Molyphos coatings, compared to chromate conversion coatings, allows Nortel to eliminate the beryllium copper gaskets and the tin lead precoat required to achieve continuous conductivity in some applications, further reducing toxicity. Fourth, for end use applications that require painting, Molyphos allows the use of powder paints, rather than liquid volatile organic content based paints required by chromate coated products.

Multipurpose Exopolymer as a Raw Material: Levan, an unusual polysaccharide, is being developed as a raw material to replace petrochemicals in many industries. This polymer of fructose has an extremely low intrinsic viscosity so that it requires less energy to handle, does not swell in water, is heat- and acidstable, and causes no skin or eye irritation, even on prolonged, direct contact. Levan is a strong adhesive, forms oxygen-barrier films, can be derivatized to make powerful surfactants, can be extruded into plastics, and can replace petrochemicals in certain personal care products.

Cost is a critical factor in determining commercial success of a raw material. Levan is made from sucrose, the disaccharide of glucose and fructose, which currently sells for $0.17 per kilogram. Levan is an exopolymer. Unlike products from corn, soy, and waste biomass that require significant amounts of energy and solvents for separation from cells, levan is naturally exported from producing cells. Either sugar beets or sugar cane can be the source. Sugar beets are grown on marginal lands. Processing energy needs are minimal; some beet sugar processors sell excess electricity to the grid. Sugar cane is an excellent CO2 sink. The byproduct, glucose, is a basic feedstock for numerous chemicals, providing additional revenue.

Levan is a multifunctional, raw material. It meets three standards: (1) Safety: levan is safe for users and the environment. (2) Sustainability: levan is derived from a renewable resource. (3) Security: sucrose, the feedstock, comes from sugar beets and sugar cane, both produced in the United States and in many regions around the world. Montana Polysaccharides has been producing levan in 5,000-liter fermenters since . During , the company initiated sales of levan in the adhesive and personal care industries.

Mycopesticides and Mycoattractants: Certain mold fungi, called entomopathogenic fungi, kill insects and use their carcasses as platforms for disseminating spores. With limited success, the pesticide industry has attempted to deploy entomopathogenic fungal spores to kill pests such as termites and ants. The spores of entomopathogenic fungi repel many of these insects, however, and insects have natural defenses against them. Soldier insects guarding the nest keep spore-contaminated foragers from entering in order to protect the queen and the colony from infection.

Fungi Perfecti has developed methods to deploy the presporulating mycelia of the entomopathogenic fungi Metarhizium and Beauveria as natural agents to attract and kill termites and ants. The novelty of this technology is the discovery by Fungi Perfecti that ants, termites, and flies are attracted to entomopathogenic fungi in their mycelial state, prior to sporulation. Fungi Perfecti isolated fungi from naturally infected insects and then cultured the fungi selectively to create strains that delay spore production for several weeks. The presporulating mycelia emit powerful attractants, trail-following elicitors, and feeding stimulants, which draw select pests to a chosen site, from where they spread the infectious fungi throughout the targeted nest and ultimately to the queen. In choice tests, termites prefer the presporulating mycelium of Metarhizium anisopliae to wood as food. The infected colony, upon sporulation, repels subsequent insect invasions.

This mycotechnology is economical and scaleable; it uses current cell culture methods. It has been awarded two patents, with more pending. Tests at Texas A & M University and the U.S. Department of Agriculture show this technology works against Formosan termites, eastern subterranean termites, and fire ants. Subsequent tests show positive results in controlling carpenter ants and fungus gnats. This discovery may well replace toxic pesticides and lead to novel methods for controlling insect pests worldwide, protecting the environment, people, and other organisms.

NAFION Membrane Technology: Membrane technology is now recognized as state-of-the-art for chloralkali chemical production, which constitutes the second largest commodity chemical volume produced globally. NAFION membranes are acknowledged as the world leader in bringing about a technology 'revolution," which has made the membrane electrolyzer system the technology of choice over the incumbent mercury amalgam cells and asbestos diaphragm electrolyzers. While significantly reducing the environmental impact of the old technologies, membrane systems confer the advantages of a new electrolysis process with lower investment and lower operating costs. Before NAFION and membrane technology, the production of chloralkali chemicals was dependent on either mercury amalgam cells or asbestos diaphragm systems.

Wile [sic] these systems might be operated safely, they pose health and environmental concerns in use and disposal. Membranes, such as NAFION, now offer a more environmentally friendly and economically attractive alternative, which accounts for the rapid global adoption of membrane technology. Another rapidly emerging application of NAFION is in the area of alternative energy, where electricity is produced from the 'combustionless burning" of hydrogen with oxygen in air via a membrane fuel cell. Fuel cell technology, with hydrogen as a fuel, is pollution-free. NAFION membranes often are cited in the many commercial developments of membrane fuel cell systems. As membrane fuel cells mature in the commercial mass market, more global energy needs will be served by renewable, sustainable, and environmentally friendly sources of power.

Nalco ACT &#; Advanced Condensate Treatment for Boiler Systems: The ONDEO Nalco Chemical Company of Naperville, Illinois, a wholly owned subsidiary of Suez, initiated a research program to develop a safer and more environmentally friendly alternative to the use of amines in boiler water treatment as corrosion inhibitors. Nalco in fact did discover an innovative approach to limit boiler condensate corrosion without the use of any nitrogen bearing chemistry. Nalco received a United States patent for this approach in . In , the commercial application program was fully introduced throughout the United States and to the rest of world. During the start of the millennium, those who operate boiler systems have begun to switch from an amine based corrosion inhibition treatment, to the safer Nalco ACT program. The use of the new ACT program is gaining momentum as the operators of boiler systems enjoy excellent corrosion protection while using a more environmentally friendly and safer alternative to amines.

Nalco Fuel Tech OxOUT® Process: Nalco Fuel Tech develops and markets air pollution control technologies worldwide. Their flagship technology, NOXOUT®, reduces harmful nitric oxide emissions of stationary combustion sources to yield nitrogen gas and water, leaving no disposal solids. Nitrogen oxide (Ox), the pollutant targeted in NOXOUT® technologies, is a "primary" pollutant, and reducing it directly reduces acid rain, particulate matter less than 2.5 microns in diameter, and greenhouse gases and mitigates nitrogen eutrophication sensitive watersheds. Ox also is a precursor in the formation of ground-level ozone that, along with Ox, is one of EPA&#;s six criteria pollutants. More than 100 million of our nation&#;s citizens and many more global inhabitants live in areas that are classified "nonattainment for ozone," [i.e., ambient air ozone levels exceed 120 parts-per-billion (ppb)].

High ozone levels are linked to many forms of respiratory problems, leading EPA to promulgate the new National Ambient Air Quality Standard of 0.080 ppm for an 8 hour period to adequately protect human health and welfare. The NOXOUT® process meets today&#;s environmental challenges by using less toxic chemistry, reducing or eliminating toxic releases to the environment, converting wastes to more environmentally acceptable discharges, and reducing energy consumption.

The NOXOUT® process provides an economical solution for complying with the stringent regulatory requirements for Ox reduction from fuel combustion sources. NOXOUT® can reduce Ox emissions by 75% compared to the 20 to 50% reduction from existing treatment. The NOXOUT® process is being used commercially. It can be used on new combustion units for small industrial units to large utility installations, or it can be retrofitted to existing units. The environmental benefits are significant Ox reduction, elimination of byproduct disposal, toxic use elimination of Superfund Amendment and Reauthorization Act Title III chemicals, and increased energy efficiency.

Nalco LAZON Technology: The U.S. paper industry suffers more than $1 billion per year in lost production alone due to biological contamination problems. Nalco LAZON Technology gives papermakers a new integrated approach that allows them to improve control of microorganisms with significantly lower environmental impact. This technology is a unique bundling of innovations that includes a synergistic biocide combination, two new monitoring technologies, and specialized feed equipment. The primary component of LAZON Technology is the chemistry, a combination of the nonhalogen oxidant peracetic acid and a standard organic biocontrol agent, which together provide antimicrobial activity that is far greater than expected from the individual components. Improved microbiological control is demonstrated with the Nalco BIOWATCHTM Optical Fouling Monitor.

Minimal or no environmental impact is assured by Nalco&#;s BIOWATCH TRA-CIDE® system, which rapidly measures biocide toxicity and microbial ATP onsite. Finally, a specially designed chemical feed system and Nalco&#;s PORTAFEED ® returnable container complete the program. This interlocking network of novel technology decreases biocide use, measures product performance and residual toxicity, and minimizes the chances of accidental biocide release during transportation or product feed. This Nalco technology is a complete program that improves safety, increases energy conservation, reduces operating costs, and minimizes point source release.

Nalco NALMET® Heavy Metal Removal Technology: Stricter NPDES discharge limits for effluent metals impact both metal and nonmetal industries. The parts-per-billion (ppb) limits for heavy metals removal cannot be met by traditional metal precipitation processes. Membrane processes such as ion exchange, ultrafiltration, and reverse osmosis are historically recommended for metal removal. They require significant capital investment and still require pretreatment of these waste streams. A chemical removal process that can reduce metals to acceptable NPDES levels represents an important new technology for industrial waste treatment.

Nalco has developed NALMET®, a patented program for metal removal. This low-toxicity technology includes a liquid polymer containing a metal chelating functional group that simultaneously precipitates metals and clarifies the waste stream, all in one product. It also includes an automated chemical feed system with patented sensor technology to guarantee standard treatment. The program allows customers to have their NALMET®-generated sludge reclaimed by our partner company. The benefits of the NALMET® program are that sludge volumes are reduced 25 to 90%, product overfeed is reduced, environmental releases of treatment chemical are reduced, a less toxic treatment chemical is used, and customers consistently meet ppb metals discharge limits. Through Nalco&#;s integrated, innovative approach, our customers achieve pollution prevention. Cradle-to-grave environmental management is achieved with environmental toxicity reduction.

NALCO&#;s APEXTM Program: Sustainable Technology for Paint Detackification: For decades, manufacturers have used hazardous melamine&#;formaldehyde&#;acid colloids to detackify paint overspray in spray booths. Melamine is an irritant, however, and chronic exposure may cause cancer or reproductive damage. Formaldehyde is a known carcinogen according to the Occupational Safety and Health Administration (OSHA). Further, the colloid is derived from feedstocks based on nonrenewable petroleum or natural gas. In searching for an alternative, U.S.-based manufacturing companies established an initiative to create a green method for paint detackification using innovative chemistry. NALCO developed the APEXTM program to support this initiative.

The APEXTM program consists of an etherified, cationically modified corn starch mixed with a small amount of a proprietary amphoteric polymer and a polybasic aluminum salt. It is formulated from over 99 percent sustainable resources. When added to a paint system at a pH above 7.0, APEXTM generates a highly cross-linked "sweep floc" that rapidly coagulates and completely detackifies paint solids, creating an easily dewaterable sludge. The APEXTM program completely eliminates formaldehyde and other harmful, nonrenewable raw materials in these applications.

The APEXTM program benefits every manufacturing company that adopts it by: (1) reducing total costs of operation (typically over 30 percent); (2) reducing chemical use (typically over 80 percent); (3) reducing the generation and transportation of wastes (typically over 50 percent); (4) reducing water use; and (5) reducing emissions of volatile organic compounds (VOCs). A large automotive plant in Alabama first implemented APEXTM, where it reduced solid waste generation by 267,000 pounds and saved $90,000 in disposal costs. It reduced VOC generation by over 3,000 pounds (an 80% reduction). It also reduced the frequency of booth cleaning from weekly to once per quarter, saving an additional $160,000 in operating costs and significantly reducing use of cleaning chemicals. NALCO&#;s APEXTM program is currently used in 85 assembly plants.

n-Alkyl Propionate Ester Solvents: Union Carbide Corporation, A Subsidiary of The Dow Chemical Company manufactures a family of three n-alkyl propionate ester solvents under the UCAR trademark. These solvents, consisting of n-propyl propionate, n-butyl propionate and n-pentyl propionate, are quickly replacing other solvents as more environmentally friendly alternatives due to their non-HAP (Hazardous Air Pollutant) status by the US Environmental Protection Agency (EPA), superior solvency, low ozone-forming potential and low odor.

Nanophase Mn(VII) Oxide: Synthesis using Green Technology and Applications: The formation and stabilization of nanophase Mn(VII) oxide (i.e., NM7O) is central to the ChK Group&#;s innovative technology. The starting material is a beige-colored mineral, hydrated Mn(II); upon addition of 1,4-phenylenediamine (PDA), it forms NM7O, which is violet-colored. The mechanism appears to be the oxidation of PDA to 1,4-benzoquinone in the presence of air, which then oxidizes the hydrated Mn(II) to NM7O. Scanning electron microscope (SEM) analysis shows a globular NM7O mass with particle sizes of 50&#;100 nm. Cyclic voltammetry and optical spectroscopy confirm the Mn7+ oxidation state.

NM7O is a safe product compared to harsh, toxic competing products. It is nonflammable and is safe for disposal in municipal landfills after use. NM7O is a super Lewis acid: it attacks compounds with lone pairs of electrons, such as cyclohexylamine and cyclohexanone. It removes odors by destroying amine compounds and converting thiol groups to disulfides. It also neutralizes surrogates for chemical warfare agents (CWAs) such as 2-chloroethyl ethyl sulfide (CEES, a mustard gas analog) and dimethyl methylphosphonate (DMMP, a sarin gas analog). In addition, it makes a good polish for silver.

ChK recently discovered that NM7O is good algaecide and bactericide; it does not, however, destroy aquatic fauna or flora. After reduction, the violet-colored NM7O changes to brown-black-colored, environmentally safe Mn(IV) oxide, allowing its use as an optical sensor. ChK has coated NM7O on and impregnated it into nonwoven and melt-blown fabrics. The treated fabrics can be incorporated into wipes and liners for consumer and industrial uses, clothing, and materials for military and homeland security uses.

The NM7O manufacturing process has received a U.S. patent; another patent is pending on its use to destroy CWAs; and ChK has filed provisional patents on NM7O-coated fabrics and the use of NM7O to destroy nuisance and pathogenic microorganisms. ChK has successfully manufactured clay-coated NM7O on a pilot scale.

National Conversion to Low Sudsing Hand Dish Detergents for Industrial, Institutional, and Especially Consumer Application: In the United States, almost all dish detergents or liquid detergents used for hand dish washing are anionic based, with specifically high foaming properties formulated purposely into the product to deliver a consumer aesthetic. To provide this sudsing characteristic, multiple anionic and foam boosters are used/needed to deliver the effect. The addition of all these extra chemicals is unnecessary to deliver actual cleaning performance and oily soil emulsification. This can be achieved by using nonionic surfactants, straight chain linear alcohol ethoxylates or APGs (alkyl polyglycosides) or other low foaming environmentally suitable alternatives to alkylbenzene sulfonate and foam boosters formulation types.

Nationwide use of this technology in all dish detergents would reduce overall toxicity due to the discharge of high sudsing dish products in rivers and streams. In addition, overall water usage would decrease due to faster manufacturing and overall reduced energy consumption of operations providing this product category to all U.S. market sectors: consumer, industrial, and institutional. This formulation strategy can be available immediately nationwide and can be manufactured readily by all national brand companies.

National Microscale Chemistry Center: The Leader in Worldwide Implementation of Microscale Technology: The simplest definition of Green Chemistry is "the use of chemistry techniques and methodologies that reduce or eliminate the use or generation of feedstocks, products, byproducts, solvents, reagents, etc., that are hazardous to human health or the environment." While more commonly being applied to industrial applications, the concepts of Green Chemistry also have been incorporated into education pedagogy, using microscale laboratory methods. The microscale chemistry technique is a laboratory-based educational program, resulting in waste reduction at the source; elimination of toxic emissions, fire, and accident hazards; enhancement of a healthful laboratory environment; and significant cost savings.

Microscale methodology uses minute amounts of chemicals (50 mg of solids, 500 µL of liquids on average); new methods for determining physical properties; milder and safer alternative reaction conditions; alternative benign solvents; and different synthetic pathways, often employing catalytic and other environmentally safe techniques. The National Microscale Chemistry Center was established at Merrimack College in . The center offers workshops, training, and other related support to teachers and industrial chemists in microscale chemistry techniques. Currently, more than 2,000 institutions in the United States have, either fully or partly, adopted this approach. NMC2 is also the lead site of an international consortium promoting the microscale/Green Chemistry revolution.

NATRASURFTM PS-111 Polymeric Surfactant: Achieving Next Generation Mildness in Personal Care Products with a Reduced Environmental Footprint: The production of personal cleansing products, such as shampoos, body washes, and facial cleansers, consumes sizable, ever-increasing volumes of surfactants. Traditionally, the industry used largely nonrenewable, petroleum-derived synthetic detergents to achieve mildness in personal cleansers. Although these well-established surfactants are safe and cost-effective, they could be improved in their mildness, renewability, manufacturing processes, and biodegradability. Johnson & Johnson and AkzoNobel have collaborated to develop NATRASURFTM PS-111, an innovative, starch-based polymeric surfactant (PS) for formulating mild personal care products.

PS-111 is based on the patented discovery that PSs overcome the problem of surfactant-induced irritation because they cannot penetrate living tissue. NATRASURFTM PS-111, the first personal care ingredient of its kind, delivers the cleaning and foaming performance of traditional surfactants and has virtually no irritation potential. NATRASURFTM PS-111 minimizes environmental impacts throughout its lifecycle. PS-111 is sodium hydrolyzed potato starch dodecenylsuccinate, a 90 percent renewable material derived by reacting hydrolyzed potato starch with an alkenylsuccinic anhydride. This low-temperature, aqueous esterification offers many advantages over traditional esterifications, including energy efficiency and atom economy. The starch ester used for PS-111 is nonirritating to skin and eyes, nonallergenic, nontoxic to humans and aquatic organisms, nonbioaccumulative, and readily biodegradable.

PS-111 is supplied to manufacturers as a self-preserving, spray-dried powder; this eliminates the need for chemical preservatives and reduces the energy used to store and ship conventional aqueous surfactant solutions. PS-111 has the potential to replace millions of pounds per year of nonrenewable, poorly biodegradable surfactants and emulsifiers. Further, this technology can be readily leveraged for use in agricultural, household, and industrial applications. NATRASURFTM PS-111 exemplifies how green chemistry can enable cost-effective, sustainable materials that benefit both consumers and the environment without sacrificing performance or efficacy. In December , Johnson & Johnson launched the AVEENO® Pure Renewal line of shampoos, the first products containing NATRASURFTM PS-111.

Natural Recycling of Plastics through Chemical and Biological Degradation: Modern synthetic polymer manufacturing has reached a high level of efficient resource utilization. An energy-efficient system of producing additives based on natural polymers and other chemicals provides an effective means of achieving an alternative to plastics recycling by allowing timed degradation followed by systemic incorporation back into natural organic cycles. The system is based on the continued use of conventional plastics processing machinery and results in a product that has the advantages of existing plastics materials with the added benefit of timed degradation in appropriate environments.

After disintegration, the elements are available to be incorporated into humus and other soil constituents. The additives work by providing degradation catalysts based on natural organic unsaturated fatty acids and other unsaturates and benign metal cations with multiple oxidation states (such as iron). By combining these with conventional thermoplastic polymers, oxidative degradation of typical plastics can be achieved. In addition, a naturally biodegradable polymer, such as starch or cellulose, is combined initiating biological attack and microbial colonization of the plastic. In natural environments this starts a slow oxidative biodegradation, similar to that for lignin, which allows incorporation of the carbon directly into humus and growing plants.

Nature"s Avenger® Organic Herbicide: A Fast-Acting, Highly Effective, Organic Alternative to Synthetic and Natural Herbicides: Nature"s Avenger® Organic Herbicide (NAO) is a GRAS (generally recognized as safe), highly biodegradable, extremely effective, nonselective, post-emergent herbicide that is approved by the EPA for organic agricultural production. Its active ingredient, d-limonene (citrus oil), is found naturally in more than 300 herbs, edible plants, and fruits. D-Limonene is used in many soaps, detergents, commercial cleaners, deodorizers, shampoos, and mouthwashes. It has proven to be a strong, natural, degreasing agent that acts by stripping away the waxy cuticle from weeds, subsequently dehydrating and killing them. D-Limonene is also a flavoring agent in many foods.

The volatility of d-limonene makes it a relatively weak herbicide. Cutting Edge Formulations (CEF) has spent considerable resources to develop proprietary emulsions that reduce the volatility of d-limonene substantially. Their emulsions ensure that d-limonene remains on plant surfaces longer and thus eradicates weeds more quickly. CEF research showed that increasing the pH significantly enhances the herbicidal efficacy. A mixture of proprietary inert ingredients also contributes to activity. NAO is comparable in effectiveness to glyphosate and paraquat, which are synthetic, non-organic herbicides. NAO also acts faster.

In consumer and professional markets, the availability of a safe, efficacious, organic herbicide provides an important alternative to both synthetic products and less-effective natural products. In the organic agricultural market, organic growers control weeds primarily with mechanical tillage and hand labor, which is extremely expensive at approximately $1,000 per acre. Combining mechanical tillage with NAO in areas that cannot be mechanically tilled would bring an organic grower"s cost for NAO into a range of $45-80 per acre, which is within the range that traditional, non-organic growers pay for weed control. The availability of an easy-to-use, effective, cost-effective organic herbicide will revolutionize how organic growers control weeds.

During , NAO received listing by the Organic Materials Review Institute (OMRI).

New Asymmetric Hydroxylation Technology for the Commercial Manufacture of Indoxacarb: Indoxacarb is a major new insecticide marketed worldwide by DuPont Crop Protection. The U.S. EPA has designated indoxacarb as both a reduced-risk pesticide and an organophosphate replacement. Indoxacarb is the insecticidally active S-form of a racemic pair; the R-form is not active.

It is undesirable to manufacture and apply racemic mixtures of pesticides, due both to the environmental burden of the inactive enantiomer and to the waste generated in its production. Recognizing this, scientists at DuPont developed new proprietary technology for the asymmetric synthesis of indoxacarb. The first-generation process used cinchonine to catalyze an asymmetric hydroxylation, affording a 50-percent enantiomerically enriched product. DuPont used this technology for its first commercial production of indoxacarb in January . Then, improving on its earlier technology, DuPont developed a second-generation process that uses proprietary complexes of chiral diamine ligands and zirconium to carry out the critical asymmetric hydroxylation in high yield with high enantiomeric excesses.

Commercial production of the first fully enriched indoxacarb (with over 98 percent enantiomeric excess) began in September . At current production volumes, DuPont&#;s new synthesis of indoxacarb is reducing the total material burden on the environment by hundreds of tons per year over the first-generation process. In the United States, indoxacarb is marketed as DuPont Steward® Insecticide and DuPont Avaunt® Insecticide; it is currently registered in over 70 countries. Worldwide sales were $130 million in and are expected to reach $150 million in .

New Biomass Catalytic Reforming Process for Solid Oxide Fuel Cell Power Generation: Zivatech&#;s technology is based on analyzing, testing, and evaluating a new reforming process for converting biomass and other secondary waste streams into a syngas outlet stream rich in hydrogen gas for powering a directly interconnected solid oxide fuel cell (SOFC). These waste sources are rich in methane and carbon dioxide; the new process uses an effective catalytic reformer to convert them efficiently into a syngas outlet stream. The stream is used as feed into the anode of an integrated fuel cell of a solid oxide structure.

Conversion of these waste streams to synthesis gas for use in SOFC-based electricity generation systems is of increasing importance to both commercial and remote residential energy consumers from energetic, economic, and clean energy points of view. Renewable waste biogas resources are of increased interest to the clean and highly efficient energy generation market. In addition, Zivatech&#;s innovative process to convert carbon dioxide-rich methane gas inside an in-situ reactor using their reaction and catalysis system is under increased consideration in current and future industrial efforts. This is considered an additional benefit of Zivatech&#;s work. Projected energy and capital savings from the use of the integrated new process are in the 30 to 35% range compared to existing natural gas- and diesel-based direct combustion technology.

New Catalyst for Producing ULTEM® Thermoplastic Resin: GE Plastics produces an engineering thermoplastic known as ULTEM® polyetherimide resin. The production of this resin involves several complicated synthetic conversions and generates both an aqueous waste stream containing organic materials and an organic waste stream. The key step in the process depends on a catalyst that has been a research "target of opportunity" for several years. Laboratory studies indicated that the amount of waste generated from this step could be significantly reduced using several members of a new catalyst class.

A small plant trial verified the early findings. In , the most promising member of this new catalyst class was streamlined, and a full plant trial was conducted in the ULTEM® manufacturing plant. Based on the full plant trial, the following pollution prevention benefits were demonstrated:

the volume of organic waste stream for off-site disposal was reduced by 90 percent or 123,000 pounds a year;

the waterbased organic waste for on-site thermal oxidization was reduced by 60 percent or 300,000 pounds a year;

50 percent less catalyst was consumed due to greater effectiveness per pound of catalyst;

the amount of waste from the manufacture of the catalyst itself was reduced by 75 percent or 39,000 pounds a year;

the amount of energy required to produce each pound of the resin was reduced by 25 percent or 5 x 109 BTU/yr; and

the amount of a workplace hazardous by-product was reduced by 90 percent.

In addition to these health and environmental benefits, the new catalyst system also offers several significant economic advantages. This catalyst technology is the cornerstone of new process chemistry for manufacturing the ULTEM® resin that will eliminate completely the need for a thermal oxidizer.

New Generation Adiponitrile Technology: A new generation nickel catalyst system has been discovered and taken through pilot plant demonstration for the hydrocyanation of butadiene to adiponitrile. This new catalyst, developed through a molecular architecture approach to the design and construction of homogeneous catalysts, is dramatically more active, more selective and more robust than the current commercial catalyst operating in our Joint Venture Butachimie plant.

These properties result in the reduction of organic byproducts from this process by more than 35% and reduction of inorganic byproducts by more than 50%. In addition, they result in the concomitant reduction in energy requirements for this process while also providing additional capacity from existing investment. Moreover, process simplifications enabled by this technology dramatically reduce the capital requirements for grassroots facilities planned in the future to support growth in the Nylon-6,6 and Nylon-6 marketplaces. Overall this technology results in improved environmental performance, lower manufacturing costs and increased capacity from existing investment through source reduction rather than tailpipe treatment.

New Green Commercial Biocatalytic Route to Atorvastatin Calcium, the Lipitor API: Atorvastatin is the active pharmaceutical ingredient (API) in Lipitor. Since its launch in , Lipitor has been the most-prescribed branded cholesterol-lowering medication in the world. This success, together with Pfizer&#;s commitment to continuous improvement, made the production of atorvastatin an obvious target for improvement. Pfizer challenged itself to make dramatic improvements in both the efficiency and environmental performance of the manufacturing route to atorvastatin. The original manufacturing process required a chiral starting material. Because optimizing this process would not achieve the transformational changes that Pfizer sought, the company developed a completely new, more efficient, commercial route to atorvastatin calcium using a biocatalytic process.

The new green process incorporates a water-based 2-deoxyribose-5-phosphate aldolase (DERA) enzyme at the beginning of the route to make a lactol from an amino aldehyde (i.e., 3-phthalimidopropionaldehyde; PPA) and acetaldehyde. The synthesis eliminates the use of cyanide or azide moieties to introduce nitrogen because it is already present in the lactol. In contrast to the original synthesis, the DERA enzyme sets both stereocenters with high selectivity in water at room temperature. Converting the resulting lactol into isopropyl acetonide atorvastatin (IAA) is extremely efficient: it involves four high-yield chemical steps (oxidation, esterification, deprotection, Paal Knorr) with only the IAA product being isolated as a solid.

Finally, IAA is converted to atorvastatin calcium, the API product. Pfizer&#;s green process substantially reduces the environmental impact by eliminating hazardous steps and reducing or eliminating required chemicals. For example, the new synthesis eliminates the previous high-pressure hydrogenation step with its associated metal catalysts. It also avoids pyrophoric n-butyl lithium and its associated butane waste gas. The need for significant other reagents and solvents has either been eliminated or dramatically reduced. The U.S. Food and Drug Administration (FDA) approved the new manufacturing process in April . Pfizer manufactured commercial scale validation batches in and is currently transitioning to full-scale commercial manufacture.

New Green Technology for Eliminating Hydrogen Sulfide in Aqueous Systems, Especially Petroleum Industry Systems: The occurrence of hydrogen sulfide (H2S) in aqueous systems is a major concern of many industries. This concern is especially acute in the international oil and gas industry. H2S constitutes a serious health, environmental, and economic problem in virtually all major oil and gas production operations. Massive global reservoirs and water systems are now heavily contaminated with corrosive, poisonous H2S and harmful iron sulfide precipitates that plug pipelines, impeding oil and gas production.

The source of H2S is the reduction of soluble sulfate (SO4) in the water by indigenous, aerobic, sulfate-reducing bacteria (SRB). To combat H2S formation, the industry has used biocides such as glutaraldehyde, acrolein, formaldehyde, quaternary amines, and chlorine extensively. However, SRB are becoming resistant to them, necessitating the use of increasingly toxic and dangerous biocides.

LATA&#;s biocompetitive exclusion (BCX) technology is designed to attack SRB. The BCX process is initiated and sustained by patented, environmentally friendly formulas named Max-Well that contain a combination of inorganic nitrate and nitrite. These formulas target and directly manipulate the indigenous microflora of hydrocarbon-bearing reservoirs and a wide variety of surface injection and produced water systems. Low concentrations of Max-Well act as alternate electron acceptors for indigenous, nitrate-reducing bacteria (NRB) so that they subsequently flourish and out-compete SRB for essential growth nutrients.

The nitrite component is toxic to SRB and also reacts chemically with existing H2S to form soluble, nonhazardous SO4. The end result of the growth of beneficial NRB populations is the production of nonhazardous nitrogen gas, elimination of existing H2S in the system, and continuous blocking of new H2S and iron sulfide production. One successful field project with a major oil company is leading to treatment expansions in the United States and elsewhere. Another ongoing field trial with a major oil company is destroying and controlling H2S in an oil and gas reservoir.

New Lead Free Materials for Replacement of Existing Primary Explosives: Lead azide (LA) and lead styphnate (LS) are widely used in ordinance as priming mixtures for propellants and as detonators for secondary explosives. Annually, the U.S. Army requires well over 1,000 pounds of LA. The United States uses 60,000&#;80,000 pounds of LS containing approximately 30,000 pounds of lead annually as percussion primers in military and commercial small-caliber ammunition. During use and disposal, these compounds release lead, a toxic heavy metal, into the environment. Further, their manufacture requires toxic or carcinogenic materials.

In , President Clinton issued Executive Order to reduce or eliminate the procurement of hazardous substances and chemicals by federal facilities. In compliance, the CAD/PAD group (i.e., Cartridge Activated Device/Propellant Activated Device group) at the Naval Surface Warfare Center-Indian Head (NSWC-IH) began a program to replace LA and LS with substitutes free of mercury, lead, and barium. Pacific Scientific Energetic Materials Co. (PSEMC) in Chandler, Arizona has been a leader in developing drop-in replacements for LA and LS that incorporate no toxic or environmentally undesirable elements. Because LA and LS have specific and complex properties, PSEMC spent over ten years developing environmentally benign replacements for these materials from concept through synthesis to qualification.

DBX-1 (Cu(I) 5-nitrotetrazolate) is an LA replacement that has undergone qualification testing and is being scaled up to production levels for commercial and military uses. DBX-1 offers high oxidative, hydrolytic, and thermal stability, improved safety characteristics and compatibility, and output performance equal to or exceeding that of LA.

KDNP (potassium 5,7-dinitro-[2,1,3]-benzoadiazol-4-oleate-3-oxide) is an LS replacement suitable for service use; it qualified for weapons development in . KDNP has high thermal stability, improved safety and compatibility, and output performance equal to or better than that of LS. PSEMC has applied for several patents on both KDNP and DBX-1.

New Manufacturing Route for Arzoxifene Hydrochloride: Arzoxifene hydrochloride (HCl) is an investigational new drug candidate currently in phase III clinical trials. Prior to manufacturing arzoxifene HCl commercially, Eli Lilly reviewed its original manufacturing process. The review identified several major environmental burdens including a large excess of trifluoroacetic acid as a solvent, an extremely high loading of palladium catalyst, and extensive use of methylene chloride as a solvent. Eli Lilly decided to abandon this route and accept the risk of designing and developing a greener route. Moreover, Eli Lilly had to discover, develop, and introduce the new route on an accelerated schedule to ensure that ongoing patient needs would be met.

An intensive effort by chemists, engineers, and environmental professionals resulted in the discovery of a new route that meets these requirements. The new process eliminates trifluoroacetic acid and methylene chloride. It reduces the amount of palladium&#;carbon catalyst and subsequent contaminated waste by over 100-fold. Several innovations across reaction methodology and reaction engineering also enable the new route. Fundamental discoveries include replacing benzyl with diethylcarbamyl (DEC) as the phenol protecting group and implementing novel sulfide oxidation conditions. The DEC protecting group meets the needs of the synthesis and is still removable. This change enables alternative oxidation conditions, which allow the novel route to succeed.

Process mass intensity (PMI) is the total mass of raw materials put into a process (including water) for every kilogram of drug produced. Overall, the new route has a net PMI of 145 kilograms per kilogram of arzoxifene HCl, which is 31-percent less than the original route. Eli Lilly demonstrated its new route at a commercial scale in Lafayette, IN during . It finished validating the process in and has now manufactured commercial quantities. Eli Lilly&#;s application of the 12 green chemistry principles led it to reinvestigate its synthetic route and significantly improve its manufacturing process.

New One-Step, Chromate-Free Anticorrosion Coatings for Aluminum Alloys and HDG Steel: Corrosion protection by paints and organic coatings is a common practice. Around 600,000 metric tons of chromates are used in the paint industry for chromate conversion coatings (CCC) and as pigments annually. Chromates in the hexavalent state of oxidation have been identified as toxic and carcinogenic by the EPA. Chromates&#; self-healing property makes it difficult to replace. However, chromate exposures cause a gamut of health problems like ulcers, irritation of the nasal mucosa, holes in the nasal septum, skin ulcers, allergic reactions and nasal and lung cancer.

For good anticorrosion properties paints are formulated using high molecular-weight polymers. These polymers need the use of solvents which are Volatile Organic Compounds (VOC). During curing and drying of the paint these VOCs evaporate posing an occupational safety hazard.

Our invention is a one-step, low-VOC primer system for use on aluminum alloys and hot-dip galvanized (HDG) steel. The new primer obviates the use of chromates totally and yet gives an equivalent performance. Essentially it consists of water-dispersed resins, a crosslinker, an organofunctional silane and selected pigments. With a suitable corrosion inhibitor added, an ASTM B-117 resistance of over hours is obtained for the primer with or without topcoat on both substrates. The resin component is epoxy-based (a bisphenol-A epoxy or an epoxy-novolac resin) with small additions of other resins such as polyurethanes and/or acrylates.

New Organic Corrosion Inhibitors Help Replace Toxic Heavy Metals and Reduce Solvent Emissions: The coatings industry in the United States has had to focus its efforts to develop products that are compliant with an ever-expanding set of Federal, state, and local regulations, all designed to reduce or eliminate materials that pose a threat to either human health and safety or more broadly, environmental safety. The Irgacor family of organic corrosion inhibitors was designed and developed specifically to replace the standard anticorrosive pigments that are based on heavy metals such as lead, chromium, zinc, strontium, and barium.

These heavy metals are classified as being harmful to humans and/or the environment. In addition to the toxicity generally associated with them, heavy metal-based anticorrosive pigments are not particularly effective in low volatile organic content (VOC) waterborne coatings due to incompatibility. Irgacor organic corrosion inhibitors are free of heavy metals. They offer effective replacements for heavy-metal-based products and can produce commercially viable waterborne and high solids solvent-based coatings.

Replacement of all conventional corrosion inhibitors by these organic corrosion inhibitors could result in a potential overall annual source reduction of heavy-metal-based inhibitors of approximately 11.0 million pounds (4.2 million pounds chromate, 3.9 million pounds zinc/nonchromate, and 3.0 million pounds barium borates and silicates). Irgacor corrosion inhibitors are typically used at levels (based on total solids) of 1.5% to 4% compared to 10% to 20% or more for anticorrosive pigments.

The volume of Irgacor necessary to replace the 11.0 million pounds, therefore, will be only 2.0 million pounds. In addition, if Irgacor can further stimulate the replacement of solvent-based systems with waterborne coatings in the maintenance, auto finish, and marine markets by 20%, the annual volume of VOCs being emitted to the atmosphere would be reduced by 6.7 million pounds (from 8.0 million pounds to 1.3 million pounds). Irgacor organic corrosion inhibitors provide both long-term anticorrosive properties as well as excellent protection against flash rust. This provides the coatings industry with effective materials to further the development of waterborne coatings as replacements for solvent-based, higher VOC products.

New Reducing Sugar Assay: The chemical measurement of reducing sugars [sugars containing hemiacetal/hemiketal groups] is common in biochemical research and teaching laboratories. The currently available methods depend on the reaction of copper ions in hot alkaline solution with complexing and color-forming reagents. Typically, tartrate is used as the complexing agent and a solution of molybdenum and arsenate ions for the color-forming reagent [the arsenomolybdate reagent]. The arsenomolybdate reagent has a limited shelf-life and is extremely toxic. This presents formidable problems in the use and disposal of the assay solution. This solution must be stored as waste and disposed of commercially. The original assay outlined here is a procedure that uses a more stable complexing agent (EDTA) and replaces arsenate with phosphate in the color-forming complex. The materials produced in this assay are much more benign.

New Technology Converts Waste to Valuable Intermediates: Methylchlorosilanes, intermediates for the growing silicone industry, are produced by the reaction of elemental silicon with methyl chloride in a fluidized bed reactor. As with most chemical processes, conversion of reactants to products is not 100%; and while the percentage of waste is small for this process, these waste streams become more significant as the production volume of this industry continues to grow.

A significant fraction of the wastes produced by this "direct process" reaction are high-boiling methylchlorodisilanes that have been disposed of in the past by quenching them to form a nonhazardous landfillable material. In pursuit of reducing wastes and recovering value from the fed raw materials, Dow Corning has developed a process that provides for the conversion of these waste materials into valuable monosilanes by reacting the methylchlorodisilanes with hydrogen gas to form methylhydrogenchlorosilanes. Thus not only are the wastes associated with the production of chlorosilanes reduced, but the value of the raw materials are recovered as intermediates important to a wide range of siloxane products.

Once this new technology is implemented in Dow Corning&#;s basic silicone plants, total cost savings will be $3 million per year. This number can be expected to rise significantly as the production capacity of these plants increase.

New Water-Based Organic Corrosion Inhibitor: In , the anticorrosive pigments market for North America totaled approximately 33 million pounds and had a value of approximately $55 million. Strontium chromate, barium phosphosilicate, barium borosilicates, modified phosphates, and zinc phosphate accounted for the majority of anticorrosive pigments. These and other traditional corrosion inhibitors include known carcinogens, flammable oils and solvents, hazardous air pollutants, marine pollutants, and chemicals that cause eutrophication of ecosystems.

HALOX® 510 is the trade name for 1,3-propanediamine, N,N-dimethyl-, monobenzoate, a water-based organic corrosion inhibitor for direct-to-metal coating applications. It replaces corrosion inhibitors formulated with heavy metals such as hexavalent chromium, cadmium, lead, strontium, barium, and mercury. It contains no nitrites or other toxic chemicals, no eutrophication chemicals such as phosphates, and no marine pollutants such as zinc oxide and zinc phosphate. Its applications include direct-to-metal finishes (e.g., railcar coatings), automotive finishes, light industrial primers for metals, weld seam flash rust protection, temporary corrosion protection, general maintenance coatings (e.g., hand rails, metal decking), and synthetic and semisynthetic metalworking fluids.

HALOX® 510 imparts both anti-flash rust and long-term corrosion properties to waterborne coatings for steel, aluminum, galvanized steel, cast iron, and zinc alloys. HALOX® 510 interacts strongly with a corroding metal at the active anodic sites, forming a thin coating over the metal and restricting the access of other corrosive ions to the metal. Its alkaline pH also reduces the corrosion rate of the underlying metal. It is added to paint during manufacture or prior to applying the paint. It prevents ferrous substrates from flash rusting caused by the presence of water and oxygen as the paint dries. In addition, it does not adversely affect paint gloss.

HALOX® 510 has been in commerce since . In November , The Sherwin-Williams Company approved HALOX® 510 for its automotive products division.

New, Environmentally Protective Aircraft De-Icing Technology: For flight safety, snow and ice must be removed from airplanes before takeoff. Hot ethylene and propylene glycol, toxic chemicals used to de-ice airplanes at airports, usually run off the airplane onto the pavement and may escape into streams or ground water. Recently ethylene glycol along with other water-soluble organic chemicals such as MTBE have come under increased regulatory scrutiny. When glycol runoff seeps into groundwater, it can contaminate drinking water wells. In surface waters, it can harm wildlife. Some airports are installing multi-million-dollar catch basins to retain and dispose of this glycol runoff.

The Air Force Research Laboratory Air Vehicles Directorate (AFRL/VA) and independent inventor, Lee Williams have developed a high efficiency forced air deicer that utilizes compressed air to blow snow and unattached ice off of airplane wings and applies a thin film of hot glycol on the cleaned wing to melt any residual ice. The specialized forced air/glycol application system reduces by 50% to as much as 90% the amount of glycol required to de-ice a jet aircraft. Not only does the technology offer a marked cost savings but also the reduction in glycol use is a tremendous benefit to the environment.

Next Generation Fire-Resistant Fluids: Triaryl phosphate esters constitute a major industrial product category for fire-resistant hydraulic fluid and lubricant applications. Tertiary butylphenyl phosphate (TBPP) esters, a more specific class in this category, have a growing share of these markets due to their greater stability and lower toxicity compared to phosphate esters derived from naturally occurring cresols and xylenols. Current production methods yield TBPP esters with 10 to 45% tri-phenyl phosphate, a less stable component and a known esterase enzyme inhibitor that also is known to degrade the hydrolytic stability crucial for hydraulic fluid and lubricant applications.

Two synthetic approaches were developed to produce TBPP esters in high yield with less than 5% triphenyl phosphate. Both use commercially available raw materials and existing technology for production. The processes do not adversely impact environmental emissions or effluents. Most importantly, these new TBPP esters will be cost-effective to produce, given the performance advantages they bring to the marketplace. These next generation TBPP esters are more stable and less hazardous for many applications reducing environmental concerns about recycling and disposal, as well as reducing potential worker exposure hazards with much lower esterase inhibition properties. A patent has been filed on these TBPP esters and on the methods to manufacture them. Plans are in place to implement production of these novel products in .

NexterraTM Carpet: Modified PET Carpet Backing: Carpet tile backings have previously been made of polymers such as poly(vinyl chloride) (PVC), polyurethane, or mixtures of various thermoplastics that are derived from petrochemicals. The manufacture or disposal of some of these backing materials raises environmental concerns. Further, the energy required for the physical separation of the tile backing and the face fiber (usually by grinding or air elutriation) adds to the cost of recycling current tile backings. Physical separation also leads to impure component streams for recycling.

Beaulieu has developed a modified polyethylene terephthalate (PET) backing system that contains a much lower percentage of products derived from virgin petroleum, requires significantly less energy to produce, and offers new solutions to carpet tile recycling. Beaulieu had already been purchasing postconsumer PET bottles and converting them into carpet fiber. Now, however, Beaulieu is also converting plastic PET bottles into a pliable, flexible carpet tile backing system using a unique transesterification process (patent allowed). T

his process lowers both the molecular weight and the melting point of the polymer. Beaulieu&#;s modified PET polymer allows the company to use postconsumer ground glass as a filler in their backing. Altogether, their backing system contains 85 percent postconsumer materials and only 15 percent virgin petrochemicals by weight. Traditional carpet tiles contain approximately 50 percent virgin petrochemicals. The exclusive modified PET backing enables more cost-effective and energy-efficient recycling.

The solubility of the polymer in polar solvents allows separation of the carpet tile backing from the face fiber (usually nylon 6 or 6,6). During recycling, Beaulieu uses a glycol monomer bath at 150&#;180 °C to dissolve the polymer, separating it and the glass from the insoluble face fiber. Beaulieu launched NexterraTM carpet tiles in May . The company estimates its product sales at $1&#;5 million, and is expecting significant sales growth during .

Nitamin Steady Delivery Fertilizers for Improved Nitrogen Efficiency in Crops: Worldwide, farmers apply approximately 82 million metric tons of nitrogen fertilizer, primarily urea, to cropland annually. Plants are often unable to take up all of the nitrogen released into the soil from urea hydrolysis and salt-based fertilizers such as ammonium nitrate, so the excess nitrogen leaches through the soil and contaminates nearby waterways. Agricultural nitrogen is a major contributor to the increasing nitrate levels in many waterways around the world. These excess nitrates create hypoxic areas in which the levels of dissolved oxygen are too low to support life.

Nitamin® fertilizers provide an economic solution to this problem by slowing the rate at which nitrogen becomes available to the plant. By reacting urea with ammonia and formaldehyde under specific conditions to form a blend of small urea-formaldehyde polymers and cyclic compounds, Georgia-Pacific can control the rate at which the nitrogen is released to plants. The primary Nitamin® fertilizer product releases nitrogen for approximately 90 days, corresponding well to the requirements of many crops. This controlled delivery allows the plant to use more of the applied nitrogen, resulting in reduced application rates and reduced leaching. Nitamin® fertilizer reduces the amount of nitrogen used by 25 percent (onions and tomatoes) to 55 percent (cabbage). In other studies with potatoes, onions, and tomatoes, Nitamin® fertilizer increased crop yields by 7 54 percent.

Based on U.S. figures alone, even a 5 percent reduction in the amount of nitrogen applied to crops could eliminate the application of 810 million pounds of nitrogen annually. This improved efficiency of nitrogen use coupled with affordability is the highlight of this technology. Georgia-Pacific first commercialized its technology in January . During , universities and growers ran over 80 trials with different crops to verify the marketability of Nitamin® fertilizer. During spring , Georgia-Pacific will commercialize a liquid Nitamin® fertilizer for use on vegetables.

N-Methylmorpholine-N-Oxide (NMMO): A Novel, Non-toxic, Reusable Solvent for Cellulose as Source Reduction in the Production of Textile Fibers: For decades, scientists had been searching for an environmentally friendly means of forming a cellulosic fiber. The standard procedure for producing cellulosic fibers had been the viscose process, invented in . There were no neutral organic solvents for dissolving cellulose until when Dee Lynn Johnson, working in the laboratories of Eastman Kodak, discovered that N-methylmorpholine-N-oxide (NMMO) is a solvent for cellulose. In addition, he demonstrated that the cellulose solution can be filtered and the cellulose filaments regenerated by precipitation into water.

Furthermore, the NMMO could be recovered by evaporating the water and reused. This new solvent has now been commercialized by Huntsman Petrochemical Corporation, and several fiber manufacturers have developed commercial processes for producing the fibers. Fibers made by use of NMMO are called lyocell fibers, meaning cellulose spun from solution. The previous viscose process produces rayon fibers, but it requires a chemical reaction between carbon disulfide and cellulose in the presence of a strong base to produce a xanthate complex. Carbon disulfide is highly flammable and toxic to humans as well as being a greenhouse gas. Further, to produce fibers, the xanthate must be regenerated by extrusion into an acid coagulating bath where it decomposes and produces polluting byproducts that are discharged into water.

No-Clean Soldering: CTS Corporation Resistor Networks produces solid ceramic resistor networks in various single in-line, dual in-line, surface mount, and through-hole packages with standard or custom circuit designs. Through CTS Corporation"s commitment to a responsible environmental policy, many of its manufacturing methods have been modified with the goal of reducing or eliminating hazardous waste byproducts. One such method to reduce waste was the implementation of a No-Clean soldering process. This No-Clean soldering process, which began in March of , has eliminated the use of wave oil, soldering fluxes, and solvent cleaning. Changing to the No-Clean soldering process involved installing hoods over the solder pots. Using the hoods, an inert atmosphere, oil and flux are no longer required. The parts are clean after solder and thus no solvent cleaning is needed.

Previously, TCA (1,1,1-trichloroethane) and TCE (1,1,2-trichloroethylene) were used as part of a post-solder cleaning operation to remove flux and wave oil residues. Due to the elimination of flux and wave oil, these cleaning operations became unnecessary. Therefore, the amounts of waste TCA and TCE from soldering operations were reduced from 9,900 pounds and 226,000 pounds in , respectively, to zero in . As an added benefit of eliminating solvent-based cleaning operations, air emissions due to the use of these chemicals have dramatically decreased. From through , TCA and TCE related air emissions from soldering operations have been reduced from 99,000 pounds and 250,000 pounds, respectively, to zero. A cleaning operation, not related to soldering, generated a small amount of TCE air emissions in . This operation was eliminated in June of . The No-Clean soldering process has eliminated the generation of waste oil, flux, and cleaning solvents at the solder operation. Workers are no longer exposed to fumes from fluxes, oils, and cleaning solvents, which are typical of soldering operations. The product quality also has been improved.

Non Chromate Chemical Conversion Alternative Coating: The chemicals that we displaced were Chromic Acid, CAS # 133-82-0, and Potassium Ferricyanide CAS# -665-2. These Components are 54% of traditional process solutions. They are on the EPA list of hazardous or toxic chemicals and chrome and cyanide are listed materials for effluent limitation in the categorical pretreatment standard. We replaced them with a product containing Potassium Permanganate (KMnO4) CAS# -7, a very powerful oxidizer. KMnO4 will oxidize both iron and manganese in the metal ores to convert ferrous (2+) into the ferric (3+) state, and 2+ manganese into the 4+ state, to generate the permanganate ion MnO4, and manganese dioxide MnO2.

This liberates nascent (elemental) oxygen molecules. The stoichemetric amount of KmnO4 required to oxidize 1 mg of iron is 0.91 mg KMnO4. To oxidize 1 mg of manganese requires 1.92 mg of KMnO4. It then reduces these items to insoluble oxides, which are easily removed by filtration. The actual amount of KMnO4 needed has been found by us to be less then indicated by stoichimetry. It is thought that this is because of the catalytic influence of KMnO4 on the reactions. Heat, pH. and process temperatures are integral to the process. Process solutions function best in the range of 130-140 degrees F. and with pH. between the 7.0 and 8.0 range. Processing time varies from 7-15 minutes depending on the amount of oxidation required, with the resultant oxidation ranging from between a medium gold-brown (7-10 minutes) to a dark gold-brown (10-15 minutes). Rinsing is accomplished in de-ionized water.

Non Toxic Antifouling: IMC has developed a process to apply pure copper to a variety of substrates including aluminum, wood, fiberglass, and steel as a near permanent nontoxic antifouling that will not leach poisons into the environment and does not use solvents in the application process. The process is achieved through an electric arc used to melt the metal propelled by clean compressed air. The coating is permanently welded to the substrate and repels all types of marine nuisances, including the "zebra" mussels which are now a very expensive problem throughout the United States. The process is being used currently to protect power plants, cooling water intakes, ships, buoys, and other structures.

Noncyanide Silver Electroplating: A proprietary, noncyanide silver electroplating process, Techni-Silver Cy-Less L, was developed by Technic. Cyanide[-] based processes for electroplating have been extensively used in the United States for the last 50 years. Due to the hazardous nature of cyanide, extensive safety precautions must be incorporated when manufacturing electroplating chemicals, transporting the solutions to user sites, using the electroplating process, and disposing waste solutions. For example, if cyanide based solutions become too acidic, large amounts of poisonous cyanide gas are created. Historically, the electroplating industry has suffered many accidents due to the use of cyanide, which on a few occasions have resulted in death. Alternatives to cyanide-based solutions had been developed for all metals commercially electroplated except silver.

The noncyanide silver electroplating process developed by Technic provides an alternative that is noticeably less toxic than the cyanide process and inherently safer with regard to accident potential. In addition, tests clearly show that the noncyanide formulation is capable of producing sound, thick (i.e., around 125 [micrometer]) silver deposits that are extremely fine-grained and exhibit properties comparable to those produced in silver cyanide formulations. With the success of the noncyanide chemistry, Technic has made it possible to operate an entire plating facility without having to use any cyanide compounds.

Non-Destructive Testing of Corrosion Under Coatings: Surface corrosion on aluminum aircraft skins and around joints and fasteners is often the precursor to buried corrosion. Aircraft paints are routinely removed to reveal the presence of corrosion on the surface of metal structures and the aircraft is subsequently repainted. Aircraft painting and repainting operations result in significant emissions of volatile organics, organic and inorganic hazardous air pollutants, and hazardous waste. The objective of this project is to develop nondestructive inspection techniques to detect the presence of corrosion under an organic film in order to reduce the amount of painting and depainting that is performed and thus reduce the release of VOC and the generation of hazardous waste. This project will develop: (1) a spectral NDE technique employing an optical reflectance probe in the near/mid IR region combined with Directional Hemispherical Reflectance (DHR) and FTIR integrated detector; (2) Wide-area spectral imaging (WASI) using spectral filters and high-resolution focal plane cameras to allow rapid initial assessment of sub-paint corrosion; and (3) a Scanning Kelvin Probe (SKP) electrochemical method employing a calibrated capacitance probe to indirectly measure corrosion potential across a surface. Challenges to be overcome include probe positioning and electrical noise.

The project consists of five tasks over four years: (1) baseline measurements of unexposed coatings and typical corrosion products to build up a database of standards; (2) evaluation of aged aircraft components; (3) optimization of measuring systems at varying levels of corrosion and their modification for field use; (4) prototype verification (in conjunction with NAWCAD); and (5) preparation of a transition plan for cost-effective applications.

Minimizing the number of times the aircraft exterior coatings are stripped and reapplied provides substantial pollution prevention and cost saving opportunities. The inspection and measurement techniques can be used to target and map specific areas that require maintenance due to corrosion, thus eliminating the need to completely strip and reapply the exterior coatings. The inspection and measurement techniques provide a means to verify the condition of coating thus allowing for a switch to a condition-based rather than schedule-based maintenance. The inspection and measurement techniques provide a means to verify the condition of the primer and surface preparation once the topcoat has been removed thus eliminating a portion of the rework that now routinely occurs.

Nonhalogenated Flame Retardant for Use in High-Performance Adhesives and Coatings: Deaths due to fire claim thousands of lives every year all over the world. The challenge is to make products that will burn more slowly or not at all when exposed to fire, allowing occupants to escape and giving firefighters a chance to save lives and property. For decades, fire-retardant systems were made up of halogenated materials including bromine, chlorine, and antimony. These materials have recently come under scrutiny, however. They have been found to accumulate in the environment and in humans. This has led many domestic and international organizations to regulate and phase out these materials, as is the case with decabromodiphenyl ether (decaBDE). Many customers are requiring their suppliers to provide products that are halogen-free. The challenge is finding effective, nonhalogenated replacements.

Berry Plastics has shown that melamine borate (i.e., Budit 313 made by Chemische Fabrik Budenheim and distributed by Flame Chk) is an effective replacement in the pressure-sensitive adhesives it manufactures. Melamine borate is not expected to harm humans or aquatic environments. In contact with heat, it decomposes, acts as a heat sink, and releases inert nitrogen gases, which dilute the oxygen and flammable gases. It inhibits burning, prevents fire from spreading, and reduces the emission of toxic fumes by building a char barrier. The char barrier greatly diminishes the fuel available to fire.

The current challenge with nonhalogenated flame retardants is that more of the material is required to produce the same effect as the halogenated flame retardants. Thus, each application being made flame retardant requires a unique formula to balance flame retardancy with product functionality. The technology is not a one-to-one replacement and will require more research, but the cost is expected to be competitive with the halogenated systems. In November, , Flame Chk submitted a Premanufacture Notification and Low Volume Exemption for melamine borate to EPA.

Non-Hazardous Degreaser that Degreases as Efficiently as Trichloroethane and Outperforms Aqueous Products: Degreasing techniques have relied heavily on chlorinated solvents. While these solvents are highly effective in removing grease and oils from metals, at the same time they raise serious environmental and health concerns. Ozone depleting products like 1,1,1 Trichloroethane (1,1,1 TCA) and Trichlorotrifloroethane (CFC 113) have been phased out under the Clean Air Act Amendment, leaving users of these products little choice other than to replace them. A number of new nonhazardous cleaners have been introduced as alternatives, but few provide the effectiveness of a chlorinated solvent and most require users to accept a longer cleaning process and add costly new equipment.

Solvent Kleene, Inc. developed D-Greeze 500-LO as a safe replacement degreaser/cleaner that does not force companies to compromise cleaning performance for safety. In independent testing, D-Greeze 500-LO was identified as a safe alternative that could also outperform trichloroethane. While safe products such as aqueous-based cleaners are slow to perform, require heating, and involve an investment in costly new equipment and processes such as wastewater treatment, D-Greeze 500-LO can be easily integrated into an existing cleaning environment without a significant investment in new equipment or processes. Additionally, D-Greeze 500-LO is recyclable. A spent solution can be easily recovered and reused, minimizing both the hazardous waste stream generated and purchases of new cleaner.

Non-Polluting Composites Remanufacturing and Repair for Military Applications: The technical objective is to research, develop, and demonstrate a unique, affordable, environmentally friendly family of polymer-matrix composite (PMC) manufacturing and repair technologies for stand alone repair of current, soon to be fielded, and future DoD structures. Repair concepts and technologies will be demonstrated on DoD specific problems, including the design and implementation of a non-autoclave repair procedure for the Army&#;s complex integrated polymer composite lightweight armor designs used on the Composite Armored Vehicle and the Crusader Self-Propelled Howitzer (SPH); the development, demonstration, and documentation of a repair-friendly processing method for the remanufacture of the Navy&#;s FY02+ fielding of the Advanced Enclosure Mast Sensor System (AEMSS) including multifunctional material development; and the development of several advanced concepts for non-autoclave manufacture and repair of thin composite skins for aircraft and Army rotorcraft.

This program investigates a variety of novel composite processing and cure methods, including vacuum assisted resin transfer molding (VARTM), the multi resin co injection process, electromagnetic PMC curing techniques, and novel portable radiation (ultraviolet and electron beam) cure techniques to solve pollution problems in composites re-manufacturing and repair for military applications. A key to success is tight control over temperature during processing, reducing residual stresses and providing a consistent glass transition temperature (Tg) and consistent mechanical properties using recently invented composite manufacturing techniques and optimizing them for repair of complex DoD PMC structures.

This program will create technologies that enable out of autoclave processing as well as reduction of emissions from adhesive bonding operations. Used in tandem, these techniques can substantially reduce pollutants and waste in composite repair and re-manufacturing. These technologies offer the additional benefit of significantly decreasing the need for recycling scrap and waste materials by enabling efficient material use and reducing the number of processing steps required for the manufacture of multi-functional PMC components (e.g., Crusader and AEMSS) by up to 80 percent. In AEMSS alone, cost savings in excess of $10M over the next 6-7 years are anticipated.

Novel Applications of Polymer Composite from Renewable Materials: Metal corrosion costs the United States about 4.2% of its gross national product, or more than $250 billion in . To improve the longevity of the engineered material, the surface coatings must be refurbished to meet design requirements. Recoating the surface involves paint stripping and application of a fresh paint coating. Traditional stripping methods employ the organic solvent methylene chloride. Methylene chloride is carcinogenic and poses a health risk to the maintenance crew. Consequently, the aircraft maintenance industry has begun to utilize alternative approaches for depainting aircraft. One method that has proved reliable is dry-blasting to remove the paint coating mechanically.

The depainting process using blast media, however, is reported to be the largest single source of solid waste on military bases where aircraft repainting is performed. The work of Dr. Dharmaraj Raghavan at Howard University addresses the development of an organic coating removal technique based upon renewable plastic media. As such, the degradable dry-blast process is developed so as to eliminate 90 to 97% of the waste by biological or chemical degradation of the spent media. The degradation of solid media waste (based on renewable polymer) results in the production of speciality solvents that are environmentally safe and are value-added chemicals.

Another application where degradability of renewable polymer composite can be exploited is in membrane design. Membranes represent a worldwide market approaching $1 billion, annually. Membranes have found wide applications in industry, particularly in the separations industry. In the design of these membranes, solvents used include acetone, dimethyl sulfoxide, dimethyl formamide, and dimethyl acetamide. There is a general concern of the exposure of the working crew to carcinogenic solvents during the preparation of membranes.

To address these concerns, Dr. Raghavan has designed a compatabilizer-based polymer composite, where the major component is renewable polymeric material and the minor component is nondegradable synthetic polymer. The technology is based on the degradability of the renewable polymer in protic solvent/enzymic system and the ability to formulate a porous microstructure of synthetic polymer. The degradation of the renewable polymer results in the production of chemicals that are environmentally safe and can be used in the synthesis of renewable polymer.

Novel Chemical Analysis Technologies by Water Liquid Chromatography, Raman Spectroscopy, and High Speed Gas Chromatography: Dr. Synovec&#;s research addresses the development of novel liquid and gas chromatographic chemical analysis technology and related methodologies that are consistent with the goals of the Green Chemistry Program and pollution prevention. The goal of this research has been to develop unique chromatographic instrumentation and methods for laboratory, field and process analysis that reduce the toxicity and volume of consumable materials used in separations-based analyses, while enhancing the performance and information gleaned from the analyzer. This goal is a major research initiative at the Center for Process Analytical Chemistry (CPAC). The chemical analyzers and methodologies that have been produced by these research efforts benefit United States industry by enhancing the applicability of liquid and gas chromatography in a variety of arenas: routine and automated EPA methods, industrial process chemical analysis, conventional bench-top analysis, and remote chemical monitoring. A reduction in industrial pollution is a key result of these technologies by minimizing chemical waste through optimum process control.

Novel Device for Removing Mercury from Produced Water and Vapor Streams: Significant amounts of mercury can be present in the vapor and produced water generated by offshore drilling operations. Mercury in produced water associates itself with various impurities in the water in the form of organometallic, colloidal, ionic, and metallic species and as dissolved solids and gases. The broad range of organic and inorganic constituents in these streams makes treatment difficult. Treatments such as sulfide-impregnated carbon- or carbamate-based media that rely on a single stage to remove all mercury have been field-tested with poor results including organic fouling of the treatment media.

The novel MYCELX device uses a three-stage approach. Each upstream stage removes components that would otherwise tend to foul the subsequent stage. Stage 1 uses solubility and weak interactions. Stage 1 filtration media are impregnated with a curable viscoelastic rheology modifier, MYCELX HRMTM, which is the reaction product of drying and semidrying oils with isobutyl methacrylate. These media exhibit high affinity for colloidal mercury and insoluble organic compounds, binding them into a cohesive mass. Stage 2 uses Lewis acid-base reactions. In stage 2, a mixture of natural zeolite, MYCELX-impregnated carbon, and granular activated carbon exhibits high affinity for ionic and organically bound mercury and for soluble organic compounds, causing them to precipitate.

The final stage uses redox potential. This stage incorporates a matrix of braided copper wire electroplated with precious metals into an anisotropic electroless reduction module that isolates and extracts elemental mercury. Tests of the three-stage unit with mercury-laden (63.6 ppm) produced water from the field were successful at bringing the mercury levels below 0.5 ppb without a decrease in performance efficiency because of fouling. This device eliminates worker exposure to toxic compounds such as dimethyl mercury. It also eliminates mercury discharges into the oceans and atmosphere. MYCELX did pilot performance tests and applied for a patent for this technology in .

Novel Green Chemistries Extend the Useful Life of Automobile Catalytic Converters and Reduce Exhaust Gaseous Emissions: For the last 50 years, phosphorus in the form of zinc dialkyldithiophosphate (ZDDP) has been the most cost-effective antiwear, antioxidant, and anticorrosion component of engine oil. When ZDDP fulfills its function in the engine, however, the phosphorus can enter the exhaust stream, either by consumption or volatilization (released as a vapor). This phosphorus interacts with and decreases the effectiveness of catalytic converters used by automotive manufacturers to reduce exhaust gas emissions. This phenomenon, called catalyst deactivation, inhibits the ability of auto manufacturers to meet the EPA&#;s requirements for a 120,000-mile or 10-year warranty on the catalyst system.

In , the engine oil industry in the United States set an upper limit for phosphorus in engine oil at 0.08 weight percent. The same limit for phosphorus continues today. Although a phosphorus limit was set to protect catalysts, the phosphorus still present in the oil can volatize from the engine, then react with and deactivate the catalyst. Some ZDDPs are more prone than others to volatilize and, therefore, to deactivate catalysts. Concerns about losses in catalyst efficiency forced formulators either to design engine oils with lower concentrations of traditional ZDDP or to develop cost-effective, low-volatility ZDDP technology.

Lubrizol developed a new, low-volatility ZDDP technology and tested it for two years and 100,000 miles in New York City taxicabs. Taxicabs using oil with Lubrizol&#;s ZDDP technology had an average of 46 percent lower volatile phosphorus, 10 percent lower oxides of nitrogen (NOX), and 15 percent lower carbon monoxide (CO) than taxicabs using oil containing traditional ZDDP technology. In , the Lubrizol Corporation introduced its patent-pending, low-volatility ZDDP technology to provide engine oil formulators with an alternative to designing higher-cost engine oils with lower levels of ZDDP.

Novel In-Situ Zeolite Coatings in Monoliths: A novel, in situ method of depositing binderless zeolite catalysts in monolith reactor systems has been developed at the University of Cincinnati. In situ coatings of zeolites on monolith substrates maximize the effectiveness of the "shape-selective" aspects of zeolite catalysis. This technology can be used for a wide variety of zeolites, currently used extensively in the petrochemical industry. It has been shown that binderless zeolites used in monoliths exhibit enhanced performance, minimizing the formation of high molecular weight hydrocarbons with minimal diffusional limitations.

Two specific studies were conducted to demonstrate the effectiveness of these binderless zeolites in monoliths: conversion of methanol to gasoline hydrocarbons and catalytic cracking of n-hexane. The main technical advantages of monolith reactors are low pressure drop, improved performance due to less plugging and channeling, and high surface area per unit volume of reactor. The technology also offers many benefits for human health and the environment. For instance, alcohol obtained from fermented agricultural wastes can be converted to gasoline-range hydrocarbons on monolith reactors.

Besides producing useful fuel, this reaction produces no hydrocarbons larger than C12, which are difficult to burn and exhibit low biodegradation rates if released to soil and ground water. Also, this alternative fuel source conserves nonrenewable resources like petroleum and natural gas while simultaneously reducing dependence on imported crude oil. As a result of lower heavy hydrocarbon content, these fuels are cleaner burning and do not add further carbon dioxide to the environment.

Novel Process for Producing Polyols Based on Natural Oils: In recent years, the gradual shift of industry away from petroleum-based feedstocks toward less price-sensitive, renewable resources has focused on the polyurethane industry. These opportunities spawned a new generation of biorefineries that are bringing new products and processes to market. The Dow Chemical Company started exploring the use of seed oils as raw materials in the late s and subsequently envisioned a seed oil refinery as a new source of monomers and polymers.

Several technologies emerged to enable the use of renewable feedstocks in polyurethanes. One of these, Union Carbide&#;s hydroformylation and reduction technology, is critical for enabling the practical use of seed oils to produce polyols for polyurethane applications. The strategy adopted by Dow involves the methanolysis of triglycerides to discrete fatty acid components followed by the selective functionalization of the fatty acid methyl esters in a controlled fashion to prepare designed polyols. Fatty acid methyl esters with a tightly controlled functionality enable the preparation of polyols with a range of molecular weights, polydispersities, and functionalities that are similar to conventional polyols. The process creates very little waste; its only byproduct is glycerol. The Dow process allows the preparation of key intermediates and final products from a variety of seed oils ranging from commodity soybean oil to high-oleic seed oils such as NatreonTM sunflower oil.

RENUVATM technology is Dow&#;s commercial implementation of natural oils to produce polyols for the polyurethane industry. This novel technology enables the production of high quality, oil- and odor-free polyols. These polyols have the broadest range of applicability and the possibility of the highest natural content in the final polymer structure achievable in the industry. Compared with the chlorohydrin process for preparing conventional polyols, the Dow process reduces fossil fuel use by approximately 74 percent. Dow began commercial implementation during .

Novel Solvent-Free Fluoropolymer Coating Process: Fluoropolymers and other specialty polymer coatings are used widely. Conventionally, these coatings are applied using liquid-based methods. Polymer formulations are dissolved in a solvent or emulsified as a powder in a liquid medium, applied to the part, and then cured and dried with heat. The problems with this approach include the adverse human health and environmental effects related to the key processing agent and surfactant, perfluorooctanoic acid (PFOA); solvent waste; and energy-intensive curing processes.

GVD Corporation has developed solvent-free, chemically pure polytetrafluoroethylene (PTFE, Teflon®) polymer coatings formed by initiated chemical vapor deposition (iCVD). In GVD&#;s green coating process, a precursor gas such as hexafluoropropylene oxide decomposes as it passes over heated metal filaments to produce reactive molecules that migrate to the surface of the part and polymerize to form the desired coating. GVD selects precursors and operating conditions that use minimal energy and low temperatures.

This green technology is valuable for creating ultra-thin (10 nm to 10 micron) layers of insoluble, infusible polymers (like PTFE), which are hard to process by conventional means. GVD&#;s PTFE coatings are deposited from the vapor phase and are spectroscopically indistinguishable from conventional PTFE coatings. Critically, GVD&#;s clean PTFE process does not use any of the solvents or surfactants (e.g., PFOA) incorporated into spray-on PTFE formulations. GVD&#;s vapor-deposited, conformal PTFE coatings are well-suited to high-surface-area substrates and those with micro- and nanoscale features, such as foams, microelectromechanical systems, and carbon nanotubes. GVD&#;s coatings can be deposited at room temperature such that they can easily coat even facial tissue and other temperature-sensitive substrates. Other iCVD polymer compositions include cross-linkable silicones, functional coatings, cross-linked hydrogel coatings, antimicrobial coatings, and even electrically conductive polymer coatings.

GVD PTFE-coated parts and coating services are being sold commercially. During , GVD negotiated a multiyear PTFE manufacturing agreement with a major semiconductor equipment manufacturer.

Novel Superspreading Siliconized Surfactants: Silicone surfactants are a unique class of materials because of their high surface activity and easy-to-tune properties. The most common structures are poly(alkylene oxide)-substituted polydimethylsiloxanes, but these surfactants suffer from hydrolytic instability in alkaline or acidic environments.

Momentive&#;s novel technology combines the reduced surface tension and low-use levels typical of silicone-based surfactants with the stability in acidic and alkaline environments that is more typical of hydrocarbon surfactants. Momentive&#;s surfactants are stable in aqueous solutions from pH 2 to pH 12 without decomposition. These surfactants reduce the equilibrium surface tension of aqueous solutions to 21.5 mN/m at 0.1 weight percent, exhibit low critical micelle concentrations, and provide superspreading properties.

Momentive&#;s pH-stable, siliconized surfactants provide benefits typically achieved only with fluorinated surfactants. In aqueous solutions, these materials approach the low surface tensions required for many current fluorosurfactant applications, and the silicon-containing portions provide friction reduction similar to that of the perfluorinated backbones. The acidic and basic stability of the new surfactants is similar to that of surfactants based on perfluorooctane sulfonate (PFOS). Momentive&#;s materials can replace fluorosurfactants, which have come under scrutiny for their environmental persistence and bioaccumulation.

Silwet® Superspreader agricultural adjuvants represent another use of this technology. By helping water spread over and penetrate low-energy surfaces, superspreading surfactants help farmers conserve water while they control pests. Because they improve spray coverage, superspreaders allow lower rates of pesticide use. Because this novel class of superspreading adjuvants is pH-stable, the shelf life of pesticide formulations containing these surfactants is longer, and it is practical to package them in smaller containers, making their benefits available to the entire pesticide marketplace. Momentive has filed several patent applications for its pH-stable siliconized surfactants.

Novel, One-Step, Chromate-Free Coatings Containing Anticorrosion Pigments to Replace Chromate Pretreatment and Pigments: Paints and organic coatings are often used to protect metals and alloys from corrosion. The paint industry uses approximately 600,000 metric tons of chromates annually for chromate conversion coatings and as pigments. The "self-healing" property of chromates makes them difficult to replace. Hexavalent chromate, Cr(VI), has been identified as toxic and carcinogenic, however; it is subject to regulation by various government bodies. Chromate exposures cause a gamut of health problems including ulcers, irritation of the nasal mucosa, holes in the nasal septum, skin ulcers, allergic reactions, and nasal and lung cancer.

Paints are formulated with high-molecular-weight polymers for good anticorrosion properties. These polymers require solvents that are volatile organic compounds (VOCs). During curing and drying of the paint, these VOCs evaporate, posing an occupational safety hazard.

Professor van Ooij invented a one-step, low-VOC, anticorrosion primer system for use on metals, particularly aerospace aluminum alloys. The system can be applied directly to the metal, eliminating the chromate conversion coating. The novel primer is produced by mixing organofunctional bis-silanes with waterborne resins like acrylates (e.g., Maincote AE58 acrylic resin from Rohm & Haas), polyurethanes, or epoxies (like Daubond D from Daubert Industries, Inc.). To mimic the self-healing properties of chromate pigments, Professor van Ooij developed a synergistic silane-polymer structure incorporating commercial pigments such as zinc phosphate. The pigments leach out of the paint layer very slowly and only when corrosion starts to develop. This novel primer eliminates chromates entirely, yet performs equally well. Further, it cures at elevated temperature or at room temperature, leading to tremendous cost savings.

Professor van Ooij is commercializing his primer system through a small business that he founded, ECOSIL Technologies LLC. Many companies including DuPont, PPG, Sherwin Williams, Hentzen Paints, and BASF have received samples and are about to launch more intensive cooperation with ECOSIL.

NuloTM Technology: HAP-Free, Low-VOC, Water-Based, Air-Dry Coatings: The NuloTM technology is a water-based coating developed to replace solvent-based paints in steel joist dip painting operations. The most transfer-efficient method to paint open-weave steel joists is by dipping the joists into vats filled with paint. Traditionally, the joist industry used solvent-based alkyd paints containing 3.5 pounds or more of volatile organic compounds (VOCs) per gallon. Conventional water-based paints have not been successful in dipping operations because of their high cost, poor film properties, and problems with their stability. Time and pH fluctuations cause these paints to thicken and can turn them into an unusable gelatinous mass in the dip tank.

Century Industrial Coatings developed NuloTM as a new water-based paint that satisfies the joist industry&#;s needs for reduced VOC emissions, stability in dip tanks, comparable cost, and product performance equal to that of solvent-based paints. NuloTM paints contain no hazardous air pollutants (HAPs), have VOC levels of only 0.47 pounds per gallon, and have the appearance of solvent-based paints. The viscosity of NuloTM paints is controlled with water, not volatile organic solvents. The benefits of using the NuloTM paints to replace solvent-based paints include reduction of VOC emissions by 86 percent, elimination of HAP emissions, elimination of flammability and combustion problems, and reduced impact on human health and the environment.

NuloTM dip primers have been in continuous commercial use since July . NuloTM primers have already replaced approximately 1 million gallons of solvent-based primers, eliminating about 2.89 million pounds of VOC releases to the atmosphere. Replacing solvent-based primers with NuloTM primers in joist plants would eliminate an estimated 12.1 million pounds of VOC emissions each year. Century is in the process of expanding its technology to other painting processes and industry sectors.

N-Vinyl Formamide: The "Greening" of a Green Replacement for Acrylamide: Acrylamide is produced at volumes of over 200 million kg/year and is used worldwide to generate polyacrylamide. Acrylamide has been documented as a neurotoxin in human epidemiological studies; it is also a potential carcinogen. The Toxics Release Inventory (TRI) shows that 85 facilities released over 6.3 million pounds of acrylamide into the environment. N-vinyl formamide (NVF), an isomer of acrylamide, is readily polymerized to poly(N-vinyl formamide). NVF is neither a carcinogen nor a neurotoxin.

Polymers incorporating NVF can perform most of the same applications as acrylamide polymers. Unfortunately, the current commercial production process for NVF exhibits a cost disadvantage that is tied to "green disadvantages". Professor Beckman has created an NVF synthesis that is intensified, uses lower process temperatures, produces less waste, and uses less hazardous raw materials than the current commercial synthesis. He has also found that hydrolyzed homopolymers and copolymers of NVF form covalent gels in the presence of reducing sugars. These gels are sufficiently robust to allow their use in oil recovery, replacing currently used polyacrylamide-chromium(III) gels in preventing the production of waste water during oil production. Polyvinyl amine-sugar gels can also replace chlorinated compounds during the processing of paper.

Olefins by High-Intensity Oxidation: Ethylene is the highest-volume, highest-value commodity chemical. Over 120 million tons are produced annually with a value of over $100 billion. The conventional path to ethylene is the energy-intensive steam cracking of ethane. This approach consumes approximately 500 trillion British thermal units per year (Btu/yr), the equivalent of over 80 million barrels of oil. Steam cracking also suffers from poor selectivity for ethylene, but is well-established and has favorable process economics.

Velocys is at the cutting edge of microchannel process technology, a platform with the potential to provide substantial cost and energy savings. With the support of the U.S. Department of Energy&#;s Industrial Technologies Program, Velocys has been collaborating with Dow Chemical Company and Pacific Northwest National Laboratory. Velocys and its partners have developed a breakthrough process for producing ethylene. The process uses oxidative dehydrogenation in Velocys&#;s proprietary microchannel process technology architecture, along with carefully controlled temperature and a catalyst adapted to the microchannel environment. This approach improves feedstock use and saves substantial energy. These benefits stem from the novel reaction path and the unique ability of microchannel devices to tailor reaction rates and temperatures. The process can provide higher selectivities, conversions, and throughputs than the conventional steam cracking process, which is equilibrium-limited. Dr. Terry Mazanec, Senior Technical Program Manager at Velocys, leads a multidisciplinary team that has demonstrated that microchannel oxidative dehydrogenation can achieve the economic targets set by Dow, the world&#;s leading producer of ethylene.

The potential benefits of this novel, oxidative dehydrogenation route to ethylene are substantial. By , Velocys&#;s process could save 150 trillion Btu per year, eliminate more than eight million pounds per year of oxides of nitrogen (NOX), and eliminate more than 10 million pounds per year of sulfur oxides (SOX). Velocys has scheduled construction of its first commercial demonstration facility during .

One-Component, UV-Curable, Waterborne Polyurethane Coatings : In the &#;s, Bayer MaterialScience (BMS) developed water-based unsaturated polyesters that were UV- or peroxide-curable and reduced volatile organic compounds (VOCs) and very hazardous air pollutants (VHAPs). Unfortunately, this technology did not displace the acid-catalyzed nitrocellulose lacquer systems. In , Bayer&#;s two-component (2K) water-based polyurethane coatings entered the wood coatings market. This technology displaced high-VOC and high-VHAP coating systems and won the Presidential Green Chemistry Award, but it was limited in its user-friendliness and slow drying speeds, especially on automated wood coating lines. In , BMS developed a one-component (1K), UV-curable, waterborne polyurethane with reduced VOCs and VHAPs for wood coatings.

In this nominated process, BMS reacts a polyisocyanate and a polyol in a BMS production facility to create a polyisocyanate prepolymer. They then react this with a UV-curable polyol through an isocyanate&#;alcohol reaction to form 1K, UV-curable waterborne polyurethanes.

The process develops high-molecular-weight polymers (over 200,000 g/mol) in water without residual isocyanate monomer or polyisocyanate prepolymer. The product contains ultra-low VOCs because BMS&#;s proprietary process removes the acetone carrier after manufacturing. Renowned manufacturers of office furniture now advertise products made with BMS coating systems as having low emissions and being environmentally compatible. Large furniture companies are increasingly specifying coating systems with low or no solvent. BMS coatings cure in just seconds under UV light and meet low- or no-solvent specifications very cost-effectively.

Between and , commercial use of this coating system to replace acid-catalyzed varnishes or nitrocellulose lacquers resulted in reductions of 50&#;90 percent for VOCs and 50&#;99 percent for VHAPs, which is equivalent to removing 2.6 million pounds of organic solvents and 49,000 pounds of formaldehyde from the U.S. environment. Emerging markets for BMS&#;s 1K UV-curable waterborne polyurethane include aerospace and defense, site-applied UV-cured flooring, sunshine-cured wood decking, special effects coatings, and wet-strength papers.

On-line Detection of Subsurface Pollutants by Thermal Extraction Cone Penetrometry-Thermal Desorption Gas Chromatography/Mass Spectrometry: The ability to rapidly assess or monitor the disposition of environmental contaminants at purported or existing hazardous waste sites is an essential component of the nation"s environmental restoration program. Last year, 900 independent environmental testing labs analyzed five million samples in support of regulatory programs. Soil samples have to be collected from surface to ground water and then shipped off-site for analysis with waiting periods exceeding months. Soil samples, which represent approximately half the total number, are extracted with solvent then further separated using additional solvent to produce chemical-specific fractions. Each fraction is then analyzed by an appropriate method. The proposed technology is aimed at reducing or eliminating solvent usage during the sample collection and sample analysis process by collecting and detecting organic pollutants at depth without bringing the actual soil sample to the surface.

A thermal extraction cone penetrometry probe coupled to an ultrafast gas chromatography/mass spectrometer (TECP-TDGC/MS) has been developed to collect and analyze subsurface organic contaminants in situ. The TECP is capable of heating the soil to 300 °C, which is sufficient to collect volatile and semivolatile organics bound to soil, in the presence of soil-water content as high as 30%. Rather than using solvents to extract organics from soil, the TECP uses heat, then traps the hot vapor in a Peltier-cooled thermal desorption GC sample inlet for on-line analysis. In addition, the proposed technology reduces solvent usage when decontaminating sample collection probes and utensils used to homogenize samples. No other technology exists that is capable of thermally extracting organics as diverse as PCBs, explosives, or PAHs under these conditions. When combined with the ION Fingerprint DetectionJ software, ultrafast TDGC/MS is capable of analyzing complex environmental samples in less than 5 minutes.

On-Site Generation of Mixed Oxidants as a Safe, Green Alternative to Chlorine Gas and Concentrated Bulk Bleach: Although chlorine gas and bulk bleach have been used for 100 years to disinfect water and have saved countless lives in the process, these hazardous chemicals are now pervasive around the world. MIOX has developed on-site generation (OSG) of chlorine-based mixed oxidant solution (MOS) using low-cost salt brine (aqueous NaCl). This technology converts a brine solution electrolytically on-site and on-demand to produce MOS, which is a 0.4 or 0.8 percent chlorine-based disinfectant that is stored and metered at concentrations of less than one percent.

This process is superior to bulk bleach and chlorine gas in safety, effectiveness, and cost. It eliminates the hazards associated with traditional technologies, reduces energy outputs, and inactivates water-borne pathogens immune to chlorine disinfection. Further, transporting salt rather than fresh bulk liquid bleach reduces the addition of carbon to the atmosphere by 3&#;6-fold. MIOX&#;s technology is scalable from individual use to large cities. It offers significant chemical benefits including reducing the byproducts of chlorine disinfection, reducing disagreeable tastes and odors, reducing maintenance required by residual chlorine in water distribution systems, and eliminating biofilms. MIOX equipment produces a safe solution with capital payback periods of approximately three to five years.

MIOX&#;s technology replaces hazardous chlorine gas and bulk sodium hypochlorite with OSG of MOS using sodium chloride, water, and electricity as the feedstocks. Salt is a harmless, renewable green chemical feedstock. More important, however, MOS is safer with regard to accident potential, has low operating costs, and produces treated water that is safer for humans because the MOS disinfectant kills microorganisms more effectively and produces fewer harmful chlorinated byproducts. The removal of biofilms from heat exchangers, piping systems, and other surfaces by MOS increases the efficiency of this equipment, which also reduces carbon footprints.

During , MIOX launched RIO, its product line to generate industry-leading, onsite, on-demand disinfectant.

OpenairTM Plasma Surface Treatment: Reducing Emissions of Volatile Organic Compounds and Improving Environmentally Sensitive Paint Processes: World-class manufacturing processes require surface treatments that produce clean, highly activated surfaces for optimal adhesive bonding, coating, and printing. OpenairTM is the first industrial surface-preparation process to use plasma for nanoscale cleaning and surface activation. The OpenairTM process provides reliable, cost-effective, environmentally friendly surface treatment of metals, ceramics, glass, and polymers to enable the highest-quality bonding, coating, and printing.

This enabling technology allows full automation with total process control. OpenairTM plasma treatment breaks up organic contaminants on the surface of the part to be painted; the resulting small molecules vaporize or are oxidized to carbon dioxide (CO2) and water vapor. OpenairTM plasma treatment removes dust and neutralizes static. It activates surfaces by incorporating oxygen-containing functional groups that can form strong chemical bonds to the applied paint. Plasma treatment allows true chemical bonding between the substrate and paints. Compared to current processes, plasma treatment technology eliminates or reduces solvents, adhesion promoters, primers, volatile organic compound (VOC) emissions, wastewater streams, non-degrading parts from landfills, and high energy use. Previously, the technology had only been successful in treating small plastic components.

Plasmatreat and Ford Motor Company expanded plasma treatment technology to large, complex parts such as automotive bumpers made of thermoplastic olefins. Transferring the technology to large parts was difficult, primarily because suitable, large-scale processing equipment did not exist. Ford&#;s Dearborn, MI laboratory developed such equipment, opening a huge market for OpenairTM plasma technology. Large paint facilities adopting this technology can eliminate annually over one million gallons of toxic wastewater and tens of thousands of gallons of highly toxic sodium hydroxide, hydrochloric acid, and flocculating agents. Because a single plasma treatment replaces multistage power-wash systems, dry-off ovens, solvent wiping, and adhesion-promoting primers, the process has a shorter cycle time and a smaller fixed capital investment. During , two patent applications were filed for the technology.

Optifilm Enhancer 400 &#; A Nonvolatile Coalescent for Formulating High-Performance, Reduced-VOC Architectural Coatings: Attainment of mandated ambient ozone standards continues to present great difficulties in urban areas of the United States, where both nitrogen oxides (NOX) and anthropogenic volatile organic compounds (VOCs) are present at high levels in ground-level air pollution. State and local regulatory agencies have identified paints and coatings and, more specifically, architectural coatings as significant sources of VOCs. Consequently, these agencies have developed regulations limiting the amount of VOCs in architectural coating formulations. Currently, the strictest limits exist in California&#;s South Coast Air Quality Management District.

Traditional waterborne latex architectural coatings for interior and exterior applications require additives referred to as coalescents or coalescing aids. These additives allow the latex particles in the coating resin to form a contiguous film after application and to provide the protective properties and appearance required of the coating. In the past, the typical coalescents have been VOCs, which have been implicated as contributors to the formation of ground-level ozone.

In response to the need to reduce VOCs in architectural coatings, Eastman Chemical Company has developed Optifilm Enhancer 400, a nonvolatile alternative to traditional coalescents. Optifilm Enhancer 400 allows paint manufacturers more flexibility to achieve the performance they require; it also reduces or eliminates the contribution of the coalescent to ozone formation. When tested neat by ASTM D, Optifilm Enhancer 400 is 99.3 percent nonvolatile; it has excellent efficiency to coalesce latex paints while maintaining a good balance of performance properties. Optifilm Enhancer 400 delivers excellent film integrity, touch-up properties, and scrub resistance, even in paints formulated to very low VOC contents. Paints using Optifilm 400 have also demonstrated good exterior durability after 3 years of exposure. Optifilm Enhancer 400 has been in use in commercially available architectural coatings since .

Overcoming the Recalcitrance of Cellulosic Biomass and Envisioning the Role of Biomass in a Sustainable World: This project addresses technical and visionary issues associated with utilizing plant biomass, the only foreseeable sustainable source of organic fuels, chemicals, and materials. The project involves multiple topics related to consolidated processing, a widely applicable potential breakthrough in cellulose processing entailing production of cellulose enzymes, hydrolysis of biomass components, and fermentation of resulting soluble carbohydrates in a single process step. Additional project elements aimed at overcoming the recalcitrance of cellulose biomass encompass aspects of applied enzymology and microbiology, kinetics and reactor design for enzymatic hydrolysis of cellulose, pretreatment of biomass using compressed hot water, and conversion of paper sludge.

Process design and analysis work support the contention that advanced biomass-based processes have the potential to be cost-competitive with petroleum-based processes even at low oil prices. Accomplishments involving resource and policy analysis include analysis that identifies and explores the potential of biomass-based processes to have near-zero net CO2 emissions, prioritizes among uses for the large but ultimately limited biomass resource, and seeks to reconcile the vast range of estimates for the magnitude of potential biomass availability for industrial uses.

Oxidizer Scrubber Project: Dynacs in conjunction with the National Aeronautics and Space Administration (NASA) developed an innovative process that converts hypergolic oxidizer waste to fertilizer for use at KSC [Kennedy Space Center] and CCAS [Cape Canaveral Air Station]. The Toxic Vapor Detection (TVD) Laboratory at KSC has demonstrated with laboratory and field tests, a proposed nitrogen oxides (Ox) scrubber system change that is beneficial to KSC and other users of Ox scrubbers. This system will replace the current oxidizer scrubber liquor with one that lowers the Ox emissions.

As a result, the spent solution can be used as a fertilizer, thereby eliminating the second largest hazardous waste stream and reducing the overall operation costs at KSC and CCAS. Cost savings attributed to this project relate to the elimination of waste disposal costs ($70,600 per year) and a cost avoidance of approximately $16,300 per year in fertilizer purchases. This process was developed to meet Executive Order No. (Federal Compliance with Right-To-Know Laws and Pollution Prevention Requirements, dated August 6, ) and Executive Order No. (Federal Acquisition, Recycling, and Waste Prevention, dated October 20, ).

Oxygenation of Hydrocarbons by Photocatalysis: A Green Alternative: The chemical industry is a significant component of the domestic economy, generating well over $250 billion in sales and a trade surplus exceeding $15 billion in each of the last five years. The industry is also a major source of industrial waste and is the dominant source of hazardous waste in the United States. The costs of handling, treating, and disposing of wastes generated annually in the United States have reached 2.2% of gross domestic product and continue to rise. The chemical manufacturing industry generates more than 1.5 billion tons of hazardous waste and 9 billion tons of nonhazardous waste annually. Organic chemicals constitute the largest source of the toxic releases. Many of these releases can be minimized by improving the conventional housekeeping methods and pollution prevention techniques. H

owever, cleaner production methods can be achieved by adopting green synthetic methods. In recent years, there has been considerable work aimed at utilizing semiconductor photocatalysts for a variety of applications. High-value oxygenated organic compounds have been successfully synthesized from linear and cyclic hydrocarbons by a low-temperature photocatalytic oxidation using the semiconducting material titanium dioxide (TiO2). Various hydrocarbons were partially oxidized in both aqueous and gaseous phase reactors using ultraviolet light and titanium dioxide under mild conditions.

The conversions and selectivities obtained for the partial oxidation of hydrocarbons have been comparable to those achieved with the conventional method. For example, vapor phase photocatalytic oxidation of toluene with air, using a continuous reactor at 160 °C and 27 mW/cm2 irradiation, resulted in a 12% conversion per pass to benzaldehyde and benzoic acid, with 95% selectivity to benzaldehyde. The gas phase photocatalytic reactors eliminated the separation step involved with liquid solvents and catalyst slurry mixtures and minimized the adsorption of products to the catalyst. Initial life-cycle analysis studies have shown that this technology has the potential to reduce water contaminants and eliminate the use of toxic metal catalysts and solvents.

Light-induced catalysis expands the possibilities of using molecular oxygen in partial oxidation reactions that are now being conducted with far more expensive polluting oxidants. This technology also promises the potential of visible light-induced chemistry for commercially important syntheses. Furthermore, the high selectivity and mild conditions achieved with photochemical routes will be especially attractive for the manufacturing of fine chemicals.

Oxygen-Enhanced Combustion for Ox Control: The abundance of coal and expected high costs for other fossil fuels, such as natural gas, suggest that coal-fired power plants will still be in use for some time. Coal-fired utilities are also, however, major emitters of pollutants, such as nitrogen oxides (NOX). Praxair&#;s Oxygen-Enhanced Combustion (OEC) technology for NOX control is a unique combination of reduced NOX emissions and enhanced combustion. In OEC, oxygen replaces a small portion of the combustion air in a staged combustion system, increasing the local temperature under fuel-rich conditions. These higher flame temperatures convert NOX to N2 in the flame zone. In equipment from laboratory-scale furnaces to a nominal 125-megawatt power plant, oxygen- enhanced staged combustion reduces NOX emissions by as much as 60 percent without the operational problems commonly associated with staged combustion. An OEC system operated for most of the and ozone seasons at the Northwest Utilities 125-megawatt Mt. Tom Station, achieving NOX emissions of less than 0.15 pounds per million Btu. In two industrial boilers at the P.H. Gladfleter Paper Company in Pennsylvania, OEC systems reduced NOX emissions by over 40 percent.

By minimizing NOX formation in the combustion zone, OEC reduces or eliminates the need for postcombustion cleanup technologies such as selective catalytic reduction (SCR) that require ammonia. By minimizing the need for SCR systems, Praxair&#;s OEC technology also minimizes the production, transportation, and storage of ammonia. Because ammonia is hazardous, minimizing its use increases the safety of both plant personnel and the public. Further, because ammonia production requires natural gas, minimizing ammonia also helps preserve this important natural resource. Making broad assumptions about 600 coal-fired plants in 22 states, Praxair estimates that OEC technology could eliminate the use of over 500 million pounds of ammonia per year and atmospheric emissions of over 30 million pounds of ammonia in flue gas per year.

P4rimerTM: A Non-Toxic, Heavy-Metal-Free Primer Fueled by Red Phosphorus for Small Arms Cartridges: Small arms primer designs have not undergone major changes since , when the U.S. Army Ordnance Department (USAOD) introduced formulations based on lead styphnate as noncorrosive primers. These primers release considerably more lead during a typical training session in an indoor firing range than recommended under current exposure guidelines set by the U.S. military. Red phosphorous (RP) has been patented as a substitute for use in percussion caps, but RP primers are unstable and tend to produce corrosive byproducts. After limited use, they were eventually abandoned.

The chemical stability of RP remained an issue until manufacturers began using polymers to microencapsulate water-sensitive oxidizing agents. Encapsulating the hygroscopic lighter alkali and alkali earth metal nitrates in polymers greatly reduces the rate at which they take up water. Encapsulated in polymers, the abandoned phosphorous primer formulas have proven to be effective primer mixtures without the stability and hygroscopicity issues. P4rimerTM is a unique combination suitable for use as a percussion priming composition. It contains phosphorus, potassium nitrate, pentaerythritol tetranitrate (PETN, a high explosive), aluminum, and a polymer-based binder. P4rimerTM is encapsulated during manufacture with an epoxy coating that reduces the active catalytic sites for conversion into phosphoric acid. It is less hazardous, less explosive, more thermally stable, and less costly than formulations based on lead styphnate. Its combustion products are bioavailable and recyclable. It maintains the necessary chemical energy to ignite propellant efficiently.

At the Lake City Army Ammunition Plant alone, a formulation containing 26 metric tons of RP and 64 metric tons of potassium nitrate can now replace 71 metric tons of lead nitrate, 49 metric tons of barium nitrate, and 22 metric tons of antimony sulfide. According to a survey by the U.S. Department of Commerce, there are seven other large commercial U.S. cartridge sites manufacturing formulations based on lead styphnate.

Paclitaxel Process Improvements: Paclitaxel is a chemotherapeutic agent used to treat ovarian, breast, and other cancers. Hauser has developed a green technology centered around a self-patented process improvement by which cephalomannine and related ozone oxidizable compounds are separated from paclitaxel and other non-oxidizable compounds in biomass extract (ozonolysis technology). Hauser develops, manufactures, and markets special products from natural sources. Hauser&#;s proprietary extraction and purification processes enable the company to produce natural extracts at a higher quality, yield, and concentration than conventional procedures. Hauser employs proprietary technologies in combination with conventional techniques to process natural raw materials and to produce specialized natural products.

Hauser utilizes this technology to produce bulk quantities of the anticancer compound paclitaxel from Yew trees. The implementation of Hauser&#;s ozonolysis technology in the isolation of paclitaxel spurred many environmental and human health benefits. Several processing solvents (including methylene chloride), their subsequent air emissions (43,000 pounds annually), and significant wastes (254,000 pounds annually) have been eliminated. In addition, the use of natural resources was improved by incorporating renewable feedstocks (422,000 pounds recycled annually). A filter media that required disposal as a hazardous waste was also replaced with an indefinitely reusable alternative (eliminating 100,000 pounds of waste annually). Most importantly, these improvements have made the most effective anticancer drug in history more cost-effective to produce and more affordable to those in need. The financial impact of all of the process changes has resulted in a 50% decrease in the cost of manufacturing paclitaxel.

Paris II Solvent Design Software: Industrial solvents whose continued use raises concern for worker health and toxins in the environment need to be replaced cost-effectively. We created PARIS II to address this need. PARIS II is an acronym for Program for Assisting the Replacement of Industrial Solvents, Version 2. This software tool identifies pure chemicals or designs mixtures that can serve as alternatives to more hazardous substances currently in use. The "greener" solvents formulated by PARIS II have improved environmental properties, but can perform as well as those they were designed to replace.

The theoretical basis for the PARIS II program is the observation that the mathematical expressions governing solvent behavior are universal, and that the performance of each solvent is quantified by a number of coefficients representing various physical and chemical properties, e.g., viscosity, diffusivity, etc. The solvent&#;s features used by PARIS II include dynamic and equilibrium properties, environmental behavior (VOC index and environmental index), and performance and safety requirements. By applying this representation to solvent design, PARIS II can identify alternative solvents by matching coefficients rapidly. A ranked list of replacement solvents can be created within minutes. PARIS II provides a cost-effective approach to pollution prevention because users do not have to change equipment or modify their chemical processes in order to adopt safer, "greener" solvents.

Passive Treatment of Metal-Contaminated Water: A serious environmental consequence of the mining legacy in the United States is large flows of water laden with metals, usually known as acid mine drainage. These waters have concentrations of hazardous contaminants such as arsenic, cadmium, and lead that are harmful to human health and aquatic ecosystems. The typical treatment for these waters is to add industrial chemicals to precipitate the metals and then send the water through clarifying, settling, and filtering tanks. Such a labor- and material-intensive process is expensive; it is also impossible to use at the remote sites of many of the abandoned mines within the western United States.

Passive treatment is a process for removing contaminant metals from water using natural materials such as wood chips, sawdust, hay, manure, and limestone instead of industrial chemicals. The breakdown of these materials is catalyzed by natural bacterial consortia to produce sulfide, carbonate, and hydroxide ions that precipitate the contaminating metals. Natural, constructed, wetland structures filter these precipitates from water. The process does not require continuous monitoring. It requires only periodic inspections and sampling, cutting annual operating costs in half. This method of treatment is more sustainable ecologically than are conventional, active-treatment systems. Passive treatment both looks green and is chemically green.

Passive treatment was first successful at the Westfork Lead Mine in Missouri; since then, full-scale systems have been built for several private clients. The systems at all of these sites eliminate active precipitating chemicals, eliminate energy and material-intensive separation steps, and remove metal contaminants such as lead, cadmium, and arsenic, as well as zinc, copper, and mineral acidity from the water. Following these successes, the EPA recently adopted this technology at two places in the Ten Mile Creek Superfund Site near Helena, MT for a savings of over $100,000 per year.

Patterned Channel-Constrained Process for Additive Electroless Metal Deposition: Channel-constrained metallization (CCM) is described as a process for the fabrication of patterned metal features useful as etchmasks and electrical interconnects for microelectronics applications. The method creates a reactivity template through patterned exposure and development of a photoresist film to uncover an underlying ligand self-assembled monolayer (SAM) coating the substrate to be plated. A Pd(II) catalyst, selectively and covalently bound to the uncovered ligand sites, initiates additive, patterned electroless (EL) metal deposition of the substrate. Because the photoresist channel walls confine lateral EL metal deposition, the deposited metal film faithfully replicates the pattern of the mask used to expose the photoresist. Adhesion of the EL deposit, which is controlled by the strength of the Pd(II)-ligand bond, is sufficient to pass an ASTM tape peel test even on flat, unroughened surfaces. Consequently, the use of adhesive Sn(II) salts is not required for CCM, avoiding environmental problems associated with the use and disposal of Sn, accelerators, and substrate surface etchants currently employed with standard subtractive EL processes. The additive nature of catalyst and metal deposition characteristic of CCM further minimizes both reagent use and the generation of plating waste relative to subtractive methods, providing additional environmental and cost advantages for the process.

Perchlorate-Free Pyrotechnic Composition for Military Training Munitions: The U.S. Department of Defense uses many types of nonlethal training munitions on its installations and ranges. Two of the most widely used devices are M116A1 hand grenade simulators and M115A2 ground-burst simulators. Both simulators have traditionally employed a pyrotechnic composition based on potassium perchlorate and flaked aluminum, which react to produce the spectacular visual and auditory effects (i.e., flash and bang) required to prepare soldiers, sailors, airmen, and marines for combat.

Recently, there has been increasing awareness of the environmental and human health impacts of perchlorate compounds and concern for uses that release them into the environment. Perchlorate is both highly soluble in water and persistent; it has now been found in drinking water in at least 34 states.

Grucci, Inc. (the manufacturer of the simulators) joined a team of U.S. Army scientists and engineers to design a chemical composition that is less toxic, but still produces the same pyrotechnic effects. The team formulated, tested and evaluated several perchlorate-free compositions. They used a unique environmental health assessment strategy to predict the toxicity and other hazards of the candidate compositions and to ensure that any potential environmental risks were reduced to an acceptable level.

The selected formulation consists of black powder and flaked aluminum. This composition has passed all qualification, hazard classification, and production testing, and the U.S. Army has approved its use in hand grenade and ground-burst simulators. In early , Grucci will change all production of M115A2 and M116A1 simulators to this perchlorate-free, black powder based composition. This change will reduce the use of potassium perchlorate by approximately ten tons per year across the Department of Defense. Work is now underway to eliminate perchlorate from other munitions, including booby trap simulators, nonlethal stun grenades, and training rocket warheads.

Photoacylation and Photoalkylation of Quinones: Dr. Kraus, a professor of chemistry at Iowa State University, has developed the photoacylation and photoalkylation of quinones as an environmentally benign alternative to certain Friedel-Crafts reactions. This reaction can be conducted in supercritical carbon dioxide and is a good example of both atom economy and the more stringent criterion of reaction mass efficiency. Photoacylation produces adducts which have been used in very direct syntheses of benzodiazepines such as valium, natural products such as frenolicin, and antioxidants such as tert-butylhydroquinone. His research (eight publications, two patents, and one patent disclosure) has made available new and direct pathways for the synthesis of commercially important products. His publications have led to a renewed interest in this photochemical reaction

Picaridin: A Safe, Effective, and Environmentally Friendly Insect Repellent that People Will Use: Under a commitment to Responsible Care®, LANXESS Corporation and its parent company, LANXESS Deutschland GmbH (formerly part of Bayer AG), developed, manufacture, and market picaridin, an insect repellent. Picaridin offers a safe, effective, user-friendly, and environmentally responsible alternative to traditional repellents that are based on the widely known and frequently employed active ingredient diethyl-m-toluamide (DEET). Unpleasant odors, stickiness, and cautions associated with many formulations of insect repellent too frequently may deter people from using these products, thus leaving themselves unprotected from the risk of bites, infection, and disease.

Picaridin results from scientific innovations that overcome the cosmetic disadvantages that keep people from using insect repellents. The LANXESS active ingredient is marketed globally under the registered trademark BAYREPEL®; generically, it is recognized as picaridin in the United States, where LANXESS introduced it in . Picaridin was developed to increase efficacy against a broad range of insects and to improve cosmetic performance. Its attributes include (1) broad effectiveness against mosquitoes, ticks, sandflies, and horseflies; (2) cosmetic acceptability: gentle on the skin, non-sticky, almost no scent to humans; (3) not damaging to plastics, fibers, coatings, or sealing compounds; (4) can be used during pregnancy and breast-feeding; and (5) safe for children age two and older.

Picaridin is a custom molecule developed under a hypothesis that repellency is triggered by action on specific olfactory receptors of insects. Three-dimensional modeling was used to map a molecule to interact with the insects&#; receptors. Picaridin undergoes a fast and thorough primary biodegradation, yielding the more stable metabolite, picaridin acid. In tests carried out in Germany, neither groundwater nor tap water contained residues of picaridin or picaridin acid, indicating the complete degradation and removal of the substances by sewage treatment plants and groundwater conditioning systems.

PICKLEX®: An Environmentally Safe Metal Surface Preparation and Pretreatment Chemical: Governments all over the world are trying to ban the use of chromate conversion coating on aluminum and other nonferrous metals. PICKLEX® replaces this traditional chromate process as well as the zinc phosphate process used to pretreat steel. PICKLEX® is an environmentally safe, nonhazardous, water-based product. In one treatment, it removes surface rust, white rust, weld scale, and laser scale from metal surfaces and also provides coating. Applied to a metal surface, PICKLEX® provides long-term rust protection. Used to prepare, treat, and coat metal surfaces prior to finishing, it requires no waste treatment or disposal at all. PICKLEX® works at room temperature and, therefore, requires no special heating system. Users can apply it easily to a metal surface with a sprayer, with a brush, or simply by dipping the metal item into a bath of PICKLEX®. The U.S. EPA&#;s laboratory in Cincinnati, Ohio has tested this product and validated it as a nonpolluting, cost-effective conditioner for metal surfaces.

This single product is the answer to a host of pollution problems associated with many of today&#;s metal treatment chemicals. Many small and medium-sized companies have been using PICKLEX® in its various grades since and have experienced exceptional results with zero waste for disposal. In addition, PICKLEX® 20 (a derivative of PICKLEX®) has been used by several large companies, including one that fabricates steel structures for the military.

Pollution Preventing Lithographic Inks: Conventional printing techniques use solvents that contribute to pollution through evaporation and cleaning processes. Professor Cussler has developed a new ink that eliminates these emissions. A pollution preventing lithographic ink works conventionally at pH less than 7, but becomes its own emulsifying agent at higher pH. As a result, it can be washed off printing presses with aqueous base. The emulsification kinetics are not predicted by conventional correlations. Instead, they are consistent with an interfacial reaction between hydroxide and ink resin, which produces a soap layer that can be removed by shear. The results imply a strategy for other pollution preventing technologies.

Polyacrylamide Technology Reduces Soil Erosion: Irrigated agriculture produces one-third of earth&#;s total harvested crop and comprises one-half of the total value of all harvested crop yet it comprises only one-sixth of the world&#;s cropland. Erodible irrigated soils typically lose over 20 tons of soil per acre per year under furrow irrigation. Scientists at the Northwest Irrigation and Soils Research Laboratory developed and verified the use of a polyacrylamide (PAM) to reduce sediment loss by an average of 94 percent . In farmers used PAM to control erosion on an estimated 600,000 acres of furrow irrigated land, saving an estimated 12 million tons of soil in the third year of use. The key to developing an economical PAM technology for use in agriculture is in the conditions under which the primary reactive components polymer and soil were allowed to react. The conventional method applied polymers directly to the soil surface and mixed them with the soil to a maximum depth of six inches.

This method was effective, but required the use of up to 500 pounds per acre of polymer and sometimes required the application of a second agent used to activate the PAM. Associated costs made this method impractical for agricultural applications. The project sponsors altered the traditional approach by first dissolving very small quantities of water soluble PAM (10 mg per liter) in the irrigation source water and supplying furrows with the amended water only during the irrigation advance phase, i.e., during that time when irrigation water initially advances along the furrow and first wets the soil.

This procedure greatly simplified the use of the polymer, minimized the amount of reactants required, and selectively limited PAM-soil stabilization reactions to those soil surfaces that were exposed to furrow-stream shear flow. This efficient methodology required only 1 to 2 pounds per acre of PAM and was equal or more effective than previous soil conservation approaches. PAM technology sustains agriculture/soil productivity because millions of tons of soil and associated fertilizers/pesticides remain in the field. Its use substantially reduces maintenance expenses (more than $100,000 per year for some irrigated tracts) required to remove and dispose of sediment from regional irrigation systems and reservoirs, and can save farmers $25 to $50 per acre by eliminating on-farm pond/ditch cleaning and soil redistribution costs.

Reduction of sediment in rivers and reservoirs can be expected to reduce frequency and intensity of algal blooms, reduce turbidity, sedimentation of stream bottoms, and decelerate sedimentation reduction of reservoir capacities, and wear and impairment of hydroelectric generation capacities. This nontoxic, environmentally safe, and affordable chemical will provide irrigated agriculture a tool to greatly reduce sediment and associated pollutant contributions to streams and other water sources. Its use will help preserve irrigated agriculture production which is twice as productive as rainfed agriculture.

Polycarbonate/Polydimethylsiloxane Copolymers for Thermal Print Media: The process to make polycarbonates using bischloroformates and bisphenols or diols was developed and commercialized in the early s by the Polymer Products Unit of the Eastman Kodak Company in Rochester, New York. The original process to produce the polycarbonate of bisphenol A, diethylene glycol, and bisaminopropyl polydimethylsiloxane was developed in and commercialized in for use in a new thermal print media product. Concerns over waste and air emissions, as well as cost and capacity issues, prompted a research and development effort to replace this polymer before production volumes increased to forecasted high levels. The new process to produce a similar polycarbonate/polydimethyl siloxane copolymer was certified early in .

Improvements include the following: (1) the new process is made in the solvent in which the polymer is coated, and is delivered to the manufacturing department dissolved in that solvent, eliminating the methanol precipitation, methanol washing, and vacuum drying steps; (2) in the new process, triethylamine is used as the acid acceptor instead of pyridine, making the water wash waste streams less hazardous; (3) the new process uses the commercially available diethylene glycol bischloroformate, eliminating the need to manufacture the bisphenol A bischloroformate at Kodak in Rochester (the bisphenol A bischloroformate synthesis uses phosgene as a key reactant, and its purification produces large quantities of hazardous waste containing heptane and silica gel). The new process will yield over 1.2 million pounds of hazardous waste reductions and more than 3,000 pounds of air emissions reductions from to .

Polyelectrolytes: Reduce Your Carbon Footprint Using an Eco-Friendly Technology to Disperse Wax in Water without Heat: Emulsions containing waxes are common ingredients in wood or tile polishes, personal care products, coatings, and sealants. The traditional process of making oil&#;wax&#;water emulsions generally requires heating two mixing vessels: one for the aqueous phase and another for the oil phase. The temperature of each vessel needs to be higher than the melting point of the wax in the oil phase. Typically, steam, hot water, or cold water pumped through jackets around the vessels control the temperature. Once formed, emulsions must be cooled very carefully because the rate of cooling affects the aesthetics of traditional emulsions.

Previous cold process technologies solved the problems of multiple mixing vessels and the necessity of heating and cooling. Because existing cold process emulsions do not contain wax, however, they tend to feel more like gels than like conventional emulsions.

JEEN&#;s Jeesperse Cold Process Wax (CPW) revolutionizes the science of making emulsions with wax. The combination of waxes and polyelectrolytes in Jeesperse products allows formation of complete emulsions without either heating or cooling. It uses only one mixing vessel and reduces manufacturing time by 50&#;75 percent over conventional processes. Sodium polyacrylate is the first polyelectrolyte used in Jeesperse CPW products, but many other polyelectrolytes can be used. In the future, natural gums in combination with natural waxes will lead to natural CPW products. Natural gums that can be used to create CPW products include sodium polyaspartate, sodium alginate, carrageenan, guar, and xanthan.

Jeesperse CPWs do contain wax and will make emulsions that feel like conventional, heat process ones. The ability to use waxes in cold process emulsions will expand the use of cold process manufacturing. During , JEEN applied for U.S. patents. The nominated technology is available commercially as Jeesperse CPW.

Polymers and Plastics from Lignin Biomass: The most easily available as well as renewable supply of carbon is biomass: the trees, shrubs, and foliage around us. Meeting society&#;s needs from trees requires that new chemistry and technology be invented to convert plant mass into industrial supplies, consumer goods, and the drugs we use. Cellulose, the major component of wood plants, is already well-used to make paper and chemicals. Lignin, the other one-fifth to one-third of the plant, is often landfilled or burned as a byproduct at the rate of 20 million tons per year. This means that, on average, one quarter of every tree harvested is wasted. Through 15 years of research, the Center for Forest Products has developed methods to convert lignin and wood into the polymers, plastics, and engineering materials that society will need in the future.

The methods involve reacting lignin with a polymer building block in the presence of a salt and peroxide bleaching agent to generate a new graft copolymer. This simple and fairly general reaction allows a byproduct of the paper industry to be converted into water treatment chemicals for purifying water, dewatering agents for compacting sewage sludge, chemicals for insulation and furniture foams, biodegradable and consumer plastics, binders for wood-plastic composites, and reinforcing fillers for tire rubber. In addition, this modified lignin can replace up to 37 million tons of monomers such as acrylamide, styrene, vinyl chloride, and acrylomidomethylpropane, all of which are flammable, toxic, explosive, or carcinogenic. By developing a chemical method to alter lignin, future generations can obtain the supplies and materials they need while harvesting fewer trees, wasting less of each tree, and depending less on toxic and carcinogenic compounds.

Positive Environmental Impact of Novel Crankcase Lubricant Technology: Phosphorus in the form of zinc dialkyldithiophosphate (ZDP) is the most cost-effective antiwear, antioxidant, and anticorrosion agent available for engine oil. Phosphorus, however, can enter engine exhaust and decrease the ability of catalytic converters to reduce emissions. This effect, called catalyst deactivation, makes it difficult for automotive manufacturers to meet EPA&#;s requirements for lengthy warranties on catalyst systems. To protect against wear and safeguard the catalyst, industry has restricted phosphorus in lubricants to 0.06&#;0.08 percent by weight. Even at these low levels, however, phosphorus can volatilize and deactivate the catalyst. Lubrizol has developed the HyperZDPTM System, a low-volatility ZDP. In partnership with Valvoline, it has studied the performance of Hyper ZDPTM technology and that of conventional ZDP technology. In Valvoline motor oils, HyperZDPTM reduced phosphorus deposition on the exhaust catalyst by 30&#;50 percent after 100,000 miles.

Road testing for 100,000 miles reduced non-methane organic gases by 20 percent, NOX (nitrogen oxides) by 40 percent, and carbon monoxide (CO) by 35 percent. Chassis dynamometer testing showed NOX reductions of 30 percent. Bench testing showed reductions in T50 across different catalysts. Lubrizol then modeled T50 values for total hydrocarbons (THC), CO, and NOX as functions of catalyst characteristics and phosphorus levels on the catalyst.

The models showed the strongly beneficial, statistically significant impact of Valvoline motor oils with HyperZDPTM on catalyst performance. Environmental Resources Management Ltd. conducted a lifecycle analysis consistent with ISO . Compared to conventional ZDP, HyperZDPTM produced very significant reductions in photochemical oxidation, acidification, global warming potential, and human toxicity along with a minor reduction in aquatic toxicity and a minor increase in resource depletion. After Lubrizol introduced its API SM/ILSAC GF-4 low-volatility ZDDP technology in , Valvoline began using it universally in passenger car motor oils. Lubrizol received a patent for this technology in .

PostSaver®: PostSaver® is a patented invention that can substantially reduce the leaching of toxic wood preservatives from treated wood commodities in ground contact. A PostSaver® wrap will extend the useful service life of treated wood commodities using only a fraction of the preservative typically required for ground contact. PostSaver® wrap is a thick, UV-stabilized polyethylene film that has an internal bitumen coating. The bitumen inner layer protects wood in contact with this tar-like substance; the outer polyethylene film layer hinders decay and insect attack further and prevents water absorption. PostSaver® wrap adheres to wood commodities such as posts, lumber, and poles under slight pressure and heat from a mechanical applicator.

PostSaver® wrap is unlike typical wood preservative groundline-remedial treatment wraps; it does not contain additional toxic preservatives to supplement the wood preservatives that have already leached from wood in service. In contrast, PostSaver® wrap is applied to new wood prior to its being put into service. PostSaver® wrap can reduce the leaching of any wood preservatives in a treated commodity, can reduce the actual loading of toxic, wood-preservative chemicals needed to protect wood in ground contact, and can help extend the service life of durable heartwood species. PostSaver® may also expand the use of more leachable, less toxic wood preservatives such as borates.

PostSaver® wrap currently has worldwide sales in over six countries. During , PostSaver USA had manufacturing and implementation sites located in Coos Bay, OR and Mechanic Falls, ME.

Practical Asymmetric Catalytic Hydrogenation: Over 50 percent of the world&#;s pharmaceuticals are single enantiomers; sales of chiral drugs were $159 billion in . A growing challenge is to develop cost-effective, green chemical catalytic processes to make chiral molecules. Asymmetric chemocatalysis is one of the most competitive replacements for classic chiral resolutions, which generally require large volumes of solvents, chiral resolving agents, and even waste treatment of unwanted enantiomers. The cleanest and most cost-effective reductant available is hydrogen. Asymmetric hydrogenation accounts for over 70 percent of the current methods for commercial asymmetric chemocatalysis. Fundamental, innovative chemical methods are needed to develop these green chemical processes. Breakthroughs in this area will have broad applicability in industry.

Professor Zhang and his group have developed novel transition-metal-reduction catalysts for the practical synthesis of chiral alcohols, amines, acids, amino alcohols, diols, and alpha- and beta-amino acids. They have investigated the fundamental factors controlling enantioselectivity and invented a toolbox of practical chiral ligands for the asymmetric hydrogenation of ketones, alkenes, imines, and aromatic compounds. They have observed high activity (up to 50,000 turnovers) and enantioselectivity (up to 99 percent enantiomeric excess) for the hydrogenation of some substrates. They have demonstrated the synthetic utility of asymmetric hydrogenation in the green chemical processes with challenging asymmetric transformations for important biologically active compounds such as Lipitor®, Cymbalta®, and carbopenem.

Professor Zhang&#;s technology has numerous patents. He is commercializing it through Chiral Quest, Inc., which is providing his chiral technology to pharmaceutical and fine chemical companies including Phoenix, Pfizer, Merck, and Eli Lilly. Phoenix Chemicals Ltd. is currently manufacturing the Lipitor® side-chain using Chiral Quest&#;s technology.

PreKote® Surface Pretreatment: Replacing Hexavalent Chromium with an Environmentally Safe Solution: Hexavalent chromium (Cr(VI)) is the industry standard for corrosion protection on aluminum substrates prior to painting, but it is also toxic and hazardous. Discontinuing its use is a U.S. EPA pollution prevention priority through the Executive Order . Cr(VI) is also on the European End of Life Vehicles (ELV) Directive of nonallowable materials. Most recently, in May , the Occupational Safety and Health Administration (OSHA) reduced the permissible exposure limit (PEL) for Cr(VI) by 52 percent in the aerospace industry.

In , Pantheon Chemical began an extensive research program to find an environmentally safe replacement for chromium pretreatments, also called chromium conversion coatings. Pantheon designed PreKote® on the molecular level from environmentally safe chemicals to clean and promote paint adhesion to substrates to be coated. PreKote® has a neutral formula that is not based on metals. It eliminates the need for an acid precoating treatment. Its corrosion inhibitors are not persistent, and its surfactants are biodegradable and environmentally friendly. Unlike other pretreatments, PreKote® is suitable for use on ferrous and nonferrous metals, anodized and phosphated surfaces, many plastics, and composite materials.

After years of extensive laboratory and field testing using highly advanced techniques of surface analysis and molecular modeling, Pantheon introduced PreKote® to the U.S. market as an efficient, green substitute for chromium pretreatments. In , the United States Air Force (USAF) approved and implemented the use of PreKote® as a replacement for chromium pretreatments of aluminum substrates. Subsequently, leaders in the commercial aerospace market conducted extensive testing and implemented PreKote® for its safety, performance, and economic benefits. PreKote® technology provides superior performance while it improves environmental and worker safety by eliminating heavy metal waste streams and replacing toxic acids and solvents. It also decreases operational costs significantly by simplifying pretreatment procedures.

Premature Degradation of Coolant Oil in the Machining of Magnesium in the Automobile Industry: The research of James P. Rybarczyk at Ball State University is concentrated on a fundamental chemical study to increase the longevity of a water-based coolant, cutting oil emulsion used in the machining and manufacture of magnesium cases for the automotive industry. Water-based emulsions have virtually replaced the more toxic organic solvent-based ones, but the difficulty of water-based ones in magnesium applications involves the dissolution/reaction of the machined magnesium fines with water, producing hydrogen gas and dissolved magnesium ions.

These Mg+2 ions then interact with the emulsion, breaking the oil/water emulsion and splitting out the oil, creating scale deposits of magnesium carbonate, magnesium greases, and the virtual disintegration of both the coolant and cutting properties. This necessitates a changing of the coolant systems at a frequency of 1.5 to 2 months, as opposed to a theoretical 24 months.

This high frequency of replacement/disposal results in a significant workload cost, monetary cost, and above all, environmental cost. Rybarczyk&#;s research established the causes of the premature breakdown of the emulsion and provided seven recommendations for chemical and/or physical process modifications. The study focused on the fragility of the emulsion and on the control of pH at basic levels to minimize the water dissolution of magnesium. The study showed an increase of better than 16 times in the lifetime of the emulsion from these recommendations. The industry has currently implemented three of the recommendations, with hopefully more to follow, resulting in a 2 times to 3 times increase in emulsion lifetime.

Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel: Commercial pulp mills do not generally recover hemicelluloses because traditional hot-water extraction also extracts lignin, which can stick to and clog the mill piping and digesters. As a result, hemicelluloses are usually degraded and burned. A novel pre-pulping extraction technology discovered by researchers at the University of Maine uses green liquor, an existing wood extract stream at Kraft pulp mills, to recover hemicelluloses from hardwood chips prior to conventional pulping. The near-neutral green liquor (NNGL) is rich in oligomeric hemicelluloses that can be a valuable, renewable feedstock for biorefineries. Acetic acid is a major coproduct.

The NNGL extraction prevents pollution by recovering hemicelluloses that would otherwise be wasted, improving energy efficiency by reducing fossil fuel used by lime kilns, and using existing pulp mill facilities to create a new feedstock. Using forest products instead of corn, the current dominant renewable feedstock, could further reduce greenhouse gases and toxic chemicals. This new technology does not change the yield or physical properties of the pulp. In a demonstration of the NNGL extraction process for over 800 hours at full commercial scale, the Old Town mill in Maine produced several million gallons of extract while maintaining quality pulp output.

University of Maine researchers have successfully demonstrated both the fermentation of NNGL wood extracts into ethanol and lactic acid and the separation of acetic acid from the extract. The Old Town mill is currently designing a commercial satellite biorefinery to convert pre-pulping wood extract into biobutanol and acetic acid. Peer-reviewed analysis shows that a 1,000 ton-per-day pulp mill could produce ethanol from NNGL wood extracts at $1.63&#;$2.07 per gallon and acetic acid at $1.98&#;$2.75 per gallon. With this technology, the bleached hardwood Kraft pulp mills in the United States could recover over 1 million tons of hemicelluloses per year for biofuel and bioplastics.

PRE-TEC ®: An Environmentally Friendly Wood Treatment: Preventive Technology developed PRE-TEC ® to protect wood products against fire, termites, mold, fungus, and moisture without using toxic or dangerous chemicals. PRE-TEC ® contains a silicate&#;borate mixture that forms an insoluble borosilicate gel upon drying. This treatment protects against termites and fire at the usual levels in borate-treated wood. The insoluble silica gel combats leeching. The carbonates, silicates, and borates in the treatment provide exemplary fire retardation, termite repulsion, mold inhibition, and decay prevention. PRE-TEC ® contains no metals. The disposal of wood treated with PRE-TEC ® will pose no threat to the environment.

Various species of trees produce vastly different types of lumber. Unfortunately, traditional wood-treatment technology is not effective for all types of lumber such as red pine, the preferred lumber in the Midwest. PRE-TEC ® has successfully treated many wood products that had previously been untreatable. This allows the opening of new markets to the building industry.

PRE-TEC ® will work with the system of "green" pressure-treating wood that is already established. It is currently being tested and cleared by the International Code Council (ICC) using their "green" process for approval of treated lumber for the building industry. If PRE-TEC ® replaces only one billion board feet of copper-based wood treatments next year, over 7,000 tons of copper would not contaminate the environment through leeching or eventual disposal of copper-treated wood. PRE-TEC ® is currently undergoing further testing by independent certified test laboratories.

Primer for Anti-Fouling Paint: This technology and material is a primer to be used in conjunction with the bottom paint (antifouling paint) that is found on the bottoms of all ocean-going boats. Every year, thousands of ocean-going boats receive a coating of antifouling paint that typically must be removed and reapplied annually. Current technology mandates that the paint be sanded off. The resultant powder is dangerous, as it can be blown into the water and inhaled by the people sanding the bottom of the boat. Copper oxide is commonly used as an antifoulant, but it is toxic to all forms of life, including humans.

Every year, 1.5 million pounds of copper oxide paint dust are dumped into the ocean in the United States alone because of boat bottom sanding. A method and material have been developed that allow antifouling paint to be removed quickly, in large sheets, without sanding. The primer uses a sophisticated wax/water emulsion. Once the water from the emulsion has evaporated, the antifouling paint is applied. The boat is used, as usual. When the boat is to be hauled and the antifouling paint is to be reapplied, the old antifouling paint is removed with hot water at a temperature just above the melting point of the wax. The spent antifouling paint is easily collected in drums and either recycled or properly disposed of in a hazardous waste disposal site.

Primerless RTV Silicone Sealants/Adhesives: Room temperature vulcanizing (RTV) silicones, developed in the late "s, have played an important role in the design and superior performance of weapon systems (airplanes, missiles, electronics, ammunition, vehicles and nuclear weapons) developed by the DoD and DOE. A unique combination of properties has made them the material- of- choice for designers wanting to improve and increase weapon performance.

RTV silicones are used as adhesives, sealants, coatings, heat insulators and encapsulating materials. For RTV silicones to achieve a high level of consistent adhesion to various substrates, a saline primer is applied prior to silicone application. These primers contain 90-98% volatile organic compound (VOC) solvents, which evaporate into the air. The objective of this project is to develop, evaluate, and transition a primerless self- bonding low temperature curable addition cured silicone, which eliminates the use of high VOC primers without compromising durability, compatibility, thermal resistance and long term stability.

The project will be conducted in four phases. In phase I, current addition cured silicones available off the shelf will be modified with a bifunctional adhesion promoter compound. In phase II, a less inhibiting adhesion promoter, based on structures defined by molecular modeling will be utilized in an attempt to develop room temperature curing systems. Laboratory adhesion evaluations will be used to establish "go/no go" criteria for technology development in phase II. To expand adhesion capability to a variety of substrate materials, including plastics, novel adhesion promoting concepts will be evaluated in phase III using guidance from molecular modeling predictions. Phase IV will demonstrate the use of a new primerless silicone formulation.

By eliminating the use of the traditional primers, development of this technology will provide several benefits: a reduction of over 500,000 lb/yr of VOCs; avoidance of costs from waivers, deviations and fines associated with the use of non-compliant materials; savings derived from reduced hazardous waste disposal costs; improvement of throughput; reduction in inventory management costs; and cost savings from reduced purchasing, material handling and specification consolidation.

Producing Chemicals and Carbon from Waste Tires, Plastics, Carpet, and Biomass: Vast amounts of waste tires, plastics, and biomass have been discarded in landfills because there was no practical way to depolymerize them for reuse. BCD Group-II has developed catalytic transfer hydrogenation (CTH), a modified base-catalyzed decomposition (BCD) process that depolymerizes plastics, tires, rubber, other polymers, and biomass into chemicals or solid products with carbon contents of at least 84 percent. The CTH process is non-oxidative. Unlike pyrolysis and liquefaction processes that require temperatures of 450&#;700 °C, the CTH process converts polymers into reusable chemicals and carbon at 130&#;300 °C within 30&#;90 minutes.

The proprietary reaction medium is composed of an alkali metal carbonate or hydroxide, a hydrocarbon donor/solvent (usually a high-boiling aliphatic hydrocarbon), and a proprietary catalyst/water absorption agent. Reactive hydrogen from the hydrogen donor breaks bonds between heteroatoms to produce monomers, oligomers, polymers from copolymers, and sodium salts of anions. Products are also easily converted into syngas. Depolymerization of polyester, polyurethane, polycarbonates, or carpets by existing technologies requires much higher temperatures, higher pressures, and more expensive reagents. CTH technology can replace coke, a traditional fuel in solid oxide fuel cells (SOFCs).

Coke production from coal requires processing for 16&#;24 hours at temperatures of around 2,000 °C. The CTH technology produces carbon from tires and biomass that is useful as SOFC fuel. A U.S. patent application describing this technology was submitted (Provisional Application # 61/571,383) on July 7, . In , BCD Group-II and C-4 Polymer Inc., of Chagrin Falls, OH, completed laboratory-scale studies to depolymerize and recover polypropylene from copolymer waste generated by the food packaging and auto industries. BCD Group-II expects to complete pilot-scale tests and initiate commercial development during . Licensees of the original BCD process and an India chemical firm have expressed interest in CTH technology; the Environmental Business Cluster in Silicon Valley, California, will present this technology to venture capitalists.

Producing Industrial Chemicals by Fermenting Renewable Feedstocks at a Lower Cost: Chemical producers are searching to meet growing worldwide demands for many of today&#;s industrial chemicals with renewable feedstocks and environmentally sustainable methods. The transition to renewable feedstocks has been slow, however, because environmentally sustainable processes must be cost-competitive with traditional petroleum-based chemicals. OPX Biotechnologies (OPXBIO) has developed a proprietary platform technology called Efficiency Directed Genome Engineering (EDGETM).

This technology allows OPXBIO to develop and engineer microorganisms and bioprocesses faster and less expensively than traditional methods. OPXBIO can now develop multiple chemicals cost-effectively from multiple renewable feedstocks. In , OPXBIO developed a bioprocess for biobased acrylic acid (bioacrylic acid). OPXBIO used its EDGETM process to engineer both a microorganism to produce 3-hydroxypropionic acid (3-HP) and a process to manufacture bioacrylic acid renewably.

A key focus was developing a microbial strain with increased cellular pools of malonyl-CoA, the first committed intermediate in the 3-HP production pathway.

Many commercial products may be derived from malonyl-CoA, including fatty acids (and hence long chain alkanes), polyketides, and 3-HP. An initial lifecycle analysis (LCA) indicates that OPXBIO&#;s process for bioacrylic acid would reduce greenhouse gas emissions by more than 77 percent and crude oil use by 82 percent compared to traditional acrylic acid synthesis from propylene.

If the entire global market for acrylic acid (4.5 million tons annually) were replaced with OPXBIO&#;s bioacrylic acid, greenhouse gas emissions would be reduced by more than 5 million tons annually, and industry&#;s use of crude oil would decrease by approximately 2.5 million tons.

In , OPXBIO scaled up its process and demonstrated the fermentation and primary purification of 3-HP at 3,000 liters. If dextrose feedstock costs $0.14 per pound, metrics predict a commercial cost of bioacrylic acid at approximately $0.75 per pound. This cost is competitive with the average cost of petroleum-based acrylic acid in , making the process both environmentally and economically sustainable.

Production of Cumene with Zeolite Catalyst--The Mobil/Badger Cumene Process: About 7 billion pounds of cumene are produced each year in the United States (15 billion pounds worldwide). Most of it is converted to acetone and phenol, an intermediate in the production of epoxy resins, nylon 6, and polycarbonate plastics. Conventional cumene processes, based on Friedel Crafts alkylation of benzene with propylene, use either solid phosphoric acid (SPA) or aluminum chloride (AICl3) catalysts. Both catalysts are corrosive, hazardous when spent, and difficult to dispose of safely. And SPA, the most widely used cumene catalyst, generates heavy aromatic byproducts, once used to enhance gasoline octane, but now increasingly restricted by the U.S. Clean Air Act.

A new environmentally friendly catalytic process for producing cumene is rapidly sweeping the industry, due to its substantial environmental and economic performance advantages. In , about 70 percent of U.S. produced cumene will be made by this new technology, a Mobil/Badger joint development introduced in . The Mobil/Badger technology employs a new zeolite catalyst that is environmentally benign and significantly more stable, more active, and more selective to cumene.

Manufactured by Mobil, this zeolite requires no special handling and is returned environmentally inert to Mobil after use. The Mobil/Badger technology, proven in Badger pilot units, will remove 4.4 million pounds of SPA from use, while reducing heavy aromatic byproducts by 250 million pounds/year. Its use will boost cumene yield by 5 percent and energy efficiency by more than 15 percent, enabling U.S. industry to meet growing cumene demand with substantially reduced costs.

Production of Diverse Industrial Glycols from Renewable Six and Five-Carbon Sugars and Glycerin, the Byproduct of Biodiesel Manufacture: The world market for glycols is approximately 20 million metric tons per year. The world&#;s glycols are derived from natural gas or naphtha, except for those glycols derived from renewable feedstocks using a process developed by IPCI and its partners. The IPCI process converts C5&#;C6 monomer sugars continuously to alditols (e.g., glucose to sorbitol; fructose to mannitol) using a proprietary nickel-based catalyst in aqueous solution at pH above 10, pressure in the range of 2,000 psi, and 200 °C.

A second hydrogenolysis step converts alditols continuously to glycols in excess hydrogen using a proprietary catalyst developed by Süd-Chemie Inc. The products include propylene glycol, ethylene glycol, and butanediol isomers. IPCI can shift its process to vary the products and allow market flexibility. Glycerin (C3; a lower-valued byproduct of biodiesel production) can be directly subjected to hydrogenolysis, producing predominantly propylene glycol and ethylene glycol. Similarly, xylose and arabinose (C5-sugars) can be hydrogenated to xylitol or arabinitol, respectively, and then converted to glycols. IPCI has also developed technology to separate close-boiling glycols using extractive and azeotropic distillation.

Overall conversions of sugars to glycols exceed 85 percent, which is about twice the yield of bioethanol from fermentation. Also, glycols are over twice as valuable as ethanol. One key product is 1,4-butanediol, the acetylene-based glycol used in engineering plastics and as an important precursor. Byproducts other than glycols are low-molecular-weight alcohols (ethanol, methanol, and propanol).

The IPCI process is inherently safer than other glycol manufacturing processes. Edible sugars are safe for the environment and humans. Water is the only solvent and both process catalysts and byproduct hydrogen are recyclable.

IPCI holds five sugar-to-glycol process patents and six glycol separation patents. Süd-Chemie holds two patents for the catalysts used in this process. Following completion of two smaller plants in the United States, a 200,000-metric-ton-per-year plant was completed in China in .

Production of Isobutanol from the Synergy between Metabolic and Process Engineering: Isobutanol, an advanced biofuel, offers significant technical and commercial advantages over fossil fuels and ethanol. Isobutanol has a high octane number, good distillation qualities, low vapor pressure, high compliance value in fuels, materials compatibility, low toxicity, and the ability to reach targeted production economics. DuPont was the first to create and develop integrated biological and process technologies that use microbes to produce isobutanol from renewable resources. DuPont&#;s strategy for low-cost commercialization includes retrofitting existing ethanol plants to produce isobutanol from current ethanol-industry feedstocks (i.e., corn grain and sugarcane), lignocellulosic biomass, and macroalgae (seaweed).

A proprietary yeast strain engineered with a novel biosynthetic pathway ferments sugars from these feedstocks to isobutanol. DuPont selected key enzymes based on their isobutanol specificity and cofactor requirements, then maintained flux through to isobutanol by eliminating byproduct reactions that could compete with the chosen pathway. This yeast-based isobutanologen is a drop-in biocatalyst suitable for retrofitted ethanol plants. A major challenge in commercial isobutanol production by microbes is the intolerance of the microbes to commercially relevant aqueous titers of isobutanol. DuPont met this challenge by reducing the aqueous concentration of isobutanol in fermentations, thereby avoiding enzyme inhibition by its product while minimizing production cost and environmental footprint.

The fermentation rate, titer, and yield are significantly superior to those of traditional acetone&#;butanol&#;ethanol (ABE) fermentations. This performance demonstrates cost-effective biological production of isobutanol for chemicals and fuels. DuPont&#;s technology can displace petroleum-based syntheses for isobutanol and directly replace refined gasoline from crude oil with a greener, biobased product. Further, its advantages over incumbent technologies include reducing greenhouse gas (GHG) emissions by 40&#;70 percent, local and national economic benefits, and increased national security through domestic fuel supplies. During , DuPont began operating a large-scale demonstration plant for isobutanol in the United Kingdom in a joint venture with Butamax(TM) Advanced BioFuels.

Propylene Glycol from Renewable Resources: Propylene glycol (PG) is a commodity chemical used in everyday consumer products such as liquid detergents, hand sanitizers, pharmaceuticals, and cosmetics, as well as in industrial products such as plastics, paint, antifreeze, and aircraft deicer. The largest use of PG is as a monomer in plastics, especially fiberglass resins. Until recently, PG has been produced almost entirely from petroleum resources. Each year, worldwide PG production consumes more than two billion pounds of petroleum. To eliminate this use of petroleum and to replace the toxic feedstocks involved, Battelle scientists at Pacific Northwest National Laboratory (PNNL) developed a catalytic process for producing PG from renewable sources.

The propylene glycol from renewable sources (PGRS) process relies on a carbon-supported bifunctional metal catalyst in combination with a soluble base co-catalyst. The multistep process proceeds in a single reactor to produce PG in high selectivity and at high conversion. This safe, sustainable, cost-competitive, and commercially viable alternative converts plant-based, seed-oil-derived glycerol or plant sugar alcohols into PG, which can then be purified to meet a variety of market specifications.

The glycerol can come from a variety of sources, including the crude glycerol byproduct of biodiesel production. The PGRS process currently produces propylene glycol for the first time on a commercial scale entirely from renewable resources. A lifecycle analysis shows that the PGRS process eliminates up to 61 percent of the greenhouse gas (GHG) produced by the traditional propylene oxide route to PG. Archer Daniels Midland (ADM) commissioned and is now operating a new 100,000 metric ton per year PG facility using Battelle&#;s technology. This represents the first of its kind in the world: an operational, commercial-scale facility producing PG that meets U.S. Pharmacopeia (USP) specifications entirely from renewable resources. Other competing technologies have been unable to produce PG from renewable materials of this high-quality material at full scale.

PRS Water Damage PreClean: Biological Cleaning for Restoration and Remediation: When common structural members such as wood and concrete become contaminated by gray or black water, they typically harbor residues that produce undesirable malodors and are a potential food source for bacteria, mold, and mildew. Current technology uses petroleum-derived detergents and harsh chemicals to penetrate interstitial structural pores, break down odoriferous residues chemically, and abate the proliferation of mold and mildew. After use, current technology may leave undesirable odors, residual harsh chemicals, and even residues of the original contaminants that may continue to grow bacteria and mold.

Rochester Midland Corporation (RMC) has developed PRS Water Damage PreClean (PRS PreClean) to remediate contaminated, waterlogged structures. PRS PreClean uses an environmentally friendly, renewable detergent and special nonpathogenic bacteria in a pH-neutral aqueous solution to access and digest malodor-causing residues. Unlike traditional cleaners, PRS PreClean penetrates porous structures easily, allowing its bacteria access to the residues. The bacteria germinate and metabolize the residues in situ.

PRS PreClean is a natural, green product: its active component is living, naturally occurring, noninfectious bacteria, and its principal surfactant is naturally derived. Because bacteria carry out the necessary chemical reactions, there is no need to introduce harsh acids or bases into the environment. As a result, PRS PreClean eliminates significant amounts of hazardous materials. In one case study, PRS PreClean reduced both surface solids and bottom solids in septic tanks. In a second case study, Enviro Care Liqui Bac (a one-half concentrate of PRS PreClean) remediated damage to concrete floors, carpet, and wall cavities caused by a sewage leak in a house. After treatment, workers removed all porous building materials and cleaned nonporous materials thoroughly with disinfectant and vacuums. Subsequent testing showed no sewage bacteria.

In , this technology received EcoLogo CCD-112 certification for Biological Digestion Additives for Cleaning and Odour Control.

Pulp Mill Defoamers Based on Vegetable Oil: Defoamers are widely used in the pulp and paper industry, particularly in pulp washing. The best defoamers for brown stock washing are based on silicone oils, although some defoamers are based on paraffin oils. These defoamers have serious disadvantages, however. Silicone oils are not biodegradable and can carry over onto the paper sheets, giving them undesirable surface properties. Paraffin oil can cause dioxin formation during the pulping process.

Ashland Hercules Water Technologies has developed a new family of defoamers based on vegetable oils. These biodefoamers eliminate paraffin oil, minimize the use of silicone oil, and increase the use of natural, renewable ingredients. The technology is based on (1) a specific blend of soybean oil and castor oil that has an optimal, low surface tension; (2) lecithin, a natural product that stabilizes the system; and (3) modified silicone products that optimize the defoaming characteristics, enhance the surface properties, and promote compatibility between phases. The formulations contain vegetable oil, appropriate silicone product(s) such as modified silicone polymers, a stabilizing agent, hydrophobic silica particles, two or more surfactants and dispersants, biocides, and thickeners (natural gums and biodegradable polymers). The formulation is an effective defoamer and produces a stable emulsion. The new defoamers can be used as a concentrate without dilution or as an emulsion.

The new defoamers have been shown to be as effective as the pure silicone defoamers and analogous petroleum-based defoamers, but are more cost-effective. Ashland Hercules launched its first Advantage® biodefoamer in and its second-generation product in . These biodefoamers are being used on pulp mill washers and also on mill effluents. Although these defoamers are designed for pulp and paper applications, they also are appropriate for other non-food industrial uses. The products satisfy FDA requirements for food contact (21 CFR 176.210).

Pure Performance "Zero" VOC Latex Coating: Pure PerformanceTM was developed to address the growing need for premium paint with environmentally preferred characteristics. Pure PerformanceTM is unique because it offers the traditional features of premium paints such as durability, hiding and touch-up while also adding the additional benefits of zero VOC, minimal odor, and mildew resistance on the paint film. Pure PerformanceTM paint primarily utilizes vinyl acetate-ethylene (VAE) polymer emulsions. The VAE polymer emulsion improves water resistance and provides added durability. In addition, the polymer "self-coalesces" or melts together when drying without the need for coalescing solvents. Because this product does not require solvents, VOC (volatile organic compound) emissions and the odors associated with the solvents are eliminated.

PVC Alternative Technology: CHEMECOL"s technology can promote and expand the elimination of chlorine and phthalates, two components of polyvinyl chloride (PVC) products, which are among the synthetic chemicals that environmental activists and medical researchers claim are health risks. Several organizations are seeking to phase out the use of PVC. The European Commission, citing health risks to small children, formally decided to ban phthalates from PVC toys, and concerns about the hazards of PVC are growing in the United States.

CHEMECOL"s patented technology allows the incorporation of a liquid monomer with a metallocene polymer to form an interpenetrating network polymer system offering processing similar to PVC with the unique property characteristics of a metallocene polyolefin. The technology can be processed on conventional PVC manufacturing equipment, which will save manufacturers added capital expenditure. In addition to improved quality, new product features, and ease of processing, there are also environmental improvements with the new technology. Specifically, the liquid monomer acts and behaves like a plasticizer without being a plasticizer, preventing migration of phthalates that may be unsafe for biological systems.

An additional benefit of the technology is that no dioxins are produced during incineration, which is a common problem associated with PVC and is a particular concern for the medical industry. Even more advantageous from an environmental and cost consideration aspect is the ability to recycle products made as a result of using the technology. These commodity products may also be customized to contain enhanced product features such as increased flame retardancy, an important factor in products used for construction. As such, CHEMECOL"s technology provides the capability for development of environmentally friendly products, with enhanced product features as compared to PVC, at a system cost that is competitive with PVC.

Pyrolase® Cellulase Enzyme Breaker as a Biodegradable Replacement for Corrosive Acids and Oxidizers in Hydraulic Fracturing Operations: Hydraulic fracturing (fracking) is an advanced drilling technique used to unlock vast stores of oil and shale gas across the country. It involves pumping pressurized water, sand, and chemicals underground to open fissures in oil- and gas-containing formations such as shale and improve the flow to the surface. Fracturing uses a host of corrosive acids and oxidizers to degrade and remove fracturing fluid residues from formation pores. The fracturing process has drawn harsh criticism from environmentalists claiming that potential contamination of underground water by fracturing poses a significant environmental risk. I

n December , EPA first stated publicly that fracturing might be to blame for groundwater pollution in Wyoming. Verenium has developed Pyrolase® cellulase to replace the corrosive acids and hazardous oxidizers used in fracturing. Verenium discovered and isolated the gene for Pyrolase® cellulase, a thermostable enzyme from the eubacterium Thermotoga maritime, found in geothermally heated sediment on the ocean floor.

Pyrolase® cellulase is a broad-spectrum ß-glycosidase with both endo- and exo-glucanase activities that provides a complete viscosity break on fracturing fluids across a broader range of temperatures, wider pH ranges, and higher salinity than other commercial enzymes. Pyrolase® cellulase is also useful in a wider variety of down-hole conditions. It excels in hydrolyzing linear and cross-linked fluids, such as guar gum, derivatized guar, and carboxymethyl cellulose, at speeds easily controlled by varying the enzyme loading.

It offers superior performance with zero environmental impact. Pyrolase® cellulase is an easy-to-use liquid. One pound of biodegradable Pyrolase® cellulase can replace more than 20 pounds of hazardous chemicals, some of which are implicated in soil and water contamination. Pyrolase® cellulase is a significant step toward addressing the environmental and health concerns over hydraulic fracturing both for workers and for those living near fracturing operations. Verenium launched a campaign in to commercialize Pyrolase® cellulase to the oil and gas services industry.

Rapid Enablement of Green Processes for Chiral Alcohols by the CodexTM Panel of Robust, Divergent Evolvants of One Ancestral Ketoreductase: Chiral secondary alcohols are intermediates in the syntheses of numerous chiral active pharmaceutical ingredients (APIs). They are commonly produced from the corresponding ketones using hazardous, boron-based reducing agents or, more recently, asymmetric catalytic reduction. Because these reduction methods typically produce inadequate stereoselectivity, additional processing is required to upgrade stereopurity, and product yields are low. Greener, more economical alternatives to such hazardous reagents and their energy-and mass-intensive processes are required to produce the increasing volumes of chiral alcohols needed for current and future drugs.

Biocatalytic reduction of ketones has long been recognized as an attractive, green alternative for making chiral alcohols. This promise went largely unfulfilled, however, because the available ketoreductase (KRED) biocatalysts were hampered by narrow substrate-specificity, low activity, poor in-process stability, inadequate stereoselectivity, and productivity-limiting product inhibition.

Codexis&#;s widely applicable platform of diverse KREDs pre-evolved from a common wild-type ancestor successfully addresses these long-unmet needs for practical, greener processes to manufacture chiral alcohols.The CodexTM KRED Panel comprises diverse variants of one KRED that are pre-evolved for in-process stability and efficient manufacture. The variants contain combinatorial mutations that, as a population, confer activity on a wide structural variety of ketones and selectivity to either alcohol stereoisomer. The variants are arrayed on microtiter plates for rapid screening to find the desired activity on any new ketone substrate and to obtain Protein Sequence Activity Relationship (ProSAR) data for rapid enzyme optimization if needed. Codexis developed processes for chiral alcohol intermediates of four generic APIs with variants identified from KRED panel screens and transferred them to contract manufacturers. Codexis has used panel variants to synthesize material for more than 15 drug candidates in development. Building on its success, Codexis has since developed CodexTM panels for other generally useful biocatalytic conversions including panels of transaminase, nitrilase, acylase, halohydrin dehalogenase, and ene reductase biocatalysts.

Rational Design of Catalytic Reactions for Pollution Prevention: Chemical products manufacturing is a major industrial source of toxic and hazardous chemicals. Catalytic technologies hold the key to the development of more environmentally benign chemical processes and for the continued improvement of existing processes. Historically, the design of chemical synthesis catalysts was extraordinarily empirical. Yields of desired products and operational characteristics were normally optimized based on suites of experiments run on catalysts made from various manufacturing conditions and blends. The ability to correlate catalyst behavior to catalyst surface features was extremely limited. Accordingly, predicting the desired catalyst features for a given application and, from that, formulating a catalyst manufacturing strategy, was essentially beyond reach.

Moreover, the concept of redesigning catalysts so as to inhibit the formation of undesired coproducts, toxic materials, and wasteful pollutants was fanciful. A methodology for Rational Catalyst Technologies was developed at the University of Wisconsin that makes it possible to design and optimize catalysts by first understanding the nature of the desired catalyst surface and, from that, formulating the catalyst. This strategy for the rational design of catalytic reactions has found acceptance worldwide and has been applied successfully to link surface science research to the development of industrially important catalytic chemical reactions. Industrial collaborations or applications include ammonia catalysis, the environmental de-Ox reaction, the water gas shift reaction on magnetite, titania surface species, molybdena and vanadia catalysts for clean partial oxidation of methane, and hydrocarbon cracking over acid Y-zeolite catalysts for the clean production of isobutylene.

Reactin SeriesTM AS Copolymers: Specialty Reactive Aspartic Acid Copolymers: Reactin SeriesTM AS Copolymers are synthesized by the polymerization of an intimate mixture of aspartic acid and monosodium aspartate. The intimate mixture is obtained by dissolving diammonium aspartate and monosodium aspartate in water at greater than 70% wt solids and removing the water and copolymerizing the monomers sequentially at > 200C in a continuous reactor designed for high viscosity handling and solid phase polymerization. The copolymers are designated and patented in the molar ratio range of A (for aspartate) and S (for succinimide) from 1:10 and 10:1. The copolymers presently available are in the molecular weight, Mn, range of to . They are derivatized to the extent desired by reacting the succinimide functionality with suitable nucleophiles such as amines and alkoxides under mild conditions in aqueous media or in neat reactions. Selection of the nucleophile structure and composition dictates copolymer properties that may be obtained and, hence, suitable applications.

Reactive Distillation Technology to Reduce Waste at the Source: Mixtures are azeotropic if they can be distilled (or condensed) without a change of compostition. The existence of azeotropes in multicomponent mixtures in the absence of chemical reactions is well understood phenomenologically and theoretically. Azeotropes place a fundamental limit on the compositions attainable in mixtures by fractional distillation, but they can in some cases be 'broken&#; by carrying out chemical reaction and separation simultaneously rather than sequentially. Here, the authors report the discovery of a boiling state of constant compostion and temperature in a mixture of acetic acid, isopropanol, isopropyl acetate, and water that is simultaneously in both reaction and phase equilibrium.

This project confirmed earlier theoretical predictions by the senior author and others of the existence of reactive azeotropes that would allow combined reaction and distillation without a change in composition. This hybrid combination is also known as "catalytic" or "reactive" distillation. The technology is broadly applicable as the basis for innovative process designs to improve yields and productivity and eliminate or reduce by-product formation. The researchers built a working apparatus to prove the value of reactive distillation at higher pressures and assessed the feasibility of making dimethyl ether by reactive distillation from methanol.

Recovering and Using a Formerly Incinerated Sodium Nitrite Waste Stream to Disinfect and Stabilize Municipal Biosolids: Municipal wastewater treatment plants use biological processes to break down human waste. Sewage sludge, the residue left after biological treatment, contains innumerable pathogens that can harm humans, animals, and the environment. The treatment and disposal of sewage sludge has become an increasing problem. Municipal landfill space is limited; alternatively, applying sludge to land may restrict the land use for years, depending on how the sludge was treated.

BCR Environmental developed its Neutralizer® process as an effective, safe, verifiable, and economical solution to disinfect and stabilize municipal sludge, making it safe for use as a fertilizer. The Neutralizer® process destroys the pathogens in sewage sludge and stabilizes the sludge so that it does not attract vectors. This process generates its two principal chemicals, chlorine dioxide and nitrous acid, onsite at the wastewater treatment plant. During the process, sludge at up to 4-percent solids is treated with chlorine dioxide. Next, sodium nitrite and an acid are added; at pH 2.3, the sodium nitrite is converted to nitrous acid, which destroys any remaining pathogens and their eggs. Finally, the pH is returned to near-neutral and the treated sludge is dewatered for use as a fertilizer.

BCR collaborated with SABIC Innovative Plastics to use a waste stream from SABIC&#;s production of thermoplastic resin as the source of sodium nitrite for the Neutralizer® process. The resulting commercially viable, biologically safe fertilizer frees up landfill space, offsets the production of commercial fertilizer, reduces the production of greenhouse gasses, and saves the energy required to incinerate millions of gallons of SABIC&#;s nitrite-bearing waste stream. In December , EPA notified BCR that it had successfully completed the process for approval of its Neutralizer® process, the first process to receive this approval in the last sixteen years.

Recovery and Beneficial Use of Sodium Nitrite from a Wastewater Stream: Currently, our operation burns ~13,100 tons of a waste stream, containing ~ tons of solids, annually. This project will recover the main constituent from that waste stream, namely sodium nitrite, purify it, and market it as a technical grade product. The amount of waste that will then be incinerated will fall to ~ tons/year (containing ~400 tons/year of solids). The process will also reduce secondary waste streams, such as Ox emissions and refractory slag generated by the incinerator, and waste generated by the commercial manufacturing of sodium nitrite, typically from absorption of nitrogen oxides into aqueous sodium carbonate or sodium hydroxide. Finally, the energy requirements to treat the waste will be reduced. The long-term objective of the project is to decommission our incinerator. The waste stream to be recovered represents 75% by weight of the material in the feed to this incinerator.

Recycling Carbon Dioxide into Carbon-Neutral Liquid Fuels: The planet urgently needs a transportation fuel that is much more carbon-neutral than the 5&#;25-percent carbon-neutrality of most biofuels. Doty Energy shows that off-peak, low-carbon grid energy (mostly wind energy) and waste carbon dioxide (CO2) can be converted into clean, stable, liquid fuels: their WindFuelsTM. They plan to use waste CO2 from coal-burning power plants.

Doty Energy&#;s detailed simulations predict that plant efficiency, from input electrical energy to chemical energy in the fuels, will approach 60 percent, which is about twice what was generally expected a few years ago. Moreover, the proposed process could respond in milli-seconds to major changes in grid supply and demand. Thus, it has the potential to stabilize the grid completely, even if over half of its energy comes from wind. Carbon-neutral products that can compete in the current global market are essential to prevent a climate disaster within decades.

In Doty Energy&#;s process, water and renewable electrical power are fed into an alkaline electrolyzer, which produces hydrogen (H2) when excess low-carbon energy is locally available. Then waste CO2 and the renewable hydrogen are piped into an improved Reverse Water Gas Shift (RWGS) process, which permits practical reduction of CO2 to carbon monoxide (CO) at efficiencies approaching theoretical limits (ultimately, over 94 percent). The renewable CO and H2 are then fed into a Fischer-Tropsch Synthesis (FTS) process. The FTS reactor converts some of the CO and H2 into liquid fuels containing light hydrocarbons and alcohols. The unreacted feedstocks and undesired products are recycled efficiently. The desired liquid fuels and chemicals may be stored and distributed by conventional means such as pipelines and tanker trucks. The International Patent Searching Authority issued a completely favorable written opinion under the Patent Cooperation Treaty (PCT) for this technology and the PCT was published in September .

Recycling of Cross-Linked Materials Via "High-Pressure High-Temperature Sintering": Redefining Thermosets: In , Charles Goodyear obtained his patent for the sulfur vulcanization of rubber. His invention created one of the most difficult materials to recycle, as it will not dissolve or melt. Today, studies estimate that there are roughly 2 billion scrap tires in U.S. landfills, with this number increasing at a rate of over 273 million per year. Recently, we discovered a technique for recycling vulcanized rubber. In short, commercially available rubber powder can be "sintered" together through the adhesion of rubber particles with only the application of temperature and pressure.

The method takes advantage of the sulfur exchange chemistry that occurs at high temperatures. Through this labile bond it is possible to re-link the particles into a new chemical cross-linked network. There are two important reactions that occur in the process: the breaking of bonds (continuous stress relaxation) and the remaking of the bonds (intermittent stress relaxation). High-pressure high-temperature sintering (HPHTS) works for all thermosets in which the intermittent stress relaxation is greater than the continuous. A model has been developed based on these two reactions and it predicts the mechanical properties very well.

Overall, HPHTS transforms a useless scrap material into a valuable feed stock for new rubber parts. We have also discovered additives that can improve the efficiency of this process by slowing down and accelerating certain reactions. Finally, we have proven the mechanism of rubber sintering and have shown how to control the reaction with additives and/or by modifying the chemical structure of rubber.

Recycling Propellants in Non-Polluting Supercritical Fluids: Novel Computational Chemistry Models for Predicting Effective Solvents: Waste solid explosives and gun propellants are destroyed primarily by open pit burning and detonation or incineration. However, extraction and recycling of such explosives and propellants using a non-polluting, inert supercritical fluid (SCF) solvent such as carbon dioxide (CO2) has economic and environmental advantages. Although the ingredients in composite propellants and explosives demonstrate varying solubility in CO2, solubility is enhanced when trace amounts of simple polar modifiers are added to the SCF solvent.

The objective of this project is to determine the optimal physical conditions and chemical makeup of an effective SCF CO2 solvent with added polar modifier using well-established computational chemistry techniques.

The investigation focused on determining modifier properties and physical conditions that enhance the solubility of energetic materials in the SCF solvent using classical molecular simulation. Two complementary theoretical investigations on the properties and effectiveness of polar modified CO2 SCF solvents were pursued in parallel. The first investigation focused on the actual dynamic event for dissolution of a hexahydro-trinitro-triazine (RDX) crystal in an SCF solvent. Solvation dependence on the physical conditions of the system (far from or close to the critical point of the SCF) were examined. The second investigation focused on determining modifier properties that enhance the solubility of RDX in the SCF solvent using rigorous quantum mechanical methods.

A written report detailing predicted optimal conditions for extraction of energetic components from propellants and explosives in SCF CO2 was developed. In addition to receiving data, the user was supplied with recommendations based on the data analysis from the development of the SCF CO2 extraction system. Additionally, a program package that allows for prediction of solubility of energetic materials in multi-component SCF CO2 was developed along with a users manual and a table of recommended parameters for use in applying the model to various types of modifiers and solutes.

The principle benefits resulting from this research include the prevention of pollution associated with disposal of Army and Navy explosives and gun propellants and an associated reduction of life-cycle cost of munitions. Recycling is an alternative to open burning/incineration of gun propellants, which increasingly is restricted, and to incineration, which is not widely available and requires size reduction preprocessing.

Reduced Volatility Alkylation Process: Alkylate is considered to be a critical component of reformulated gasoline. It is a clean burning, high octane mixture of paraffins and isoparaffins and contains no sulfur, olefins, or benzene. Reduced volatility Alkylation Process (ReVAP) provides refiners with a low-cost option for risk management and olefin conversion to such a high octane, clean-burning gasoline component. The process employs an additive in the acid phase of a hydrogen fluoride (HF) alkylation which suppresses the vapor pressure of HF and reduces its tendency to form aerosols when released to the atmosphere. It is a drop-in replacement acid system for existing HF alkylation units, which minimizes capital investments.

The technology differs from existing sulfuric acid processes in that recovery and re-use of the additive is required. Separation from byproducts and recovery of the additive was deceptively complex initially. To remove all traces of acid required large capital investments and would lead to more waste generation.

With ReVAP, a simple but elegant separation vessel was designed, allowing the recovery and reuse of the additive with minimal capital costs. The additive is a commercially available product, with extremely low toxicity, high chemical and thermal stability, and is soluble with HF in all proportions. HF aerosol reductions of 60-90 percent can be achieved. These results have been combined with extensive process development chemistry and engineering to design a commercial process which is as safe as, if not safer than, existing sulfuric acid processes.

Reducing Domestic Petroleum Consumption by Twenty-five Percent: PanTerra Technologies has developed and introduced to various markets a new nano technology over the last thirty-nine months. This new technology applies to lubricants used in automobiles, transportation, industry, construction, farming, and aerospace. Initial commercialization in the metal working industry has shown actual productivity gains of over 20%, achieved in metal working applications including CNC machining and stamping. Automotive testing has shown decreases in emissions of 28%, improvements in gas mileage of 15%, and increases in motor power by 7.5%.

All improvements are accomplished simply by changing the oil lubricant used; therefore, there are no retrofit issues. The implementation of this new technology is based on the use of seed oils with a suspension of Molybdenum Disulfide (Moly) nano materials, which qualifies as a renewable resource under the Farm Security and Rural Investment Act of , House Rule . Founded in August , PanTerra&#;s Research and Development began in October of with the specific mission of producing the highest-performing renewable resource lubricants available worldwide.

Development of the initial products used in the metalworking industry was completed in April . This new lubricant technology substitutes seed esters with a moly nano particle suspension for the replacement of petroleum and chemical performance additives in the metal working industry, where the environmental and health and human safety impacts are well documented. A Fortune Specialty Chemical Company purchased a non-exclusive manufacturing license agreement in January of (MacDermid Chemical, NYSE: MRD). PanTerra opened a full-scale production facility in January , capable of producing one million gallons of finished product annually.

PanTerra registered as a small business, Veteran-owned and operated by Vietnam Veterans with Disabilities in . PanTerra&#;s Cage code is 3FXW5, Duns number . PanTerra initiated commercialization with various Federal Agencies including Army, Navy, Marine, and Air Force bases in July of , and has just started shipping product for evaluation to NASA. PanTerra has two dozen commercial clients in metalworking, and one in construction.

Patent applications include "Environmentally Safe Lubricating Composition" Number 10/176,227, International Patent Application Number PCT/US03/, and "Nano Particulate Matter and Methods of Manufacturing Same", filed September 12, [Docket number /, Registration number 41,222]. These patents protect the remarkable discovery made regarding the use of magnetic fields during the construction of nano particulate matter, and protect the suspension process that enhances the Brownian distribution of particles in fluids by using magnetic fields. The net effect of these patents provides evenly distributed particulate matter in fluids, and creates nano particles with uniform size distribution from commercially available materials. This new technology is the "secret sauce" that enables such a high degree of performance at reasonable, commercially viable costs.

This technology best fits under Use of Safer Chemicals as a primary focus area. The documented results show a significant contribution to the environment, and toward reducing the reliance on petroleum products, all while contributing toward better human health and safety. The technical summary of this technology is simple and powerful. By lowering the friction between moving surfaces in any energy-consuming device, the amount of energy required is significantly lowered. By providing a very low coefficient of friction, the amount of wear on moving parts is also lowered; therefore, any motor, tool, or surface can be operated faster, with less energy or wear than at any other time known to mankind. This is accomplished using physical properties rather than chemical interactions, thereby reducing emissions.

Reducing Nitrates in Buzzards Bay with the Production of Organic Gem® Fertilizer from New Bedford&#;s Fish Processing Wastes (An SGNB Project): AMT&#;s Organic Gem® fertilizer is manufactured in New Bedford, Massachusetts using approximately 7% of the typically 50 million annual pounds of fresh fish scraps. Organic Gem® (OG), certified by OMRI, was first made from the byproduct of their nutraceutical extraction of marine cartilage. They have developed a unique Enzymatic Digestion Engine (EDE) using proprietary enzymes that accelerate optimal digestive conditions.

The EDE strictly controls factors that could potentially denature enzymes and proteins. It is a fast, "cold" process that delivers a low-odor, efficiently absorbed fertilizer to increase plant yield and pest resistance. Presently, its markets include golf courses, turf farms, vineyards, hops, fruit trees, potatoes, cranberries, home gardens and other crops.

In New Bedford, the increased manufacture and use of OG delivers a triple economic/environmental impact by decreasing quantities and costs of illegal fish wastes going to landfill; reducing nitrate discharges from the wastewater treatment plant into Buzzards Bay, a prime recreation area; and minimizing agricultural runoff of nitrates from petrochemical-based fertilizers. With its use of an innovative processor supply chain approach, AMT anticipates servicing 100% of the local wastes within the decade. Its plans call for new EDE installations to bring cost savings to other processors and environmental benefits to other ports.

Reducing the Environmental, Health and Safety Impact of Cooling Water Treatment Programs: Typical conventional cooling water treatment programs require corrosion control, scale inhibition, and microbiological control. Common water-treatment chemicals include potentially hazardous and toxic materials. Ashland developed a turnkey application that significantly reduces the negative environmental, health, and safety impacts of cooling water treatment programs without sacrificing performance. The unique combination of SONOXIDE® ultrasonic treatment for microbiological control, ENVIROPLUS® cooling water treatment products for corrosion and scale control, and the Ultra-Serv® solid chemical inventory management program delivers a high-performance, environmentally responsible program and enhances safety by eliminating the need for liquid chemicals.

Ultra-Serv® is a solid chemical feed system that reliably dissolves and delivers a solid, concentrated form of ENVIROPLUS® corrosion and scale control product to recirculating cooling systems. The ENVIROPLUS® series of cooling water treatment products includes a patented, complex, synergistic blend of multifunctional components that provide exceptional multimetal corrosion inhibition and scale control in alkaline cooling water systems. The blend includes polymeric antiscalants (biodegradable carboxylic antiscalants), phosphonocarboxylates (including PSA, a low-P phosphonate), and other organic and inorganic components. ENVIROPLUS® products reduce the environmental impact of treated water discharge because they are inherently biodegradable and contain very low phosphorus, but no heavy metals. This profile enables plants to comply with increasingly stringent discharge limitations and allows cooling towers to operate at higher cycles of concentration, thereby reducing water consumption.

SONOXIDE® ultrasonic water treatment for microbiological control enhances health, safety, and environmental benefits even further. SONOXIDE® ultrasonic treatment provides total-system microbiological control by applying low-power, high-frequency ultrasound plus micro-bubble aeration. SONOXIDE® treatment controls total bacteria and biofilm in recirculating cooling systems, virtually eliminating the need for chemical microbicides. SONOXIDE® is currently in use in over 500 cooling systems worldwide. Ashland introduced its newest component, Ultra-Serv® in . Ashland holds a number of recent patents for this technology.

Reducing VOC Emissions by Eliminating Painting and Labeling Operations with a New Color Laser Marking System for Plastic Parts: Decorating, marking, or coding plastic parts can be a challenge. Many plastics require surface treatments before paint will adhere. In certain environments, printed marks lack durability and may require a protective topcoat. Self-adhesive labels, another option, pose similar durability problems coupled with high scrap rates. A new technology to mark plastic parts in color with a laser has been developed by M.A. Hanna Color. This technology offers dramatic improvements in the ability of processors and end users to permanently mark a wide range of plastic parts using a broad color palette. The technology is expected to replace a significant portion of plastic printing and adhesive label decorating/coding operations in most major market segments.

The results will be significant reduction in VOC emissions (via elimination of solvents in ink production, usage, and cleanup), enhanced recyclability of scrap plastic parts (unlike labels, there is no effect on melt reprocessability), and reduced liability on critical components, where safety warning labels often scrape or fall off the part. Compared to earlier first-generation laser marking of plastics, the new technology offers greater contrast between mark and background, applicability to most major classes of thermoplastics and some thermosets (since custom-additive packages and manipulation of laser energy rather than base resin reformulation is used), the ability to move beyond what was essentially a monochrome palette, and reduction in potential thermal damage to the wallstock of the part, since the new technology does not work by pyrolization. Speed, flexibility, and economics are further benefits.

Based on figures supplied by the Commerce Department and Rauche Guide to the U.S. Ink Industry, total solvent usage associated with inks for the plastics industry amounts to 22.4 million pounds (11,200 tons) annually, conservatively assuming an average solvent content of 30%. M.A. Hanna Color estimates that within the first two years of use, the new color laser marking technology could effectively replace approximately 10% of the plastics decorating processes that involve inks. Within ten years, this figure could rise to 50%. Meeting the 10% projection would eliminate approximately 1,120 tons (2.24 million pounds) of VOC emissions from the production of plastic parts in the U.S. annually.

Reduction of Carbon Tetrachloride Emissions at the Source by the Development of a New Catalyst: Phosgene is an important intermediate in the synthesis of polycarbonate plastics, highperformance polymers, agrichemical intermediates, and urethane foams. Current global production is about 10 billion pounds per year. Although the process chemistry is selective, the byproduct carbon tetrachloride, CCl4, is generated at a rate of 300 to 500 parts per million, amounting to 5 million pounds per year globally. Since carbon tetrachloride is a carcinogen, an ozone depleting chemical, and a greenhouse gas, it was necessary to reduce or eliminate this undesirable byproduct.

A DuPont team discovered a new catalyst that was produced in Siberia, Russia. After much laboratory work, it was decided to try a plant test, a scale-up of greater than 250,000 times. The catalyst was purchased, shipped from Siberia, and implemented in less than one year after the start of the program. After one and a half years of commercial production, the new catalyst has consistently demonstrated high phosgene production rates and achieved a 90% reduction in the level of carbon tetrachloride generation (to less than 50 ppm, apparently a new global record). By conceptualizing, identifying, testing, securing from Russia, and implementing a novel phosgene production catalyst (well within the proposed 18 month deadline), the team saved the business a cost of $2 million associated with the installation of a new abatement furnace, which would have been the only other alternative. Furthermore, the resulting need for fewer catalyst changes in the reactor, as well as the prevention of maintenance costs that would have been associated with the abatement furnace, will save approximately an additional $400,000 per year. The catalyst technology is being offered for license globally, which could reduce emissions of CCl4 by up to 5 million pounds per year.

Reformulation of 3MTM Neutral Cleaner and 3MTM General Purpose Cleaner for the 3MTM Twist 'n FillTM Chemical Management System Reduces Air Pollution and Employee Health Hazards: 3MTM has a long-standing commitment to product lifecycle management and pollution prevention. In , as part of that commitment, the company reformulated its 3MTM Neutral Cleaner and 3MTM General Purpose Cleaner for the 3MTM Twist 'n FillTM Chemical Management System. The reformulated cleaners significantly reduce volatile organic compounds (VOCs) in the product and maintain high-quality product performance. These new formulations are certified by Green Seal® as were the previous formulations; they are part of a portfolio of 3MTM products that can help its customers reduce their environmental footprint and provide social and economic benefits.

The previous concentrated formulations for these hard-surface cleaners included 5-10-percent solvents to provide effective cleaning. These solvents were generally low-molecular-weight alcohols or alkyl glycol ethers. They had the potential for higher skin irritation and health hazards; due to their lower flashpoints of about 100 °F, they had transportation, storage, and other regulatory issues when shipped in the concentrated formulations.

The new formulations result from a unique combination of several active ingredients including an alkyl pyrrolidone and an alkyl glucoside that provide superior cleaning and nonstreaking properties. All of the organic ingredients in the new formulations are readily biodegradable, and the primary surfactant in the formulation is made from renewable resources. Compared with previous formulations and with traditional chemical management systems, the new formulations offer several environmental and health advantages including (1) a higher flashpoint of over 175 °F, which lessens dermal irritation without using a solvent mixture; (2) an estimated reduction of 600,000 pounds in VOC emissions from product use in ; and (3) a reduction in waste from the Twist 'n FillTM system packaging. Based on its sales and production data, 3MTM estimates that these reformulations will save the company nearly $600,000 per year. The savings come from raw material costs and manufacturing process improvements.

RegenSiTM: A Wafer Reclaim Solution with a Low Carbon Footprint that Extends the Life Cycle of Silicon Test Wafers: Because a prime silicon wafer costs approximately $300, semiconductor manufacturers use test wafers, at over $100 apiece, to optimize their manufacturing processes. One large fabricator might spend $2 million monthly on test wafers. The industry uses more than 27 million prime and test wafers annually. Because silicon is the greatest material expense for fabricators, they are eager to improve their reclamation and reuse of test wafers.

Traditional wafer reclamation processes involve chemically stripping unwanted films from the wafer surface, surface planarization (i.e., mechanical polishing to remove damage or impurities), and cleaning. Wafer reclamation has been limited because each cycle of stripping and polishing reduces the thickness of the wafers; eventually, they become too thin and are discarded. Traditional processes have very low reclaim yields because they cannot remove unwanted films completely.

RegenSiTM is a novel, all-wet, single-step process that strips away most films from test wafers and limits damage to the underlying silicon. This eliminates or reduces the need for wafer surface planarization, which is energy-intensive, requires a large volume of consumables, and is expensive. RegenSiTM chemicals also have a much longer bath life, which reduces both chemical waste and worker exposure. The RegenSiTM process eliminates sulfuric, nitric, and hydrochloric acids. It reduces hydrofluoric acid 24-fold. The process has a carbon footprint 28-fold lower than the traditional three-step process and consumes 85-percent less energy. One Taiwanese manufacturer using RegenSiTM increased reclaim yields to 85 percent and reduced silicon loss by 75 percent, increasing the life of each test wafer fourfold. Another RegenSiTM customer saved 20 tons of deionized rinse water per day in each facility.

This combination of higher yields, fewer resources, greater productivity, and increased reuse leads to significant overall cost savings, energy savings, and waste reduction. Both IBM and Texas Instruments are using RegenSiTM; many others are using or testing it.

Regioregular Polythiophenes as a Platform for Organic Photovoltaic Technology: Global sustainability relies on renewable energy; solar energy promises the greatest long-term solution. At $5 per watt, however, traditional silicon-based solar cells (photovoltaics) are too expensive to have serious impact. Further, the production of silicon solar cells requires toxic and explosive gases, corrosive liquids, and suspected carcinogens.

Professor Richard D. McCullough&#;s fundamental discoveries have substantially enhanced the potential of plastic solar cells to mitigate global warming. Earlier, Professor McCullough synthesized nearly 100 percent regioregular polythiophenes (rr-PTs) with unprecedented conductivities and created an energy-efficient, comparatively inexpensive synthesis of pure rr-PTs. He can now synthesize rr-PTs in a process that dramatically reduces hazardous chemicals, consumes significantly less energy, is cheaper, and is scalable to industrially relevant levels (e.g., 100-kilogram batches).

The solubility of poly(3-hexylthiophene) enhanced by side-chain modifications enables it to be solution-processed and inkjet-printed onto various substrates, thus lowering production costs for organic solar cells. Professor McCullough&#;s synthesis of poly(3-hexylthiophene) is now the dominant technology for producing the most efficient polymer photovoltaics to date, with power conversion efficiencies of up to 5 percent.

In , Professor McCullough cofounded Plextronics, a company committed to delivering revolutionary renewable energy products. These products include organic photovoltaics and organic light-emitting diode (OLED) displays based on PlexcoreTM, Professor McCullough&#;s polythiophene technology. One of the products, Plexcore PV, is a p-type semiconductor with tunable energy and bandgap that will improve the efficiency of organic (or polymer) solar cells. It can be printed onto substrates, thus enabling large area, low-cost solar cell production that will drive the cost toward the commercially viable $1 per watt. PlexcoreTM can be adapted to various applications, so Plextronics is well-positioned to develop markets such as OLEDs, displays, solid-state white lighting, and solar cells for integrated building photovoltaics. Plextronics began kilogram-scale, commercial production of poly(3-hexylthiophene) in and established a solar cell production facility in .

ReNew Air Scrubber Technology: Rendering facilities process the inedible parts of food stock into value-added materials such as tallow, high-protein components for animal feed, and materials for the cosmetics and pharmaceutical industries. The rendering process uses high-temperature cookers to convert livestock waste into these finished products, but it also generates significant levels of malodorous volatile organic compounds (VOCs). Rendering plants trap VOCs with several devices including air scrubbers. Conventional air scrubbers rely on oxidizers, such as sodium hypochlorite, chlorine dioxide, chlorine gas, and ozone, to convert insoluble VOCs in exhaust air into water-soluble organic salts. Sodium chlorite, sodium bromide, sodium hydroxide, and mineral acids are often used during scrubber operation or cleaning.

ReNew Air Scrubber technology is a pollution control program that reduces emissions of unwanted VOCs from rendering plants. The program includes novel chemistry, a dosing system indexed to the intensity of the incoming VOC-containing gases, several air-handling system modifications, and air scrubber performance monitoring. ReNew Air Scrubber technology uses enzymes, surfactants, and 50 percent citric acid (a relatively mild organic acid) to replace conventional harsh chemicals. This technology removes odorous VOCs with efficiency that is quantifiably equal to or better than the VOC-removal efficiency of conventional technology.

The ReNew Air Scrubber technology reduces total operating costs, uses chemicals that are safer for workers and the environment, requires less water and energy to operate, and delivers air quality results equal or superior to conventional systems. It does not produce any EPA-regulated pollutants in the effluent water.

Since , when Diversey started tests at customer sites, several dozen customer sites have fully installed the ReNew Air Scrubber technology. Since its initial commercialization, this technology has saved over 54.5 million gallons of water at U.S. rendering facilities and prevented the use of over 5 million pounds of oxidizers and mineral acids.

Renewable-Resource Industrial Products: Zep has developed and introduced into the marketplace two innovative, high-performance, industry-oriented, chemical-specialty products that are safer for users and have reduced environmental impact. These products are Zep Shell Shock heavy-duty hand cleaner and Zep 70 Liquid penetrating lubricant. Both products incorporate soy methyl ester solvent (methyl soyate) derived from soybean oil, a renewable resource. Methyl soyate is a 100-percent-biodegradable solvent that contains less than 50 grams per liter of volatile organic compounds (VOCs) and has a flash point above 300 °F. It can replace the nonrenewable, petroleum-derived solvents that are typically used in these types of products.

Shell Shock contains over 87 percent of renewable ingredients. In addition to methyl soyate, Shell Shock also contains sterilized walnut shell abrasive, which is a biodegradable, renewable-resource material that facilitates the removal of heavy soils from the hands. The walnut shell abrasive replaces nonrenewable pumice, which is typically used in heavy-duty industrial hand soaps. Zep&#;s Shell Shock is formulated as an oil-in-water microemulsion that leaves hands clean, soft, and moisturized. Traditional petroleum solvent-based industrial hand cleaners with pumice tend to leave hands dry and chapped, especially during the low-humidity, winter months. The cost of Shell Shock is similar to that of traditional pumice and petroleum-based products.

Zep 70 is a nontraditional, penetrating lubricant that is an excellent alternative to petroleum-based lubricants. It provides equal if not better penetration, corrosion inhibition, and lubrication. It is formulated with more than 80-percent renewable ingredients, including soy methyl esters.

Zep has marketed Shell Shock and Zep 70 for the last 3.5 years and has received commendable feedback from its customers on the performance of both products. Since , the Zep Shell Shock and Zep 70 formulations with soy methyl esters have displaced over 312,000 pounds of petroleum solvents.

Replacement for Solvent-Based, Chromate-Containing Primer: Corrosion of bonded metal parts is a major concern for the aerospace industry. Historically, aerospace manufacturers have used solvent-based primers containing hexavalent chromium (Cr(VI)) to protect metals from corrosion. Hexavalent chromium has, however, been classified as a known human carcinogen and is subject to increasing regulations globally. In addition, the solvents in these primers contain volatile organic compounds (VOCs) that are precursors to ozone formation.

To comply with new environmental and safety regulations, major aerospace manufacturers including Boeing and Airbus are looking to qualify water-based, chromium-free primers for structural bonding applications. Aerospace manufacturers and primer suppliers have been evaluating several chromium-free corrosion inhibitors, but chromium-free primers with corrosion performance to match that of chromium-based primers are not commercially available.

TDA Research has developed a platform technology for releasable chromium-free inorganic&#;organic corrosion inhibitors. Cytec Engineered Materials, a subsidiary of Cytec Industries, is collaborating with TDA Research to develop a water-based, chromium-free, bonding primer to give corrosion performance comparable to that of chromium-based primers. The new water-based primer chemistry has synergistic effects with these chromium-free corrosion inhibitors to give excellent corrosion performance over extended periods of time. In addition to eliminating chromium, the technology also eliminates VOCs, reduces the need for refrigeration during storage, and reduces potential waste due to extended shelf life. Customers who substitute the new technology for existing solvent-based primers are expected to reduce their annual operating costs by 25 percent. A patent application was submitted in December .

Replacement Non-Toxic Sealants for Standard Chromated Sealants and Repair: The objective of this work is to formulate and test candidate non-chromated sealants that will provide equivalent or improved properties as compared to the existing chromated sealants while meeting the requirements of MIL-S-C. Additional goal is to reduce the volatile organic compound (VOC) content of the materials by 65 percent.

Sealants are required in aircraft systems and on weapons to provide protection against corrosion, prevent moisture entry, provide a fuel barrier, and provide electrical insulation. Traditionally, sealants use chromium as the primary corrosion inhibiting substance. Chromium has been designated as hazardous and is targeted for elimination in order to comply with either current or pending Occupational Safety and Health Administration (OSHA) requirements. Most sealants also contain VOCs such as methyl ethyl ketone (MEK) and toluene. Under this project team&#;s guidance, a chromate-free corrosion inhibiting sealant has been developed, tested and transitioned to the field. A new polymer has been developed that is characterized by properties beneficial to corrosion-inhibiting sealants: rapid cure times without a reduction in work life; a pleasant odor; excellent rheological properties; excellent cure at low temperatures; and high solvent resistance. The proposed work is directed towards use of this new polymer to formulate corrosion inhibiting sealants for all the types and classes of MIL-S-.

Replacement of Asbestos in the Diaphragm Cell Process for Manufacture of Chlorine and Caustic Soda: PPG has developed the Tephram® nonasbestos diaphragm for use in diaphragm electrolysis cells for the production of chlorine and caustic soda (NaOH). Approximately 75% of the chlorine and caustic soda produced in the United States is made by the electrolysis of salt brine in diaphragm electrolysis cells. In these cells, salt dissolved in water is supplied as analyte to an electrolysis cell consisting of an anode, cathode, and a diaphragm. The Tephram® diaphragm uses nonhazardous materials to replace asbestos, reducing complexity in the safe handling of raw materials and in the disposal of diaphragm materials at the end of their useful lives. The Tephram® diaphragm is not only easier to handle safely and is more environmentally friendly, it also lasts longer than does asbestos and operates with greater energy efficiency. These advantages of greater durability and efficiency combine to reduce expenditure of cell renewal labor and consumption of both materials and energy.

Replacement of Methanol Solutions with Aqueous Dispersions in Photographic Coatings: Photographic films and papers are based on coatings of small silver halide crystals. A few photons of light absorbed by a crystal are converted to a small cluster of silver atoms and this cluster serves as the catalyst for the reduction of the entire grain when the coating is immersed in a solution of a reducing agent. The contrast between exposed and subsequently reduced areas of the coating and the unexposed areas forms the basis of black and white photography. In color photography, reducing agent byproducts react with very small oil droplets of color-forming precursors in the same layer as the silver halide to produce a dye.

Differently sensitized silver halide crystals made sensitive to specific wavelengths of light are paired with oil droplets of appropriate color-forming precursors in a multiple layer sandwich to make photographic film and paper capable of giving full color images. Along with the silver halide crystals and color-forming precursors, small amounts of other organic chemicals are essential for photographic performance. Antifoggants are needed to control the stability and catalytic activity of the silver atom clusters generated by exposure. Sensitizing dyes are used to make the silver halide sensitive to different wavelengths of light. These chemicals are substantially water insoluble and their introduction into the aqueous coating melt can be accomplished by making methanol solutions of these chemicals. Mixed with the coating melt, these chemicals in these solutions rapidly adsorb onto the silver halide grains. In some cases, the low solubility of the chemical requires very dilute methanol solutions.

This, and the need to add several different dyes and antifoggants to a given photographic product results in coating melts with significant percentages of methanol. There are workplace concerns associated with such melts as well as the undesirable emission of methanol to the atmosphere during the coating and drying of the photographic product. To reduce or eliminate methanol use, Eastman Kodak Company has prepared aqueous dispersions of sensitizing dyes and antifoggants using milling techniques. Such dispersions consist of small particles (less than 1 micrometer in diameter) of the chemical of interest stabilized by surfactant and/or polymer.

Methods such as ball, sand, or media milling can be used with the processing details such as milling time and composition optimized for the chemical of interest. These dispersions are miscible with the aqueous coating melt and give chemical activity comparable, and in some cases superior, to that of methanol solutions. Using this technology, methanol emissions to the atmosphere during coating and drying has been greatly reduced even in times of increasing production. In addition, environmental concerns regarding the storage, and handling of methanol in manufacturing operations have been avoided.

Replacement of Perfluorinated Alkyl Surfactants with Nonfluorinated Surfactants in Polymer Manufacturing: All manufacturers, including Arkema, had always used perfluorinated alkyl surfactants (PFOA) and related chemicals for emulsion polymerizations of fluorinated monomers, such as vinylidene fluoride. The high reactivity of the fluorinated monomers had led to the widely accepted belief that only perfluorinated surfactants are inert and stable enough to function in these polymerizations. PFOA and related chemicals are both persistent and widely distributed at low concentrations throughout the environment. In , the EPA and major companies in the industry created the /15 PFOA Stewardship Program to reduce and eventually eliminate emissions and product content of PFOA and related chemicals. Although other participating companies pursued containment, recycling, or substitution of alternative perfluorinated surfactants, Arkema targeted the complete elimination of fluorinated surfactants from its products.

Since , Arkema has worked to eliminate perfluorinated alkyl surfactants from the manufacture of polyvinylidene fluoride (PVDF) resins. Arkema researchers first identified several hydrocarbon-based, nonfluorinated surfactants that worked well in the polymerization reaction. These surfactants have been used in consumer products such as shampoos and cleaning formulations; extensive data show that they are of low toxicity, do not bioaccumulate, and do not persist. Subsequently, an Arkema team identified fluorosurfactant-free polymerization conditions in the laboratory, optimized the reactions on a pilot scale, and successfully implemented the new processes at Arkema&#;s commercial manufacturing site. Under optimized process conditions, these new surfactants allow the production of PVDF products with properties virtually identical to those of existing products.

Arkema is currently replacing its traditional approach with these new manufacturing processes for all 40 grades of its PVDF resins. During , Arkema reduced its use of perfluorinated alkyl surfactants at its U.S. manufacturing site by roughly one-half. Its goals are 95 percent reduction by and complete elimination thereafter. This technology will reduce fluorinated surfactants in air emissions, wastewater discharges, and finished goods.

Replacing Organic Solvents and Homogeneous Catalysts with Water and Carbon Dioxide: Professor Tester and the Supercritical Fluids Research Group at MIT have advanced the use of near- and supercritical carbon dioxide and water as benign alternatives to toxic organic solvents. Their technologies limit the use of auxiliary chemicals to carbon dioxide and water, eliminating additional surfactants, catalysts, and co-solvents. Their goal is the improved understanding of chemical reactions under extreme conditions in an effort to identify industrially relevant processes that are both economically attractive and environmentally benign.

They have focused on two areas: (1) the clean and energy-efficient production of specialty chemicals in supercritical carbon dioxide; and (2) the use of water near its critical point to remediate chemical wastes and generate renewable energy. Their major contributions are novel experimental designs and protocols, precise and accurate measurements of phase behavior and reaction rate constants, and advanced theoretical models and engineering analysis of chemical kinetics.

Their recent successes include the use of carbon dioxide as both solvent and reactant for the formation of important, nitrogen-bearing, heterocyclic compounds and the adaptation of power ultrasound technology to improve the selectivity and yield of a model Diels-Alder reaction in emulsions of carbon dioxide and water. The group&#;s efforts have been documented in over 120 publications. Laboratories in the United States and in other countries now use many of the methods first introduced by the MIT Supercritical Fluids Research Group. Their detailed analyses enable generalization of their results from the laboratory bench to industrial processes.

Research, Development, and Commercialization of Environmentally Benign Thermoplastic Pressure-Sensitive Adhesive Label Products: Eliminating the problems created by pressure-sensitive adhesives (PSAs) in post-consumer waste is the most important technical barrier to expanding the use of recycled paper. Estimates are that replacement of current PSA technology with benign formulations can save tens of trillions of BTUs per year, increase the quantity of paper that can be recycled, and save the industry $650 million in non-energy-related expenses. A promising approach is the redesign of adhesive products to diminish their negative impact on paper recycling operations.

Dr. Severtson has designed thermoplastic PSA products for which fragmentation of PSA films are inhibited during repulping operations. The adhesive particles that form are easily removed by standard cleaning equipment early in the recycling process, eliminating the PSA contamination. This iterative research included the study of model PSA systems and eventually led to the development of commercial products. PSA properties have been thoroughly characterized and their screening removal efficiencies have been tested when attached to various facestocks. This research has identified the surface and bulk mechanical properties of label components and the interactions between them that govern film fragmentation.

Dr. Severtson&#;s research is allowing label manufacturers to produce commercially viable, environmentally benign thermoplastic PSA labels that meet any customer requirement. This project is an impressive demonstration of academic-industrial collaboration on green technology and its successful promotion from the laboratory to the marketplace.

Resin Wafer Technology: Resin wafer technology enables electrodeionization (EDI) to be extended well beyond its conventional applications in ultrapure water production to new processes in biobased chemical production, industrial water management, chemical production and purification, carbon dioxide (CO2) capture, and, potentially, hydrogen production. EDI is an electrically driven process that separates dilute, charged species from process streams at higher efficiency than electrodialysis, its lower-tech counterpart. Resin wafer technology replaces the loose ion exchange resins used for conventional EDI.

The performance advantages of resin wafers include (1) controlled porosity, which makes stream flow more efficient; (2) enhanced ion conductivity, which reduces power consumption; and (3) reduced leakage, which increases product recovery and cuts loss to waste streams. Resin wafer technology provides new functionalities not available with conventional EDI. These include direct immobilization of biocatalysts, which allows integrated bioconversion and separations; modification of wafer composition and format, which increases ion selectivity and direct pH control; and even in situ catalysis.

Resin wafer technology also offers the following significant green chemistry benefits: It reduces the cost of producing biobased chemicals, providing economic drivers for emerging biorefineries to displace petrorefineries. It decreases the use of fresh water and the release of wastewater in power plants. It reduces energy and chemical use during the production of organic acids, esters, and other chemicals. It enables CO2 capture from flue gases in coal power plants, and it potentially enables enhanced hydrogen production from water.

Argonne has received technical and financial support from Archer Daniels Midland Company for biobased products, Nalco Company for water management, Carbozyme Inc. for CO2 capture, and the Department of Energy for energy efficiency, renewable energy, and fossil energy. During , Argonne scaled up the technology and demonstrated it successfully on a pilot-plant scale. During the past 18 months, Argonne has been negotiating with commercial entities to commercialize the technology.

Revolutionizing Energy-Curing Resins for Food Packaging Applications: Solvent-free, energy-curing technologies have recently emerged as mainstream technologies in printing human food packages. These technologies are energy-efficient processes that use accelerated electrons or UV photons to polymerize acrylate resins into a branched network of large polymers. In contrast to solvent- or water-based technologies, these solvent-free technologies do not require prolonged energy-intensive heating and drying cycles or expensive solvent abatement systems. Overall, radiation-curing systems save an estimated 85 percent of the energy required for traditional systems. In addition, these technologies can also improve production speed and print quality.

Following the principles of green chemistry and sustainability, Cytec Industries Inc. has developed a new range of low-extractable, low-odor (LEO) acrylate resins for use in energy- curing packaging inks and overprint varnishes. Renewable resources such as tall oil derivatives and glycerol account for 15 percent of the starting materials in the LEO product line. The LEO resins are characterized by enhanced size and complexity, lower migration from the packaging matrix, and frugal synthetic processes using nontoxic and preapproved building blocks. When formulated in inks, varnishes, or adhesives, these new acrylate resins are able to meet the most stringent regulatory safety requirements. In addition, Cytec has also developed testing protocols streamlined for the study of migration of acrylates at the part-per-billion level to confirm minimal potential human exposure. Cytec launched the LEO project commercially in . During that year, LEO resins eliminated 20 tons of waste. Cytec anticipates even greater savings in the future.

ROACH TERMINALTM Insect Control: A Non-toxic Alternative that Prevents the Development of Pest Cockroach Populations: Cleary Chemical Company has developed and commercialized Roach TerminalTM, an insecticidal bait supplied as a gel or in a bait tray. In , the U.S. EPA registered Roach TerminalTM as a biopesticide. Roach TerminalTM has been tested successfully on the German cockroach, the most important household pest worldwide. This insect, like many others, stores uric acid as a source of nitrogen for retrieval during neogenesis of tissue and embryo development.

Roach TerminalTM has a novel mode of action. The active ingredient, termed a nutritional metabolism disrupter, is a composition of oxypurinol and xanthine, which act in concert to inhibit xanthine oxidase, a key enzyme in the metabolic pathway that produces uric acid. Oxypurinol is a metabolite of a human gout medication; xanthine is found naturally in foods. Cleary incorporates this active ingredient into an inert bait matrix designed to enhance the effects of the active ingredient and to attract the target pests. The insects founder when they deplete their reserves of uric acid precipitately during mating, molting, or embryo development and then cannot replenish their uric acid supply. Because they are not killed by direct toxic action, the dead insects do not contain any toxin that can move into the environment by secondary consumption. Roach TerminalTM affects insecticide-resistant and susceptible cockroach strains equally, indicating that there is no cross-resistance from other mechanisms.

Roundup ReadyTM Technology: Roundup ReadyTM technology is the mechanism by which crop selectivity to Roundup® herbicide has been introduced into crop plants. Roundup®, the world&#;s largest selling herbicide, controls almost all weeds but shows little selectivity in crops. Roundup® has excellent environmental characteristics and the active ingredient of glyphosphate has been given a category E status (evidence for not being a carcinogen) by EPA. The mode of action of the herbicide is also known precisely. A set of unique genes (Roundup ReadyTM) were discovered and introduced into crop plants to protect them from damage by the herbicide. Commercial launch began in with soybeans in the United States and will be followed by cotton and corn in to . Current research and development programs will soon thereafter lead to commercialization in other oilseed crops, such as rape seed, and in sugarbeet.

Additional potential applications include wheat, rice, forestry, and vegetable and salad crops. Roundup ReadyTM Technology has changed the spectrum of herbicides used. Farmers who planted Roundup ReadyTM soybeans in reduced herbicide use by 10 to 35 percent with better weed control and generally did not use a preemergent or residual, post-emergent herbicide. Roundup® herbicide has no 'carry-over&#; in the soil, does not limit crop rotations, and is compatible with no-till crop production (a practice that is expanding in the United States and elsewhere). This technology extends to a wider aspect of agriculture and food production the ability to use one of the most beneficial and environmentally benign farm chemicals ever discovered.

RPS Technology: Breakthrough Technology for Water-Based Paints, Coatings, Adhesives and Sealants: RPS Technology utilizes an innovative and very general approach for producing cured polymer films from polymer latex containing small amounts of metastable organosilicon compounds. These organosilicon compounds are incorporated into the polymer latex via conventional emulsion polymerization, which produces a water-based product suitable for use in a wide range of coatings and adhesives applications. After the latex is applied to a substrate, evaporation of its water triggers a chemical reaction that produces reactive silanol (i.e., Si-OH) groups. These groups react rapidly to produce cured films with excellent solvent resistance, good mechanical strength and superb adhesion to a wide variety of surfaces.

The human health and environmental benefits of RPS Technology are potentially enormous because the technology should be generally applicable for the production of water-based paints, coatings and adhesives. In addition to improving the performance of existing water-based products, RPS Technology provides excellent opportunities for creating water-based products that match or exceed the high performance of solvent-based products. Broad implementation of RPS Technology would: (1) represent a huge source reduction in VOCs; (2) improve the health of workers currently exposed to solvent-based paints, coatings and adhesives; and (3) reduce waste associated with the use of solvent-based products with limited pot-life.

RYNEX® Dry Cleaning Solution: Rynex Holdings, Ltd. has developed, demonstrated, and implemented an environmentally safe and effective dry cleaning solvent that is economical and recyclable. RYNEX® replaces traditional hazardous dry cleaning solvents including perchloroethylene and Stoddard solvent. It is composed of an oxygenated surfactant, specifically dipropylene glycol t-butyl ether (DPTB), and water.

This patented technology effectively removes water- and oil-soluble stains without the damage to delicate fibers that can occur with other dry cleaning and wet cleaning methods. RYNEX® is a complete solvent with no hazardous air or water pollutants. It has the advantage of attracting water molecules to form a water-solvent complex that exhibits extraordinary cleaning capabilities. The performance of RYNEX® is better than that of all other solvents available to the dry cleaning industry today.

RYNEX® has low volatility and is not flammable, carcinogenic, bioaccumulative, or persistent in the environment. It separates from water to allow the removal of dirt, grease, and soil without additional soaps. RYNEX® cleans water-soluble and oil-soluble stains, providing effective detergency and compatibility with existing machinery. It has superior cleaning abilities; it does not cause fabrics to shrink or cause any types of dyes to bleed. Its enhancements include greater optical brightness in garments that are also softer to the hand. Twelve major dry cleaning distributors are currently selling RYNEX®. It is being used in over 100 locations in the U.S., Europe, and Asia.

Safer, Sustainable, Biodegradable, Solid-State Chemistry for Treating Cooling Water Systems: Scale and corrosion inhibitors for liquid cooling water typically contain 10&#;15 percent active ingredients in an aqueous solution. Because many of the active ingredients are insoluble at neutral pH at these concentrations, sodium hydroxide (NaOH) is added to increase the pH and stabilize the solution. Typical formulations contain 10&#;30 percent NaOH.

APTech Group has developed chemistry so that only the active ingredients are mixed, heated, filled into recyclable containers, cooled, and allowed to cure, resulting in a unique, noncorrosive, solid-state concentrate. At the point of use, the solid-state product is reconstituted with system makeup water into a dilute solution (approximately 0.5 percent or less). NaOH is not needed because the low concentrations of the active ingredients in the dilute solution are below the solubility limits for these chemicals.

The solid-state product is not a compressed series of raw materials or physical mixtures, but a true homogenous solid state comprised of both liquids and powders blended in a proprietary process. When made into solution on demand, the product contains the same reproducible ratio of active ingredients needed to prevent scale and corrosion in water systems. This technology not only eliminates the discharge of NaOH into wastewater streams but also eliminates the potential for spills of this corrosive chemical. At present sales levels, this technology is eliminating the use of almost 280,000 pounds of NaOH each year. It is also saving 462,000 gallons of production water and 660,000 gallons of rinse water annually.

APTech Group has recently improved its technology so that its products consist of totally biodegradable materials. Potentially, this could eliminate the 106 million pounds per year of non-biodegradable materials. Finally, new energy-efficient eductor dosing systems can reduce energy consumption by 90 percent over conventional pumping systems. APTech Group has filed a patent for its eductor system.

Saf-T-Vanish®: A Zero-VOC, Green Replacement for Petroleum Solvent Vanish Oils: Tens of thousands of U.S. manufacturers who make metal parts by stamping or drawing use evaporative lubricants known as vanish oils. These oils typically contain over 90 percent highly evaporative, combustible, or flammable petroleum hydrocarbon solvents plus small amounts of lubricants. The human health and environmental impact of the solvents is of major significance. In the United States alone, vanish oils release over 120 million pounds of volatile organic compounds (VOCs) each year and expose tens of thousands of metalworking plant employees to noxious and potentially hazardous fumes.

On January 1, , South Coast Air Quality Management District (SCAQMD) Rule went into effect in Southern California, banning the use of high-VOC vanish oils from the local marketplace. Until recently, however, U.S. manufacturing had no proven, successful, environmentally friendly alternative to high-VOC vanish oils. In July , Tower Oil & Technology introduced Saf-T-Vanish®, the first truly green technology to prove itself as a successful replacement for high-VOC vanish oils. It is derived from renewable feedstock and is both fully recyclable and biodegradable. Saf-T-Vanish® is VOC-free and nonhazardous to manufacturing workers and the environment. Saf-T-Vanish® contains no mineral oils or hazardous air pollutant (HAP) ingredients; it is totally nonflammable and emits no noxious fumes.

To date, Saf-T-Vanish® has enabled the total elimination of vanish oil VOCs in hundreds of manufacturing applications throughout the United States. It has vastly improved plant and worker safety while making huge contributions to corporate environmental goals. In addition, Saf-T-Vanish® is the only commercially available, truly green technology that enables Southern California manufacturers to comply totally with SCAQMD Rule . As the manufacturing industry continues to replace conventional vanish oils, Saf-T-Vanish® could eliminate over 120 million pounds of VOCs per year from the environment.

Saturated Polyester&#;Phenolic Resin Systems Eliminate Bisphenol A and Epoxy from Interior Can Coatings for Food Packaging: Bisphenol A (BPA) is a key raw material for the binders in interior coatings of food cans, but recent animal studies have found that BPA exhibits potential endocrine-disrupting effects. Because these coatings are a significant source of consumer exposure to BPA, the food industry is demanding coatings without BPA.

Although U.S. regulatory agencies have not promulgated regulations, the elimination of BPA from interior can coating systems is a matter of public and scientific interest. Cytec has developed a new generation of BPA-free, saturated polyester resins for the main binder. These polyester resins, together with phenolic resins, can be used in interior can coatings. Coating systems based on these resins exhibit performance comparable to conventional, high-molecular-weight epoxy systems with the additional advantage of being completely free of residual epoxy resin monomers and their byproducts (e.g., BPA, bisphenol A diglycidyl ether, and its derivatives).

Cytec&#;s saturated polyester resin, DUROFTAL PE /60BGMP, has a predominantly linear structure and a molecular weight of approximately 10,000 daltons. All the monomers in its synthesis comply with food contact laws. It does not contain any significant levels of free solvent if properly cured, and it complies fully with the U.S. Food and Drug Administration&#;s (FDA&#;s) regulation 21 CFR §175.300 for polyesters.

Computer modeling indicates that DUROFTAL PE /60BGMP does not have the estrogenic properties of BPA. It is more flexible than conventional systems based on high-molecular-weight epoxy resins. Although DUROFTAL PE /60BGMP is compatible with most existing cross-linkers (predominantly phenolic resins and amino resins), Cytec designed a new, tailor-made phenolic resin for interior can coatings so the system can eliminate BPA completely and perform comparably to existing systems. Commercial sales began in . In , Cytec began its first full-scale production of the phenolic part of the system. In , Cytec&#;s first commercial sales of DUROFTAL PE /60BGMP eliminated about 10 tons of BPA.

Scalable Non-Aqueous Process to Prepare Water-Soluble Aminodiol: The p38(4) MAP (mitogen-activated protein) kinase inhibitor is a drug of the pyridinylimadazole class for the treatment of rheumatoid arthritis and, potentially, asthma and psoriasis. It blocks the destruction of joint tissue and the production of the tumor necrosis factor a (TNFa) and interleukin-1ß (IL-1ß) in monocytes and in animal models of arthritis.

Roche Carolina employs a convergent synthesis to produce this active pharmaceutical ingredient (API). One of the fragments involved in the synthetic route is 3-aminopentan-1,5-diol. Unfortunately this aminodiol intermediate is highly water-soluble, making it difficult to isolate from an aqueous reaction mixture. Extraction from the aqueous system requires a very large volume of the organic solvent, dichloromethane. Purification of the resulting viscous liquid is either by distillation or via crystalline salt, but requires multiple operational steps. This process was sufficient to produce the API for Phase I and Phase II clinical trials, but was not appropriate for manufacturing larger quantities for commercial use. A non-aqueous isolation and purification of the aminodiol fragment on a larger development scale, and subsequently, on a commercial scale, presented important technical challenges to be overcome to implement a more environmentally appropriate manufacturing process.

Roche Carolina has developed a process addressing these environmental concerns. In this new process, 3-aminopentan-1,5-diol is synthesized in two isolated steps and four chemical reactions starting from readily available and inexpensive dimethyl acetone-1,3-dicarboxylate. The company has optimized the process through significant streamlining, resulting in the use of a single solvent, which is easily recovered and recycled. The key operations involve: sodium borohydride reduction of dimethyl 3-N-tert-butoxycarbonyl-aminoglutarate, a one-pot deprotection, and purification of the 3-aminopentan-1,5-diol using an acidic resin under non-aqueous conditions. The overall yield of the new synthesis is 89 percent and the API purity is 99.5 percent. Raw material costs and operating costs are both greatly reduced.

Self-Assembled Monolayers on Mesoporous Silica Technology: A Green Alternative Synthesis of a Novel Adsorbent for Mercury Source Reduction: Mercury contamination has long been recognized as a serious threat to national and global environments. Development of innovative technologies to remove mercury without producing harmful byproducts or secondary waste is critically important to our constantly changing industries and environment. Thiol self-assembled monolayers on mesoporous silica (thiol-SAMMS) can absorb mercury and other heavy metals from low-volume waste streams, but the original synthesis of thiol-SAMMS created its own environmental problems.

SAMMS used to be functionalized in toluene. The resulting waste stream consisted of water, methanol, toluene, and traces of mercaptan. It was impractical to separate this mixture; therefore, the mixture was usually disposed of as hazardous waste. In response to this problem, scientists at U.S. Department of Energy&#;s Pacific Northwest National Laboratory (PNNL) have created and patented a green chemical process to synthesize SAMMS more efficiently. PNNL scientists use supercritical carbon dioxide (scCO2), a green solvent that allows complete silane deposition and yields a higher quality product.

With this new process, PNNL can conduct SAMMS deposition faster and more efficiently. A reaction that normally took several hours in refluxing toluene (110 °C) is complete in only a few minutes in scCO2; the reaction now produces a defect-free silane monolayer with no resid ual silane left in solution. The only byproduct is the alcohol from the hydrolysis of the alkoxysilane. The CO2 and the alcohol are readily separated; each is then captured and recycled. The SAMMS emerges from the reactor clean, dry, and ready to use. This new synthesis produces higher-quality SAMMS at one third of the original cost with virtually no waste. Steward Advanced Materials in Chattanooga, TN, has licensed the technology and will be manufacturing SAMMS using the PNNL synthesis. Other licenses are pending with an oil-and gas-filtration equipment company for offshore oil and drilling applications and a major oil company.

Separation of Racemic Tetralone: Sertraline is the active ingredient in Zoloft®, used to treat depression. Pfizer has emphasized green chemistry objectives in the separation of racemic tetralone, the starting material for the Sertraline process. Consequently, the Sertraline process is more environmentally friendly, solvent use is more efficient, process atom economy is better, waste streams are reduced, and worker safety is enhanced.

Pfizer uses a relatively new technology, multicolumn chromatography (MCC), to separate its current racemic raw material, 4(R,S)-tetralone. Pfizer has also demonstrated that the pharmaceutically undesired enantiomer, 4R-tetralone, which constitutes 50% of the process input, can be racemized, reprocessed, and separated as 4S-tetralone by MCC. Thus, the racemic starting material can be used in the downstream processing more efficiently, greatly reducing the 4R-tetralone waste stream, which is toxic to aquatic organisms. Other benefits of starting with 4S-tetralone include:

more than doubling the overall yield, reducing by one-half the volumes of ethanol (saving 800,000 gallons per year), monomethylamine (saving 65.2 metric tons per year), and catalyst (saving 4.1 metric tons per year),

eliminating a classical resolution step (saving 160 metric tons of D-(-)-mandelic acid per year),

eliminating the undesired Sertraline mandelate waste stream (nearly 500 metric tons per year),

eliminating 50% caustic (saving 150 metric tons per year) in the process and the subsequent waste steams associated with the mandelate salt break, and

eliminating a methanol recrystallization step (saving 600,000 gallons per year).

The new process could potentially reduce the raw material requirement of 4(R,S)-tetralone by 180 metric tons annually. In summary, Pfizer has dramatically improved its process by using raw materials and energy more efficiently and by reducing and eliminating waste streams. Pfizer is currently using MCC separation as part of its synthesis of Sertraline and plans to begin recycling 4R-tetralone as soon as it receives approval from the U.S. Food and Drug Administration (FDA).

Short Perfluoroalkyl Chain, Polymeric Fluorosurfactants as Wetting, Flow and Leveling Agents for Aqueous Coatings: OMNOVA has substantial business supplying latex resins to the floor care industry. These formulations require fluorosurfactants as wetting, flow and leveling agents for successful application. The fluorosurfactants currently used are typically long perfluoroalkyl chain materials supplied by 3M and others. The prevalent fluorosurfactant for floor polish is Fluorad FC-129 from 3M, which is being removed from the marketplace. Based on data contained in the 3M EPA public docket there are environmental concerns with these materials. The USEPA is now studying the general class of long perfluoroalkyl fluorinated materials for possible adverse environmental and health effects.

Through R&D, OMNOVA has discovered that fluorosurfactants based on short perfluoroalkyl oxetane polymers can replace the longer-chain fluorosurfactants in a number of applications. These Short Perfluoroalkyl Chain, Polymeric Fluorosurfactants have less potential for environmental or health concerns due to a combination of larger molecular size and reduced toxicity of the shorter perfluoroalkyl chain. Two OMNOVA products have been reviewed by US EPA and Low Volume Exemptions have been granted to manufacture these materials. Introduced commercially in , they are incorporated into commercial floor polish formulations. Research continues developing fluorosurfactants for other replacement applications.

Simplified Total Kjeldahl Nitrogen Method for Wastewater: A Green Alternative to Traditional Kjeldahl Methodology: The Total Kjeldahl Nitrogen (TKN) test is commonly performed at municipal and industrial wastewater treatment facilities to measure the concentrations of ammonia and organic nitrogen compounds. The TKN method is, however, one of the most challenging, dangerous, labor-intensive tests performed in wastewater treatment plants. This method requires digesting samples at high temperatures for several hours with strong sulfuric acid to convert the nitrogen to ammonium sulfate. Concentrated sodium hydroxide is then added to make the solution alkaline, and the liberated ammonia is distilled into a receiving solution where it is measured by back titration with sulfuric acid.

The analysis requires equipment that is expensive, fragile, and space-consuming. More recent TKN methods use metal catalysts such as mercury to speed the digestion and improve recoveries (EPA 351.2 Rev. 2.0, ). Ion-selective electrodes, the spectrophotometric phenate method, or the nesslerization method (which requires significant amounts of mercury) are often used to measure the ammonia. The TKN method also suffers from poorly understood interferences.

Nitrate, the primary interference, can oxidize ammonia to form nitrous oxide (N2O), causing negative interference. When sufficient organic matter is present, nitrate can be reduced to ammonia, causing positive interference. To date, traditional methodologies have not eliminated these interferences.

Hach Company has developed a rapid test that eliminates many of the weaknesses of traditional TKN tests. Their Simplified TKN (s-TKN) method uses two simple measurements to calculate the TKN value as the difference between the concentration of total nitrogen and that of nitrate plus nitrite. The method does not require mercury. Sample and reagent volumes are less than 10 milliliters per test. Based on the estimate that nearly 5 million TKN tests are performed annually, use of the s-TKN method could eliminate over 45 tons of mercury per year. In December , Hach commercialized its s-TKNTM method and prepackaged chemistry.

Small Scale Chemistry: Pollution Prevention in Inorganic Chemistry Instruction Program: Small-Scale Chemistry (SSC) techniques developed by Dr. Stephen Thompson at Colorado State University build pollution prevention, waste minimization, and student safety at the design stage rather than controlling it at the disposal stage. SSC inherently manifests characteristics of "green chemistry" by incorporating the principles and methodologies of source reduction. The SSC techniques and experiments result in significant waste reduction and reduced risk of chemical exposure to both students and faculty.

This is achieved through innovative experiments and methodologies that use alternate reaction conditions and alternate synthesis pathways. The concepts of SSC evolved as a solution to many of the serious problems (e.g., cost, safety, waste disposal, pedagogy) associated with chemistry laboratory instruction. Drops of chemicals used as their own containers replace liters of chemical hazardous waste in breakable glassware. The innovative use of high-tech plasticware designed for genetics research reduces cost while maintaining safety and sophistication. SSC techniques and methodologies provide a realistic approach to green chemistry and allow academic institutions to institutionalize lasting behavioral changes. SSC provides an easy to implement, affordable, and wide application remedy to a real environmental management problem faced by most college and university chemistry programs.

Sodium Silicide: A New Alkali Metal Derivative for Safe, Sustainable, and On-Demand Generation of Hydrogen: Sodium silicide (NaSi) is a stabilized, alkali metal silicide powder that reacts with any water solution to generate hydrogen instantly. SiGNa&#;s patented NaSi powder is modified to delocalize the electrons across the clathrate, forming an air-stable, free-flowing powder. In a fuel cell, NaSi produces pure hydrogen gas as needed at pressures lower than those in soda cans. NaSi overcomes the most-significant challenges that have prevented low-temperature proton exchange membrane (PEM) fuel cells from commercialization: storing high-pressure hydrogen and building costly infrastructure. NaSi is clean, sustainable, inexpensive, easily transportable, and safe for indoor use. Fuel cells powered by NaSi produce only hydrogen and water vapor; they create no greenhouse gases, toxic byproducts, or harmful emissions. Recyclable fuel cartridges deliver NaSi to any PEM fuel cell; once the NaSi is spent, the nontoxic, environmentally benign residue can be recycled as an industrial feedstock.

SiGNa&#;s NaSi technology offers significant environmental benefits throughout its lifecycle. NaSi is manufactured from renewable, sustainable materials that are independent of oil prices. The manufacturing process requires little energy and has a very small carbon footprint.

Replacing lithium batteries and internal combustion (IC) engines with NaSi fuel cells can reduce the release of greenhouse gases (GHG) by nearly 14 percent and significantly reduce the amount of toxic materials entering the waste stream. SiGNa&#;s novel hydrogen-storage approach can enable cost-effective back-up and portable fuel cells for the medical, military, transportation, disaster relief, and consumer electronics industries. SiGNa&#;s technology is proving that hydrogen fuel cells are not only commercially viable, but even more high-performing and cost-effective than batteries or small IC engines.

For example, NaSi can replace the combustion engine/gas back-up in battery-hybrid cars to extend their range by 50 miles. Also, e-bikes powered by NaSi can go 3&#;4-times farther than bicycles powered by lithium batteries. During , licensee myFC commercialized PowerTrekk, a portable hydrogen charger, in Europe.

Solder Waste Reduction Environmental Project: One operation in the manufacturing process of printed wiring boards (PWBs), Hot Air Solder Leveling (HASL), applies solder to the copper circuits on the PWB as a solderability preservative for subsequent component assembly operations at customer locations. As the PWB passes through the molten solder in the HASL process, some copper dissolves from the PWB into the solder bath. The maximum allowable copper contamination level in solder for PWB applications is 0.30%. To maintain the solder bath below the maximum copper contamination level, a fraction (1/3) of the solder bath was routinely removed from the process and replaced with fresh solder. This spent solder, due to its lead (Pb) content, was classified as a hazardous waste.

In , 372,800 pounds of solder hazardous waste was generated at Viasystems Corp.&#;s Richmond facility from the process for disposal. This was reduced to 261,720 pounds in through optimization of process parameters to minimize the copper dissolution rate. Although this was a significant waste stream reduction, this level of hazardous waste generation was still unacceptable from an environmental and cost standpoint. In addition, the required bailout of spent solder created productivity and process control issues within the process.

In , a specific waste minimization project was undertaken to further reduce the solder hazardous waste generation in the HASL process. An online solder skimmer device was developed that allows preferential removal of the copper from the HASL solder. The solder skimmer functions by continuously circulating a small portion of the solder from the HASL solder pot (480 ºF) through the skimmer, which is maintained at a temperature 100 degrees lower (380 ºF), then returning it to the main solder pot. A portable solder pot was developed to work in conjunction with the solder skimmer to eliminate solder waste generation when routine maintenance was performed. As a result of this solder waste minimization project, solder dross hazardous waste shipments were reduced from 261,720 pounds in to 29,920 pounds in . The solder waste generation was reduced from 199 pounds in to 31 pounds in on a per 1,000 panels processed basis. An overall waste reduction of over 80% was achieved. The reduction of solder waste also resulted in fresh solder cost savings of over $250,000 per year. There are now more than 50 solder skimmer devices in use on HASL processes throughout the world.

Sol-Gel Technology for Low-VOC, Non-Chromated Adhesive & Sealant Applications: The primary objective of this project is to develop and transition to the Department of Defense (DoD) and other organizations processes that eliminate the volatile organic compounds (VOC), chromates, and strong acids typically found in the metal surface treatment and priming steps conducted prior to application of adhesives and/or sealants. Secondary objectives are the reduction of hazardous wastewater streams associated with current processes and improved performance compared to these processes.

This project will develop, evaluate, and field demonstrate nonchromated, zero VOC sol-gel processes for adhesive and sealant applications. The sol-gel processes developed will replace the current approaches that are high-VOC and/or chromates. They will also eliminate the current use of strong acids and reduce the waste streams associated with the existing processes. This project will build on recent work using sol-gel technology to deposit thin organic-inorganic coatings on metal surfaces to develop good adhesion between the metal and subsequently-applied polymers (primer, adhesive, or sealant) via covalent chemical bonding. A main feature of the effort is the extensive leveraging of previous, ongoing, and proposed research.

Development of new non-chromated, zero-VOC adhesive and sealant surface preparation and primer technologies will have a major impact on both cost and performance of military and commercial aircraft. Eliminating VOCs and chromates from these processes will result in considerable cost savings due to avoiding the need for hard controls and/or fines for non-compliance. At the Naval Aviation Depot (NADEP) North Island alone, the installation of VOC-control equipment for these processes is expected to cost $15M and the installation of chromate control equipment is expected to cost $2-3M, with operation costs of approximately $250K per piece of equipment annually. However, the majority of repairs at NADEP North Island are conducted on aircraft; thus, a mandate for hard controls will incur additional costs for removal of parts and increased aircraft downtime. Consideration of cost savings from other NADEPs, U.S. Air Force air logistics centers (ALC), Army depots, and commercial usage will multiply these cost avoidance figures many-fold.

Solvair Cleaning System: Eighty percent of the 30,000 commercial drycleaning facilities in the United States use perchloroethylene. Unfortunately, perchloroethylene is a hazardous air pollutant under the Clean Air Act (CAA) and waste streams generated by perchloroethylene drycleaning are hazardous under the Resource Conservation and Recovery Act (RCRA). In California, health and environmental concerns are leading to the phase-out of perchloroethylene drycleaning; other states are proposing similar actions. Alternative solvents are available for use in conventional drycleaning systems, but all rely on evaporative hot-air-convection drying to remove the solvent from the textiles after cleaning. As a result, these alternatives have similar problems with environmental release, operator exposure, and hazardous waste streams.

Solvair initially developed its technology to replace traditional drycleaning with a safer, more environmentally friendly, more-effective cleaning technology. The Solvair system replaces evaporative hot-air-convection drying with a counter-current process including multiple liquid carbon dioxide (CO2) rinses that remove the solvent from textiles after cleaning. It allows the practical use of safer, more effective drycleaning solvents including dipropylene glycol n-butyl ether (DPnB). DPnB is miscible in liquid CO2 and is readily rinsed from textiles. It is commonly used in household cleaners, has extremely low volatility, and is biodegradable.

Compared to conventional perchloroethylene systems, the Solvair system with DPnB eliminates hazardous waste streams, reduces the amount of waste by approximately 60 percent (including eliminating contact waste water), and maximizes the recovery and reuse of fluids in the system. The CO2 in the Solvair process is a byproduct of other industrial processes and not a new source of CO2 release.

Because the Solvair cleaning technology can use a wide range of solvents, it has potential applications in many industrial and commercial cleaning applications beyond drycleaning. In December , commercial facilities using the Solvair cleaning technology processed over 3 million pounds of garments.

Solvent Replacement and Improved Selectivity in Asymmetric Catalysis Using Supercritical Carbon Dioxide: The use of supercritical carbon dioxide as a substitute for organic solvents already represents an important tool for waste reduction in the chemical industry and related areas. Coffee decaffeination, hops extraction, and essential oil production as well as waste extraction/recycling, and a number of analytical procedures already use this nontoxic, nonflammable, renewable, and inexpensive compound as a solvent. T

he extension of this approach to chemical production, using CO2 as a reaction medium, is a promising approach to pollution prevention. Of the wide range supercritical carbon dioxide reactions that have been explored, one class of reactions has shown exceptional promise. Los Alamos National Laboratory has found that asymmetric catalytic reductions, particularly hydrogenations and hydrogen transfer reactions, can be carried out in supercritical carbon dioxide with selectivities comparable or superior to those observed in conventional organic solvents.

Los Alamos has discovered, for example, that asymmetric hydrogen transfer reduction of enamides using ruthenium catalysts proceeds with enantioselectivities that exceed those in conventional solvents. The success of asymmetric catalytic reductions in CO2 is due in part to several unique properties of CO2 including tuneable solvent strength, gas miscibility, high diffusivity, and ease of separation.

In addition, the insolubility of salts, a significant limitation of CO2 as a reaction solvent, has been overcome by using lipophilic anions, particularly tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. These discoveries demonstrate an environmentally benign and potentially economically viable alternative for the synthesis of a wide range of specialty chemicals such as pharmaceuticals and agrochemicals.

Solvent Waste Reduction Via An Acetic Acid Bowl Cleaning Process: Photoresist, a photosensitive resin mixed in a carrier solvent, provides the base upon which the semiconductor circuit pattern is built on a silicon wafer. When resist is applied to the semiconductor water, it also gets applied to the equipment (the coater bowl). A variety of solvents have traditionally been used to periodically remove this resist buildup. A new chemistry has been developed by IBM process engineers that uses glacial acetic acid instead of the more traditional organic solvents.

This provides two primary benefits. It reduces the quantity of chemical, and the quantity of waste, required to clean the bowls by 97% (87,000 gallons of solvent per year) and it allows treatment of the waste solvent in the Burlington on-site biological wastewater treatment process. These chemicals use reductions and process improvements will save approximately $296,000 per year in chemical purchase and waste disposal costs and $64,000 in space and process efficiencies. Since the acetic acid and resist byproduct waste can be broken down via bacterial action at the site biological treatment plant, the new process eliminates the need to ship this wastestream off-site for treatment and disposal.

Solvent-Free Chemical Synthesis: This environmentally benign solvent-free synthetic approach utilizes neat reactants either in the presence of a catalyst or catalyzed by the surfaces of recyclable support(s) such as alumina, silica, clay, zeolites and "doped" surfaces e.g. NaIO4-silica, Oxone®-Al2O3, NaBH4-clay, persulfate-clay etc. under microwave (MW) irradiation conditions thus promoting reduction of solvents "at source" and excess chemicals in manufacturing.

This pollution prevention strategy has been targeted to industrially significant cleavage, condensation, oxidation, reduction and cyclization reactions that currently employ toxic, corrosive, and irritant chemicals and generate hazardous waste. The technology uses material science, molecular modeling and synthetic organic chemistry expertise and addresses the needs of broad chemical community (polymers, pharmaceuticals, and fine chemicals) by efficient production of valuable intermediates (enones, imines, enamines, nitroalkanes, oxidized sulfur species and heterocycles) in one-pot reactions.

Solvent-Free, Crystal-to-Crystal Photochemical Reactions: The Synthesis of Adjacent Stereogenic Quaternary Centers: Chemical structures with adjacent stereogenic quaternary carbon centers are common in biologically active substances, including natural products, pharmaceuticals, and specialty chemicals. Despite recent advances in preparative chemistry, there have been no satisfactory procedures for preparing these structures, much less so for preparing them using environmentally benign processes.

At present, most structures are obtained in low yields by circuitous routes with waste-generating purification steps. The technical challenge stems from the limitations that arise when six groups must converge with precise stereochemistry on adjacent carbons. Professor Garcia-Garibay&#;s method consists of exposing a finely powdered crystalline ketone with appropriate substitution at the a-carbons to a light source. Within hours, the ketone transforms into the desired product with no need for purification.

Notably, one can use conventional methods to add six groups at the ketone a-carbons (approximately 2.56 Å apart) easily and with excellent steric control. These substituents weaken the ketone a-bonds to extrude a CO molecule when a photon is absorbed. A short-lived biradical intermediate retains the stereochemistry of the ketone and makes the desired bond with stereoselectivity and stereospecificity that rival enzymatic processes. As an emergent technology, the photodecarboxylation of crystalline ketones is one of the most general and promising methods for synthesizing structures with adjacent stereogenic quaternary centers.

Solventless Process for Improving Fabric Performance Properties: The Nextec process delivers fabric performance benefits through a process that utilizes no solvents, has no volatile organic compounds (VOCs), utilizes essentially nontoxic starting materials, and yields inert residuals that have passed biocompatability testing. The unique patented technology that is being practiced by Nextec Applications, Inc. replaces processes in which rubbers are dissolved in toxic aromatic or chlorocarbon solvents and coated or spread on fabrics. Nextec&#;s process allows precise placement of thin polymeric films around fibers and crossover points and filling in or leaving open interstitial spaces within fabrics.

The choice of polymer, substrate and placement of polymer allows for improvement of properties such as breathable barrier performance, controlled porosity, resistance to fluids, and adhesion/release behavior. This technology has found applications including aerospace, automotive, apparel, and medical.

Solventless Process for Making Tackifiers and Adhesives: Worldwide, over 2.5 million tons of pressure-sensitive adhesives (PSAs) are manufactured annually for use in many industries, including pulp and paper, electronics, wireless telecommunications, medical devices, cosmetic and personal hygiene, and others. PSAs are made by combining tackifier dispersions with latex dispersions.

Tackifier dispersions are made either from low-temperature resins that melt at less than 100 °C or from resins that melt at higher temperatures. High-temperature resins are dissolved in organic solvents then heated to evaporate and recover excess solvent, resulting in some solvent emissions. Over time, any residual solvents in the adhesive also evaporate into the environment. Low-temperature resins are heated, melted, slowly added to hot water, and continuously stirred for over 4 hours to form an emulsion containing up to 50 weight-percent water. The emulsion is then transported to the site at which the adhesive is made. After the adhesive has been coated onto a substrate, radiant heating removes the excess water.

Argonne National Laboratory has developed a new process to make tackifier dispersions for PSAs. The Argonne process pulverizes the resin to an average particle size of less than 5 micrometers and then directly forms the dispersion in water, in just a few minutes, without dissolving the resin in solvents, melting it, or using excess water. The process does not require solvents or heat to process either high- or low-temperature resins. It also eliminates the need for transporting excess water. Argonne&#;s process is cost-effective and energy-efficient. It reduces the cost of manufacturing water-based tackifier dispersions by over 35 percent and uses less than 25 percent of the energy required by conventional processes. As a result, it reduces greenhouse gas emissions.

Argonne has filed a patent application for this technology. Dyna-Tech Adhesives, Inc. has manufactured 500 pounds of resin with an average size of 2.5 micrometers for testing.

Solventless, Low-Toxicity, Thermosetting Oligomers that Require Only Low Energy to Cure: An important technical achievement in the last 40 years has been the development of coatings, inks, and adhesives that cure essentially instantly with UV light or electron beam radiation. Equipment and processes cured these materials very efficiently without solvents or energy-intensive ovens. Although this produced a dramatic net reduction of pollution, the technology was not risk-free. The acrylic monomers and photoinitiators in traditional formulations for UV-curable coatings can be very toxic (e.g., corrosive or skin sensitizers) and odiferous; as a result, they require stringent safety controls.

Ashland&#;s resin technology uses facile chemical conversion to reduce the toxicity of traditional formulating monomers and resins, resulting in novel compounds that cure without additional photoinitiators. Ashland&#;s DREWRADTM radiation-curable acrylate oligomer resins are manufactured as 100-percent-reactive liquid resins to be formulated into radiation-curable coatings, inks, and adhesives. These products allow the application of coatings to substrates without releasing solvents into the environment. Radiation curing eliminates large, energy-intensive processing steps such as baking in gas-fired ovens. Emissions from the use of this resin product are expected to be nearly zero.

To produce DREWRADTM, Ashland selected the same essential formulation building blocks according to performance requirements. These chemicals are then reacted with ß-diketones or ß-ketoesters (or amides, anilides, etc.) in a base-catalyzed Michael addition to produce oligomers of higher molecular weight and viscosity. The product is typically of higher acrylic bond functionality and, more important, the oligomeric product possesses a photolabile ketone moiety that can initiate free-radical polymerization upon exposure to UV light. These novel compounds have virtually unlimited architectural design flexibility, enabling changes to be made that maximize the green character of each product. Ashland Water Technologies, a division of Ashland Inc., has commercialized this novel green technology. Ashland received its most recent patent for DREWRADTM in .

Solvox Special , an Anti-agglomerate and Stickies Neutralizer for the Paper Industry: The scope of papermaking over the last twenty years has changed dramatically, in large part because of the use of secondary fibers as a source of furnish. Economics have made secondary fiber a mainstay for a variety of paper producers because it is an inexpensive source of fiber and is readily available. Furthermore, legislation has mandated the use of secondary fibers whenever possible to conserve valuable natural resources. With these forces in play, there have been numerous challenges that have presented themselves not only to the paper industry but also to its chemical suppliers.

One of these challenges, "sticky" control, has provided Solvox Manufacturing Company with an opportunity to position itself as the problem-solver to customers world wide. "Stickies" refer to any insoluble resin that has tacky properties and adversely affects papermaking. Commonly used items such as Post-it® notes, address labels, and envelopes contribute to the problem of sticky control. Pressure sensitive adhesives alone cost the paper recycling industry an estimated $700 million per year. Recently, Solvox has formulated a special chemical additive, Solvox Special , that enables the paper industry to make quality paper with recycled furnish equal in quality to that made with virgin fiber. This additive is an anti-agglomerate that can be considered a stickies neutralizer. Solvox Special coats the sticky to make it dimensionally stable, thereby allowing it to be removed by mechanical means, while preventing reagglomeration of the stickies.

When compared with additives currently in use, Solvox Special reduces VOC emissions, eliminates costly downtime, and produces a higher quality end paper product. This additive is important to the paper industry and the environment for several reasons. First, this one additive does the job of three or more chemicals. But more importantly, this chemical has a very low VOC level (approximately 0.50% by weight) compared to the chemicals that it replaces (some over 50% by weight).

Additionally, it eliminates costly downtime, thereby decreasing the total cost of making paper. Finally, it is now possible to make an end paper product of high recycled content that is equal in quality to that of virgin fiber. This will lower the amount of waste paper entering our landfills. Ultimately, this will reduce the use of trees and preserve this planet for generations to come.

Source Reduction and Sustainability through Use of Mergal® 753 Antimicrobial Preservative: Product innovation is standard with high-volume agricultural products, but is less frequent with antimicrobial and biocidal preservatives. Troy developed Mergal® 753 in response to market concerns over green chemistry initiatives, sustainability, and release of volatile organic compounds (VOCs). Mergal® 753 is a concentrated aqueous dispersion of 1,2-benzisothiazolin-3-one (BIT), a widely known biocidal active ingredient; it contains no VOCs and is compatible with water-based production processes. Typical applications for industrial biocides like Mergal® 753 include adhesives, paints, coatings, and metalworking fluids.

Mergal® 753 meets basic green chemistry parameters. Troy assessed the carbon footprint of its product using the methods and tools developed by the Greenhouse Gas Protocol Initiative, a joint project of the World Business Council for Sustainable Development and the World Resources Institute. The basic calculation used to develop its carbon footprint included the "functional unit": comparing the amount of product needed by a customer for a given application. Troy&#;s conventional, dilute product requires 4.5 times the volume as the concentrated product (Mergal® 753) to treat the same amount of material at the customer&#;s facility.

The primary comparison assumed that Mergal® 753 is diluted by the customer to the same final concentration as the dilute product and that the use rate per functional unit is equivalent for the two products. With this approach, Troy estimated that the potential energy savings through replacement of its dilute product with Mergal® 753 results in a carbon dioxide (CO2) reduction equivalent to taking 5.3 passenger cars off the road each year. Additional savings would occur with increased product use, which effectively reduces worker exposure to hazardous workplace substances. Troy optimized the formulation of its product to ensure suitability with current application systems, and EPA formally registered Mergal® 753 on October 31, .

Source Reduction through Software Technology: Source reduction is the core of Chemical Safety&#;s EMS (Environmental Management Systems) software. The most recent version, EMS , introduced Chemical Safety&#;s greener chemical alternatives search tool in its material safety data sheet (MSDS) and chemical inventory modules. EMS software is the only technology that incorporates greener chemical alternatives as a key feature for inventory search, procurement, and use. EMS software offers the ability to search for and select greener chemical alternatives in a database of chemical alternatives identified by EPA as well as leading universities and institutions. Users range from chemists and researchers to manufacturing and facilities managers. With EMS software, users reduce their acquisition, use, and release of toxic and hazardous chemicals and materials used for research, manufacturing, maintenance, repair, and operations; they also maximize their acquisition and use of environmentally preferable products.

EMS software provides steps essential to efficient chemical procurement, storage, distribution, reuse, recycling, and disposal. These steps reduce unnecessary chemical purchasing, reduce the footprints of hazardous chemicals at facilities, and decrease the generation and disposal of chemical waste. Chemical Safety has incorporated EPA&#;s Design for the Environment (DfE) program into its EMS software. The DfE program evaluates the human health and environmental effects, performance, and cost of traditional and alternative technologies, materials, and processes. It helps reduce the use and disposal of chemicals of concern.

EMS software supports easy tracking of chemical containers and important data from the point materials are purchased or received through delivery, use, and storage to disposal and ultimate destruction. When users request a chemical from their company&#;s inventory that is maintained in EMS , the system prompts them to substitute a safer chemical. Clients as diverse as the Department of Energy&#;s Stanford Linear Accelerator, Novartis Vaccines and Diagnostics, E&J Gallo, the L&#;Oreal Group, Baxter Healthcare, and EPA Region 9 laboratories are currently using this EMS software.

Splittable Surfactants: Union Carbide has developed a new class of surfactants, splittable surfactants, which provide a substantial reduction in emulsified organics discharged in waste-water streams from industry. Splittable surfactants exhibit superior end-use performance, compared to current waste-treatable surfactants and other proposed treatments, which have not gained widespread use due to performance limitations. Waste streams containing splittable surfactants are quickly, easily, thoroughly, and irreversibly "split" and deactivated, via a chemical trigger, into non-surface active components, allowing rapid separation of oily waste from the water stream. A more concentrated oily waste is generated, facilitating either incineration for fuel value (industrial laundry applications), isolation for recycling (metal working fluids), or direct use (isolating lanolin from wool scouring). Before splitting and deactivation, Splittable Surfactants have an environmental profile comparable to conventional nonionic surfactants. Upon deactivation, both the hydrophilic and hydrophobic components biodegrade rapidly, and the hydrophilic component remaining in the waste water is essentially nontoxic to aquatic life. Splittable Surfactant technology represents the first industry partnership under the EPA&#;s Environmental Technology Initiative for Chemicals, and EPA has recognized these products as "a significant innovation in surfactant chemistry, one that greatly reduces risk to the aquatic environment," with its Recognition of Achievement in Pollution Prevention.

Spray-Dried Dispersions Based on Hydroxypropyl Methylcellulose Acetate Succinate for Delivery of Low-Solubility Drugs: Increasingly, drug candidates emerging from drug-discovery programs have low water solubility. Indeed, approximately 40 percent of all new drug candidates and 70 percent of new anticancer drug candidates in development are not well-absorbed orally, principally due to low water solubility. These candidates frequently have low oral bioavailability and require high doses to achieve therapeutic effects.

Bend Research has developed a novel, green, drug-delivery technology using hydroxypropyl methylcellulose acetate succinate (HPMCAS), a low-toxicity, renewable material. Spray-dried dispersions (SDDs) of low-solubility drugs and HPMCAS dissolve rapidly. They disperse in the body to enhance the bioavailability of low-solubility drugs by 10-fold or more and to reduce the dose of active pharmaceutical ingredients required for therapeutic results. Currently, the pharmaceutical industry generates an estimated 25&#;100 kilograms of waste per kilogram of product. If all low-solubility drugs were formulated as HPMCAS SDDs, the enhanced bioavailability could eliminate more than 27,000 tons of toxic pharmaceutical waste annually.

The HPMCAS SDD manufacturing process uses green chemistry and renewable materials. Typically, only the drug and HPMCAS are dissolved in an organic solvent, such as acetone, methanol, or mixtures of these with water. The dispersion is spray-dried and the solvent is recovered for reuse.

HPMCAS is an amphiphilic polymer. Its hydrophobic regions interact with low-solubility drug molecules and its hydrophilic regions allow the drug&#;HPMCAS structures to form stable colloids in aqueous solution. HPMCAS forms amorphous dispersions with a broad range of structurally diverse low-solubility drugs for use in solid, oral dosage forms. Bend&#;s technology can enable the development of many promising drug candidates that would otherwise be halted due to low solubility. Over 400 candidate drug compounds have been successfully formulated as HPMCAS SDDs; 28 have advanced to human clinical testing, including one to Phase 3. In , Bend constructed a $90 million commercial SDD production facility.

STABREX® Microorganism Control Chemical: An Environmentally Sensible Chlorine Alternative for Industrial Water Treatment: Chemical products should be designed to preserve efficacy of function, reduce toxicity, degrade rapidly and innocuously, reduce accident risk, and be made from renewable sources. A chlorine alternative is needed for microbial control. Chlorine gas is dangerous, the liquid is not stable, biofilm control is not adequate, and chlorine disinfection by-products are toxic. STABREX® Microorganism Control Chemical overcomes these deficiencies: It is much less toxic and generates less disinfection by-product. It is 10x less volatile, 50% less reactive, more stable in storage/transport, more effective against biofilms, and easier to handle. It is made from completely renewable resources.

Its use has been shown to reduce adsorbable organic halide generation in real industrial water systems by more than 60%. These technical attributes result in valuable benefits: Less environmental toxicity, less chemical waste, and lower accident potential. One hundred fifty million pounds of chlorine or its equivalent have been replaced with 38 million fewer pounds of STABREX in 5,000 water systems. Five hundred billion gallons of industrial water have been successfully treated. This innovation is original and unique: It is the first biomimetic industrial antimicrobial, having been designed to imitate compounds naturally produced in mammalian immune systems.

Stalosan F Microbial and Environmental Control for Use in Housing of All Animals: Stalosan F is an all-natural product that improves hygiene and environmental conditions for livestock when applied to damp surfaces. It has lower toxicity and provides greater safety than existing alternatives. Stalosan F is a pink powder that acts as a drying agent. It is composed of human-grade, high-quality minerals including three forms of very pure phosphate, a structural clay material, a combination of iron and copper salts, and an essential oil. This formulation makes it safer than many sulfate-based alternatives. Its low pH inhibits pathogens. Stalosan F addresses the problem of odor abatement and ammonia in external environmental bacteria, viruses, fungi, and fly larvae, all of which interfere with livestock production and pose potential harm to humans. Stalosan F also controls moisture at variable levels, where increased water pressure leads to increased water binding capacity. It can bind up to four times its own weight of water. It can be applied by hand or with a power blower.

Stalosan F is suitable for all animals, including cats, dogs, and rabbits, with special attention to livestock, including pigs, cows, poultry, horses, and sheep. Stalosan F virtually eliminates offensive odors for neighboring residents and ammonia levels within the production facility. This, in turn, creates a better environment for livestock to grow and thrive.

Stormøllen A/S, the Denmark-based manufacturer of Stalosan F, is selling this product in the agriculture markets of 64 countries. ArchAngel represents this company in the United States. Most recently, the U.S. EPA has evaluated Stalosan F for registration and found it to be safe for humans and animals. ArchAngel is anticipating U.S. EPA registration in spring .

Starch Graft Polymers as Phenolic Resin Extenders: Starch graft polymers are derived from modified starch and conventional vinyl and acrylic monomers. While starch graft polymers have been known previously, a technology developed by Sequa Chemicals overcame rheological problems associated with prior products and afforded a convenient, fluid latex-like form. Drawing on glyoxal-based paper coating technology, these new starch graft polymers also utilized a novel nonformaldehyde cross-linking system. This new technology was initially used as a replacement for conventional latex polymers made with N-methylol acrylamide (which is a source of formaldehyde emissions) as the cross-linking system.

Applications were as binders for fiberglass and polyester nonwoven mat. This provided a binder system that eliminated formaldehyde emissions and maintained good performance and reasonable economics. These starch graft emulsion polymers are water-based, nontoxic and nonirritating. Recent work has examined the use of these starch graft polymers as extenders for phenol-formaldehyde (PF) resins. An aqueous PF resin typically contains approximately 2% free formaldehyde. Approximately 1 billion pounds of aqueous PF resins are sold in the United States each year.

That adds up to approximately 20 million pounds of free formaldehyde emitted to the environment and workplace each year. It has been found that starch graft polymer products not only decrease formaldehyde emissions greatly, but also work synergistically with PF resins. Optimum performance is near the midpoint of composition. Such synergistic performance has not previously been observed with conventional latex emulsion polymers. Performance properties such as tensile strength, burst, and stiffness are improved over either the PF resin or the starch graft alone.

Extending PF resins proportionally lowers the residual unreacted phenol in the final products. Proportional reductions of formaldehyde emissions have been measured, and a scavenging effect has been noted in testing designed to evaluate exposure to workers handling treated substrate. This technology is now sold commercially in tank truck quantities and its benefits are being promoted in various industries.

Stepan Company PA Lites Polyester Polyol: Stepan Company&#;s Polyester Polyol product, manufactured using the Phthalic Anhydride Process Light Ends (PA Lites), uses a previously categorized waste as a raw material in its manufacture, thereby eliminating the material&#;s disposal via incineration. This Polyester Polyol is the basic raw material for the manufacture of various types of insulating wallboard used in the home construction and commercial building industry.

By substituting traditional raw materials with PA Lites, Stepan Company is providing the construction industry and consumer with a cost-effective alternative to traditional building construction products. Benefits from this product substitution go beyond the elimination of a waste requiring disposal. With its substitution as a raw material, it has reduced the requirement for phthalic anhydride, the traditional raw material for the polyol product, and the air emissions associated with its manufacture. As part of the development of this process, the distillation operation in the phthalic anhydride facility was also improved. An estimated 350 tons per year of organic waste material has been eliminated with the development and implementation of this technology.

This not only represents a significant reduction in waste requiring disposal by incineration, but also the air emissions associated with these processes. Since this previously categorized waste material is now used on site to produce Polyester Polyol, potential exposure to the general public during offsite transportation to disposal facilities has been eliminated. This project resulted in two economic benefits. The first is the savings associated with the transportation and disposal via fuel blending for energy recovery. On an annual basis the expected saving is $200,000. The second economic benefit is the raw material savings due to the replacement of the Pure PA with the PA Lites material on a pound for pound basis. This results in additional savings of $20,000 annually.

Stepanfoam Water-Blown Polyurethane Foam HCFC-Free, Environmentally Friendly, Rigid Polyurethane Foam: Stepan Company&#;s STEPANFOAM® Water-blown Polyurethane Foam is a product in which CFCs and HCFCs are replaced with water as the blowing agent in rigid polyurethane foam. Historically, polyurethane foams used in insulating applications incorporated Trichlorofluoroethane (CFC-11), or more recently 1,1-Dichloro-1-fluoroethane (HCFC-141b), as the blowing agent. CFCs and HCFCs have been demonstrated to play a role in the depletion of Earth"s stratospheric ozone layer and to contribute to global warming.

Traditional rigid polyurethane foam products have the potential to release CFCs and HCFCs into the environment during formulation, manufacture, use, and disposal. The replacement of these compounds with water as an innocuous blowing agent eliminates the requirement for these environmentally unfriendly compounds and the resultant emissions to the environment. Throughout the s Stepan Company has remained committed to the development of a lower cost, technologically advanced polyurethane foam which replaces environmentally unfriendly and potentially hazardous blowing agents with water. Stepan&#;s Research and Development Department and Business Teams have partnered with our customers throughout the development and continued application of this product to promote its use as a viable alternative to CFCs and HCFCs.

Sterilization of Medical Devices with Atmospheric Plasma: Atmospheric Glow Technologies (AGT) has developed an innovative method for cold sterilization of medical and dental devices using the exhaust of the patented One Atmosphere Uniform Glow Discharge Plasma® (OAUGDP®). The OAUGDP® operates in air at atmos-pheric pressure to produce reactive chemical species that include oxygen species, excited molecular oxygen species (singlet oxygens), superoxide, ozone, and oxygen radicals. The longer-lived species can be convected outside of the plasma device to sterilize objects beyond the plasma volume. AGT has performed studies that demonstrate the ability of this technology to neutralize bacterial endospores on objects with complex shapes, such as hemostats and quick disconnects.

Recently, AGT successfully passed the Association of Analytical Chemists (AOAC) Sporicidal Activity of Disinfectants Test (Official Method 966.04). This test requires the sterilization of 720 successive carriers. Analysis by AGT indicated that the carriers harbored extraneous organic debris and loads of up to 109 endospores per carrier before treatment. Materials compatibility studies performed by AGT indicated no obvious alteration in high-density polyethylene or stainless steel following treatment. AGT is maturing the OAUGDP® technology to provide an alternative means of low-temperature sterilization that will ultimately reduce reliance on chemicals such as ethylene oxide and its common nonreactive diluent, dichlorodifluoromethane (CFC-12), that pose a threat to human health and the environment.

Stoller STIMULATE: A Natural Product for Improving Crop Plant Performance and Enhancing Pest Resistance: Stoller formulates STIMULATE with the natural plant growth regulators, auxin, kinetin, and gibberellin. These plant growth regulators are present in fruits and vegetables; Stoller often uses them at concentrations lower than are present naturally in food.

The focus in crop production has been on ameliorating the imbalance of nitrogen, phosphorus, and potassium in fertilizers. By focusing on fertilizer, farmers are generally producing at only a small fraction of the genetic potential of crop seeds. Stoller has developed a model that places the growth regulator auxin at the top of plant growth and development control, an accurate estimate based on recent scientific literature. At least two premises of the Stoller model are critical to improving crop production. The first is that stress (environmental or biological) or lack of crop performance is most likely the result of an imbalance of the plant growth regulators (often referred to as hormones) in a crop plant. The second is that the halflife of the hormones has to be short in a particular organ of the plant for the rapid signaling required for "on time" plant growth control. The hormones are either hydrolyzed or conjugated after they signal a particular physiological event.

Judicious and timed application of Stoller STIMULATE in drip-irrigated crops increases crop yields; it reduces fertilizer and water use by 50% per unit of crop production. It also reduces the use of insecticides and fungicides by 50 to 100% by enhancing a plant&#;s resistance to insects and tolerance to disease organisms.

Substitution with Carbon Dioxide Eliminates Major Use of Sulfuric Acid: Crane & Company, Inc. produces specialty papers with highly technical specifications, mostly from cotton and other natural and synthetic fibers. Company products include 100% cotton social stationery, commercial printing papers, reprographic papers, synthetic fiber nonwovens, and currency and security papers. To reuse preconsumer products that either do not meet specifications or have been reclaimed from finishing operations (referred to as "broke"), Crane must process the paper into a slurry form. Because many of its papers have a high degree of permanent wet strength, Crane must use an alkaline substance and high temperatures to make the slurries. In its traditional papermaking method, Crane then adjusted the pH of the slurried broke with sulfuric acid before adding the broke to the papermaking stock.

Crane&#;s Research and Development Department initiated a toxics use reduction project aimed at replacing the sulfuric acid with a less toxic chemical. The research was successful, and Crane is now using its improved process to repulp off-specification papers. The company has replaced sulfuric acid with an innovative liquid carbon dioxide system. It has also reduced the amount of sodium hypochlorite it uses by specifying cleaner raw materials. It controls the temperature and pH of the process more closely as well. Crane reduced its use of sulfuric acid by approximately 697,000 pounds and sodium hypochlorite by 576,000 pounds between and , a combined reduction of about 46%. Overall, these improvements have reduced the costs of pulp production by 3%.

Suga®Nate: A Safer, Milder, Greener Surfactant: Although lauryl sulfate and its ethoxylated version, lauryl ether sulfate, are the two most common anionic surfactants used in formulating shampoo, body wash, and other personal care products, these ingredients are highly irritating to eyes and skin. Products formulated with ethoxylated lauryl ether sulfate also contain various levels of 1,4-dioxin, a probable human carcinogen. Finally, a large percentage of these surfactants are made from ethylene, a nonrenewable petroleum feedstock.

Colonial Chemical has developed sulfonated alkyl polyglucosides as safer surfactants: they replace lauryl alcohol with alkyl polyglucosides as the hydrophobic component. These unique, patented surfactants represent a breakthrough in mild surfactant technology. They are naturally derived, biodegradable raw materials that are nearly 90 percent renewable and could reach 100 percent renewable as development progresses. These new surfactants do not irritate eyes or skin, allowing formulators of personal care products to use totally irritation-free ingredients. Unlike ethoxylated lauryl ether sulfates, Colonial Chemical&#;s surfactants are completely free of dioxin. An unexpected property is their ability to withstand microbial contamination.

Outside testing showed that Suga®Nate 160 has reasonably good antimicrobial activity at the 16 percent active level, which is a normal concentration for a primary surfactant in higher-end shampoos. As a result, Suga®Nate can reduce or even eliminate the antimicrobial additives used in formulations. The Suga®Nate synthesis has added benefits: it is atom-economical; sodium chloride is the only byproduct; and water is the only solvent.

The relatively mild reaction conditions are closer to ambient than those of competing surfactants, and there is no need for separation or purification. The toxicity of these new surfactants is much lower than that of competing products, and the new surfactants are even less toxic than their starting materials. In , Suga®Nate was certified as a biobased product by the U.S. Department of Agriculture (USDA).

Sugars from Lignocellulosic Materials for the Production of Bio-Based Fuels and Chemicals: The disadvantages of relying on fossil fuels are well known. Environmental problems linked to fossil fuel usage include acid rain, global warming, and air and water pollution. Production and use of carbohydrate-based chemicals can overcome many of these environmental issues. Yet, widespread production and use of biobased chemicals have not occurred. The return to the carbohydrate economy is stymied in an environment of artificially low petroleum prices, an uneven playing field tilted toward the use of fossil fuels, and a lack of technology to competitively produce products from biomass. Arkenol, Inc. has developed an environmentally sound and cost competitive technology for the carbohydrate industry. While completely analogous to the petrochemical industry, Arkenol&#;s technology uses innocuous and renewable feedstocks.

The Arkenol process utilizes concentrated sulfuric acid to break down the cellulosic structure in lignocellulosic feedstocks and then, with water, to complete the new formation of individual C6 and C5 sugars for further processing into chemicals and fuels. The lignin is processed for soil amendment or solid fuel. Silica, uniquely present in rice straw, can be recovered and converted to high value precipitated silicas and zeolites. Trace amounts of sulfuric acid in the sugar solution are converted into gypsum for soil amendment or ammonium sulfate for fertilizer.

The sugars can be converted into alcohols and carbon dioxide, acids, ethers, solvents, or surfactants either by direct chemical conversion, fermentation, or a combination of both. With over 200 different chemicals and an even greater number of downstream chemical product combinations that can be derived from biomass, the market opportunities are considerable.

Arkenol is pursuing several opportunities worldwide to convert feedstocks such as rice straw, sugar cane bagasse, and municipal solid waste into ethanol and other chemicals. An advanced project in Sacramento County, California, will use Arkenol&#;s technology to divert approximately 132,000 tons per year of rice straw from open-field burning to produce up to 12 million gallons per year of ethanol and coproducts. While eliminating burning on some 60,000 acres of rice fields, the Sacramento project will provide a much needed disposal alternative for rice growers faced with the legislative mandate to phase out open-field burning.

In addition, by diverting the rice straw from open-field burning, the Sacramento project creates significant improvements in the region&#;s air quality. Avoidance of open-burning of about 140,000 tons per year of rice straw results in annual net emissions reductions of 280 tons of NOX, 173 tons of PM10, 130 tons of VOCs, 138 tons of SO2, and 4,988 tons of CO.

The successful implementation of Arkenol&#;s technology will lead to decentralized and competitive economic production of fuel ethanol and other biobased chemicals (ethanol is produced from the Arkenol process at a cost of $0.66 per gallon, compared to $1.29 per gallon from the industry standard process). Arkenol&#;s ability to use a wide variety of feedstocks will enable placement of production facilities (or "biorefineries") near the market for the products. Large scale conversion of waste materials into fuels and chemicals is a novel solution to waste management, pollution prevention, and economic development.

Supercritical Fluid Spray Application Process for Adhesives and Primers: The objective of this project is to develop low/no-VOC (volatile organic compound), non-structural adhesives to substitute for the current high-VOC, non-structural adhesives used in military applications by substituting supercritical carbon dioxide for conventional VOC solvents and carriers. It is estimated that 8.5 billion pounds of synthetic polymer adhesives are used annually, of which approximately 55 percent are VOCs. While the total DoD usage is not known, it is estimated that approximately 173,000 pounds of VOCs are released annually by Air Force aircraft operations. VOCs commonly used in applying adhesives include aromatics (e.g., toluene), ketones (e.g., acetone, methyl ethyl ketone), and others (e.g., methanol, chloroform) which negatively impact worker health and safety, adversely affect environmental standards, are ozone depleting, and result in increased hazardous material management costs including permitting and installation of sophisticated emission control equipment.

Conceptually, the UNICARB process is straightforward in that a concentrated solution of polymeric material (in this case the adhesive and adhesive primers), and other additives are mixed in situ with high-pressure (in the range of psi to psi) carbon dioxide and then sprayed. In practice, the process is complicated in that one is mixing an incompressible, highly viscous material (polymeric material and solvents) with a highly compressible fluid of very low viscosity (supercritical carbon dioxide). The solvents are mixtures of fast and slow evaporating VOCs which are chosen specifically for their ability to dissolve the polymeric material, reduce viscosity, and aid in atomization and droplet coalescence on the substrate. In the supercritical spray process, supercritical carbon dioxide replaces that fraction of the organic solvent that is needed to give the viscosity reduction necessary for spray atomization. This is also the solvent that is the primary contributor to the high VOC emissions.

For a polymeric material to be adapted to the UNICARB process, the phase behavior of that particular polymeric material (the adhesive in this case) with carbon dioxide has to be known. Mixtures of high-pressure carbon dioxide with the adhesive concentrate must exist as a single phase at elevated pressures for the UNICARB process to work. To date, little is known of the phase behavior of polymer-solvent-carbon dioxide mixtures, and determining the underlying thermodynamic and rheological behavior is an arduous trial and error process. Additionally, precipitation of solids in solution has been encountered and needs to be avoided when using this process.

This project will adapt the UNICARB spray application process to adhesives in two ways: (1) a continuous process for use in a manufacturing setting, and (2) a portable hand held batch process for use in small jobs or repair scenarios. Each of these processes requires its own unique set of phase diagrams given that the portable device operates in dynamic conditions (the materials and pressures of the system are changing with time), whereas the continuous spray operation operates in a steady state mode (the system pressure and material compositions remain constant with time). Therefore, for each adhesive adapted to the UNICARB process, two different types of phase diagrams will need to be generated.

Two adhesive systems, acrylic and neoprene, to date have been selected for study. We have completed examination of the neoprene system. The work using the neoprene has progressed slowly, due predominately to the crosslinked nature of the polymer and its resistance to dissolving in many solvents. When processed in industrial adhesives, neoprenes are exposed to very high shear, a process we wanted to avoid since it also reduces the molecular weight of the polymer that may change its properties for the purpose of this investigation. To date, we have completed carbon dioxide concentration at 9, 20, 30, 35 weight percent in toluene at temperatures of 45, 50, 60, and 70 °C. Equilibrium pressures for the phase boundaries ranged from 700 to psi.

We have completed the automation of the data acquisition process by including an automated piston controller and modifying the automated data collection computer. These changes will make it possible to increase our testing speed and accuracy by limiting the opportunity for human error.

We have found unforeseen behavior in both systems that requires further investigation. In both the acrylic and neoprene systems, the phase transition measured dynamically occurs at a higher pressure than when measured statically. The presupposition was that the dynamic transition would occur at lower pressures than static due to the time lag for separation of the solvent and polymer. We have found the opposite to be the case and that the dynamic transition found above the static phase boundary reverts back to single phase when allowed to equilibrate. A possible explanation for this phenomenon is the difference between random and nonrandom behavior and that the system in question is showing nonrandom behavior. This finding, once verified, holds important possibilities for understanding phase transitions in multicomponent systems. Our results for the neoprene system with 25% carbon dioxide show a 300 to 400 psi difference between the lower static and higher dynamic results. This is seen from 40°C to 70°C.

Supercritical&#;Solid Catalyst Reaction Process for Converting Waste Fats, Oils, and Greases into Premium Biodiesel: BioFuelBox has developed and successfully operated a process for continuous-flow production of ASTM-quality biodiesel without using toxic consumable catalysts or post-reaction purification reagents. The technology, patented by Idaho National Laboratory and licensed by BioFuelBox, uses heat and pressure in a closed system with heterogeneous catalysis and nontoxic gaseous cosolvents at supercritical conditions. The simplistic combination of these factors allows the use of historically unsuitable lipid feedstocks, including those containing microbial degradation products, heavy metals, organic sulfur, extreme fatty acid levels, and water, to produce 100-percent biodiesel (B100). The continuous-flow supercritical&#;solid catalyst (NovoStreamTM) process does not require added acid or base catalyst or the subsequent neutralization and water-washing steps typical of traditional biodiesel production.

By implementing this technology at its American Falls, Idaho facility over the past year, BioFuelBox has demonstrated the feasibility of converting over 10,000 liters per day of previously landfilled lipid waste (such as grease trap sludge) to quality, consumer-ready methyl ester fuels in high yields. Further, the NovoStreamTM process makes fuel without the significant chemical waste and massive water use that are typical of traditional biofuel synthetic processes.

The BioFuelBox technology reduces environmental impacts not only by the chemistry involved, but also by using the lowest grades of municipal and industrial waste as feedstocks. These materials, with volumes of nearly 4 billion gallons annually in the United States alone, are currently destined for disposal in landfills, where they subsequently undergo microbial degradation to form potent greenhouse gases. The patented technology has proven successful in the energy-efficient, rapid conversion of these wastes to fuels. The benefits include eliminating this portion of our nation&#;s waste burden as well as reducing the use of food-oil seeds for nonfood uses. In August , BioFuelBox produced 50,000 gallons of B100 biodiesel fuel.

SuperCTM, The Use of Supercritical Carbon Dioxide: The process SuperCTM permanently consumes large quantities of carbon dioxide (CO2) to make less-expensive, more durable, fully recyclable products from industrial wastes or ordinary cements. Even earth will serve as a material. SuperCTM is an economical answer to global warming and large-scale pollution. It employs simple reactions to sequester CO2, preventing it from entering the atmosphere. It provides lower cost alternatives to forest products, steel, aluminum, plastics, composites, and ceramics by using industrial waste streams as feedstocks. It can lengthen the service life of new, and even restore existing, concrete structures and infrastructures. It can stabilize cemented mixed and high-level nuclear waste to facilitate long-term storage without further chemical evolution.

Implementation/conversion requires minimal capital investment. The process uses supercritical CO2 (at greater than 88.3 °F and greater than 1,071 PSI) to infiltrate fully formed products made from wastes like fly ash, blast furnace slag, dust, clay, or from common cements, to produce almost any desired properties or behaviors. In this state, CO2 behaves as a super solvent. Products made this way cost less, are equal or superior in performance to those made in traditional ways, and are fully recyclable without manual segregation. They displace products made from higher energy or ecologically sensitive materials, and reduce environmental impact, health concerns, and fossil fuel consumption.

Surachi Fuel Technology: Surachi fuel technology oxygenates petroleum fuels and other alternative hydrocarbon fuels. The technology modifies the fuel with a reaction in water in the presence of a recyclable, organic, semisolid catalyst. The reaction adds a hydroxy group and hydrogen atom at the former alkene bond in the fuel. The catalyst does not stay in the fuel, but is removed after the chemical reaction for reuse. This technology works for all internal combustion fuels including diesel, gasoline, jet fuel, Bunker C, and other heavy fuel oils. Fuel Energy Service Corporation developed the Surachi technology in collaboration with the inventor. The technology allows internal combustion engines to run cleaner, quieter, and with more power, but with lower levels of soot, unburned hydrocarbons, and other harmful exhaust emissions. It expands the actual volume of the fuel and increases the Btu. The process removes most of the sulfur from fuel: the sulfur precipitates and is deposited on the semisolid catalyst, from which it can be removed. The Surachi technology does not adversely affect critical fuel characteristics, such as viscosity, low corrosivity, or other parameters that are common problems for fuel additives such as ethanol and other oxygenated species. The modified fuels are essentially identical to the original fuel in storage, holding, and handling capabilities. The Surachi process has not yet been scaled up to production volume, either as a batch or a continuous process. In , a patent was issued for this technology.

Surface Functionalized Nanomaterials: Significantly Reducing Fluorochemicals in Consumer Items: Fluorochemicals are used in many consumer products such as stain-resistant clothing, upholstery, carpets, paper, and non-stick coatings and paints. Certain fluorochemicals, however, persist in the environment, bioaccumulate, and have been deemed probable carcinogens by the EPA. Fluorochemical pollution from consumer products represents a significant environmental problem.

G3 Technology Innovations (G3i) has commercialized SFNanoTM, a technology that reduces the use of fluorochemicals by at least a factor of eight. The technology mimics the natural water-repellant surfaces of those plants whose hierarchical surface roughness limits the contact angle of fluids. Water beads up and rolls off the leaves of many plants without wetting their surfaces. The G3i technology duplicates this effect, protecting consumer products including fabric, wood, paper, and stone from water damage through a simple coating process.

The G3i technology allows the facile surface functionalization of nanoparticles with groups of functional molecules. The technology uses common, colloidal silica nanoparticles that have been commercially available for over 60 years and are generally considered safe from an environmental perspective. Nanoparticles from these silica colloids, surface-modified with 5 nm zirconia particles, provide the scaffold to attach hydrophobic molecules (carboxylates or sulfonates). Amines are added to bond covalently to the substrate, such as a textile, and a small amount of fluorochemical is added to repel oil. When applied to a surface, the particles provide a micro- or nanoscopic roughness, like that of plant leaves. The hydrophobic molecules on the nanoparticle surfaces also repel water and dirt. The innovation has multiple human health and environmental benefits. It can be applied to a wide range of consumer items, providing an effective replacement for fluorochemicals or a means to reduce their use significantly.

Recently, Scientific Certification Systems certified this technology and its high performance at low fluorochemical loadings. G3i currently sells products based on its technology in the textiles market as GreenShieldTM.

Surfactant-Free Supercritical Carbon Dioxide Fluoroolefin Polymerization Technology: Fluoropolymers exhibit a balance of high-performance properties that makes them ideal for many technologically demanding applications. Commercial fluoropolymer manufacturing practices use aqueous emulsion or suspension processes that require fluorinated surfactants that are now environmentally suspect (see "Perfluorinated Pollutant Puzzle" in Chemical & Engineering News, August 30, ). Moreover, these traditional water-based manufacturing processes strain local community water supplies and pose real health concerns when residual surfactant is not adequately isolated from the water supply.

A team of researchers at UNC-Chapel Hill and NC State University has developed a more environmentally compatible process for producing fluoropolymers that uses supercritical carbon dioxide and does not require any surfactants. The process also yields more uniform products and enables easy, one-step isolation of the final polymer product. DuPont has recently licensed the technology and commercialized the process at its Fayetteville Works site in Bladen County, NC. DuPont brought the plant on line in March of . The test and demonstration phase of the plant was highly successful and the Fayetteville Works site currently operates at plant-production capacity.

Sustainable Earth® Cleaning Products Designed for Health and the Environment: Commercial cleaning products are used daily by professionals in schools, hospitals, and commercial facilities. Although cleaning is beneficial, cleaning products commonly contain chemicals harmful to human and environmental health. High concentrations of these chemicals can negatively impact ground-level ozone concentrations, aquatic ecosystems, worker safety, and human health. Coastwide Laboratories uses green chemistry to develop products that meet rigorous performance, environmental, and human health criteria.

Their strategy involves:

(1) fully assessing all ingredients to understand their potential human health, environmental health, and lifecycle impacts;

(2) creating a product development standard, Sustainable Earth® Green Chemistry Standard 114 (SEGC 114), to establish positive criteria for product efficacy as well as human and environmental health benefits; and

(3) formulating products to meet SEGC 114.

This strategy results in entirely new formulations with remarkable benefits. Sustainable Earth® (SE) cleaning products combine reagents determined to be safer for human and environmental health with a hybrid surfactant system containing a stabilized oxidizing compound. This system eliminates conventional, potentially problematic ingredients such as alkyl glycol ethers, alkali builders, alkylphenol ethoxylates, EDTA, and ethanolamine. SE products have increased functionality and performance, use fewer, more benign ingredients, and reduce waste and emissions. Current SE products include many types of cleaners, as well as an odor eliminator, floor finish, wax stripper, and dust mop treatment. In , Coastwide introduced seven new SE products; its sales of all 21 SE products were $2.3 million.

Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for Safe Oil-Thickening Agents (Amphiphiles): Non-polymeric amphiphiles can form molecular gels or viscoelastic materials when they self-assemble by noncovalent interactions such as surface tension and capillary action. Amphiphiles can immobilize a large pool of organic or aqueous solvent into a gel. A wide variety of amphiphiles are currently derived, at least in part, from nonrenewable resources. In addition, their synthesis frequently requires multiple steps, energy-intensive purifications, and complex, expensive catalysts. Structuring an amphiphile such as vegetable oil into a gel alters its physical properties with or without altering its chemical properties.

Current structuring agents and methods used for food tend to increase the content of saturated fatty acids and trans-fatty acids in oils, which may increase the risk of vascular and heart disease. Professor John and his group have developed potent amphiphiles from biobased resources using enzyme-mediated transesterification of sugar alcohols with fatty acid donors. Upon self-assembly, these amphiphiles produce soft materials in aqueous and organic solvents. These amphiphiles exhibit superior ability to structure vegetable oils without increasing their saturated fatty acids. They are also nontoxic and biodegradable. The ease of synthesis and cheap raw materials translate into low-cost production of efficient sugar-based amphiphilic gelators.

In addition, these self-assembled gels have a remarkable ability to trap highly volatile pheromones and release them slowly, so they remain effective longer. Another application is environmentally benign oil spill recovery: when added to an oil-water mixture, Professor John&#;s amphiphiles can selectively partition into the oil phase and convert it to a gel. This technology offers the potential to replace current oil structuring agents with safe, biobased amphiphiles resulting in enhanced performance at lower cost. Currently, Professor John is developing next-generation, biobased amphiphiles to structure hydrophobic liquids such as vegetable oils and related compounds for food and cosmetic applications. Several food and personal care companies have expressed interest in licensing this technology.

Sustainable, Natural Green Chemistry for Cooling Water Treatment: Pure water evaporates from cooling towers to the atmosphere, but minerals in the water stay behind and typically require 20&#;40-percent tower discharge to avoid scale or corrosion problems. Chemicals added to inhibit scale and corrosion can save water, but low-solubility, corrosive minerals still lead to water waste. Along with wastewater, towers also discharge treatment chemicals including inorganic or organic phosphates, heavy metals, organic polymers, biocides, and halogens.

Natural green chemistry (NGC) provides a paradigm shift in cooling water treatment, with economical methods to reduce toxic and persistent chemicals, reduce water and energy use, and support sustainable water ecosystems. Patented NGC methods use the natural minerals present in water as sustainable feedstocks, providing superior corrosion and scale protection that replaces chemical treatments. An NGC pretreatment step for scale control uses proprietary high-efficiency softening equipment to remove calcium and magnesium ions, which lead to scale formation. The NGC process also polymerizes natural silica monomer to high-molecular-weight multimeric and colloidal silica particles that are stable and do not form scale.

NGC concentrates minerals in tower water, facilitating natural biostatic chemistry that reduces biocide use by 95 percent or more. NGC permits tower operation with 95-percent- reduced water waste and less than 2 percent of makeup water. NGC obviates costly systems to purify water for reuse by permitting over 99-percent evaporation of water used to remove waste heat energy in existing tower systems. NGC reduces the tower discharge volume for liquid or dry disposal and averts capital cost, chemicals, materials, and energy consumption.

NGC technology can eliminate the discharge of over 400 million pounds of organic and toxic chemicals in the United States annually. NGC can potentially reduce fresh water use by an estimated 500 billion gallons annually, with over $1.5 billion savings in costs from reduced water, chemicals, and energy.

SVP-PureTM ClO2 Process Technology: In the water and water-treatment industries, the need to reduce trihalomethane (THM) and haloacetic acid (HAA) formation, control taste and odor, remove soluble iron and manganese, and effectively eliminate bacteria and viruses has substantially increased the demand for chlorine dioxide. While several methods exist to generate ClO2, previous technologies have been limited by low efficiencies, concern over unreacted chlorite, excess chlorine/hypochlorite, and cost. Eka&#;s SVP-PureTM ClO2 process technology eliminates these concerns with its state-of-the-art aqueous sodium chlorate/acidic hydrogen peroxide process. SVP-PureTM is the first sodium chlorate based ClO2 process to receive EPA registration for use as a disinfectant in drinking water and waste water.

The two-chemical feed system adopts Eka Chemicals&#; patented hydrogen peroxide chemistry and applies a proprietary blend of sodium chlorate and hydrogen peroxide called PurateTM. In comparison to competitive technologies, SVP-PureTM chemistry requires no gaseous or liquid chlorine feed and no chloride ion addition. This process eliminates byproduct chlorine, thereby reducing the potential for the formation of THM, HAA, and chloroform disinfection byproducts.

Eka Chemicals&#; proprietary reaction vessel design optimizes mixing of feed chemicals, yielding high conversion rates. Some technologies frequently overfeed the chlorine and chlorite precursor chemicals to meet the 95% efficiency standard that results in the pass-through of feedstock chemicals to the receiving water. In contrast, SVP-PureTM incorporates a microprocessor-based electronic controller to regulate reactor feed, calculate efficiency, and control output. Fail-safe emergency shut-down logic programmed into the controller minimizes operator feedback requirements providing the safest, most user-friendly system.

Synergy CCSTM Precision Cleaning Solvent: A Government/Industry Solution to a Complex Environmental Problem: Halogenated solvents have traditionally been used to remove a broad range of soils and contaminants generated during manufacturing operations. Their use, however, has left a legacy of potential environmental and health problems. Synergy CCS(TM) (critical cleaning solvent) was developed to address these problems. Synergy CCS(TM), formulated from agriculturally-derived, naturally renewable products, is a potential replacement for many of these traditional cleaning solvents.

Synergy CCS(TM) had its beginnings at the Department of Energy"s Kansas City Plant (managed and operated by AlliedSignal Inc.) when the plant began an effort focused on the elimination of toxic, restricted, or environmentally damaging solvents. Experience derived from this solvent substitution and elimination effort proved beneficial when, through its Technology Transfer Program, Kansas City Plant personnel were asked for help by a small manufacturer needing a safe, one-step cleaning solvent. Synergy CCS(TM) Precision Cleaning Agent was formulated to meet this need. Synergy CCS(TM) is a blend of environmentally derived products that forms [sic] a safe, powerful, yet distillable precision cleaning solvent capable of being heavily loaded with contaminants. Synergy CCS(TM) is comprised of natural components that have been in industrial use for more than 45 years: d-limonene, a solvent derived from citrus byproducts, and tetrahydrofurfuryl alcohol, a solvent produced from the waste products of corn, oats, and sugar production. Individually, these materials are already used for cleaners, paint stripping formulations, and agricultural applications.

The solvent was further developed and adopted by a Hewlett-Packard Co. division, patented, and licensed to Petroferm, Inc., a worldwide leader in sales and technical support for alternative solvents and cleaning technologies. This partnership demonstrates how government and private industry can work together to develop safe chemical alternatives to solve environmental problems while simultaneously improving America"s industrial competitiveness.

Synthesis and Photopolymerization of Monomers Derived from Biorenewable Sources: Plant-derived unsaturated vegetable oils can be readily epoxidized using a novel catalytic method and employing an economically attractive, high yield, solvent-free process to give the corresponding epoxidized triglycerides. Alternatively, naturally occurring epoxidized vegetable oils can be used as directly obtained from their plant sources. The addition of an onium salt cationic photoinitiator renders these materials photopolymerizable. Further, the use of photosensitizers allows the cationic photopolymerization to be carried out using ambient sunlight.

The UV cure of the epoxidized vegetable oils takes place rapidly, with low energy, in the absence of solvents and without any air or water polluting organic volatile emissions. Furthermore, these materials are completely nontoxic. Currently, the epoxidized oils are employed in a wide variety of industrial coating, printing ink, and adhesive applications. In addition, we have demonstrated the practical use of these materials as reinforced composites that can be used for such structural, load bearing applications as building and roofing panels, pipe and conduit, boats, and for casts and splints. Since a wide variety of unsaturated vegetable oils are available with different structures, a correspondingly large number of materials with specifically tailored properties can be generated to fit specific applications. This technology has the multiple advantages of being very simple, broadly applicable, and completely environmentally benign.

Synthetic Dyes Based on Toxicological Considerations: This nomination pertains to the design of nontoxic alternatives to currently used metal-complexed dyes containing metals designated as priority pollutants. Specifically, iron-complexed dyes were synthesized as substitutes for metal-complexed dyes currently used in situations requiring colorants possessing very high photostability and resistance to removal under wet conditions. The dyes investigated were iron (Fe) complexes of ligands and provided the foundation for a pollution prevention approach to environmental problems associated with the manufacture and use of organic dyes based on chromium (Cr) and cobalt (Co).

As a starting point for this study, the Freeman group synthesized and evaluated Fe-complexed analogs of commercial azo and formazan dyes containing Cr and Co. Fe (II) sulfate was employed as the metallizing agent because it has exhibited low aquatic toxicity in studies. This investigation led to the discovery of nontoxic alternatives to high-volume chromium-based commercial black dyes, without compromising the desirable photostability of the latter. In addition, red and blue 1:2 Fe-complexed dyes (1 iron atom per 2 dye molecules) were discovered, an achievement heretofore unreported and presumed unachievable. An explanation for the dull colors that have traditionally characterized Fe-complexed dyes was also developed, providing a basis for further achievements in this area.

System for Bioremediation of Effluents: Traditional remediation of municipal, industrial, and agricultural wastewaters uses combinations of sulfuric acid, caustic, petroleum-based solvents, and synthetic emulsifiers, which are toxic or generally not biodegradable. Naturally occurring microorganisms are an alternative to chemical remediation. They are generally supplied as dormant or resting spores with low activity levels, however, making it too costly to use enough bacteria for effective treatment in many systems.

Extensive research and development by NCH Corporation has resulted in a novel, patented process for on-site fermentation that efficiently generates a renewable feedstock of naturally occurring strains of Pseudomonas and Bacillus bacteria at 30 trillion vegetative bacterial cells every 24 hours to treat wastewaters. Every 24 hours, the BioAmp® system delivers 292 gallons of liquid product, equivalent to 25&#;50 pounds of commercially available dry bacterial powdered product, directly into problematic drain lines.

The bacteria degrade the organic matter in the drains, ultimately releasing carbon dioxide (CO2) and water. This saves energy by producing active bacteria on-site and reducing the energy required for manufacturing and shipping. It costs less than 10 percent of comparable quantities of dry powdered bacteria. The BioAmp® system reduces the need for commonly used acid, caustic, and solvent drain maintainers. NCH&#;s BioAmp® system also reproducibly reduces biochemical oxygen demand (BOD) compared to baseline in a number of case studies. This type of data generation is new to the industry and demonstrates the efficacy of the BioAmp® wastewater treatment system.

During , Iowa State University tested the biobased content of BioAmp® pellets to provide data for the U.S. Department of Agriculture&#;s BioPreferred Program in the category of Biological Drain Maintenance. NCH&#;s BioAmp® system has been on the market since ; it is now in use in the food processing and petroleum refining industries with over 1,500 systems in all parts of the world.

Tandem Enzymatic-Electrochemical Methods for Green Manufacturing: Efficient Synthesis of Pharmaceuticals from Halogenated Aromatic Waste: The projects described within this document are nominated for an academic award under Focus Area I-The use of alternative synthetic pathways for green chemistry. The prevention of pollution at its source is addressed by replacement of currently used methods of oxidation and reduction (all based on metal reagents) with enzymatic and electrochemical techniques (all performed in water, alcohols, or other environmentally acceptable solvents). The combination of enzymatic transformations with electrochemistry, along with efficient design, yields unprecedented brevity in the attainment of important pharmaceuticals from metabolites of type 1 by oxidative dearomatization, a reaction that has no counterpart in traditional chemistry.

Halogenated aromatic compounds, viewed as harmful to the environment, are enzymatically converted to useful synthons and effectively removed from the hazardous waste pool with the added economic benefits of strategic conversion that would not be available through incineration of such compounds, which method would be also a contributor to green-house gases. It must be emphasized here that the enzymatic conversion of the toxic aromatic materials takes place in the very first step of the synthetic pathway and that all subsequent synthetic intermediates are harmless.

The residual mass from the enzymatic processes is suitable for disposal to municipal sewers, thus further reducing the amount of actual waste. The synthesis of a homochiral cyclitol from halobenzene by several steps involving essentially no reagents serves as one of many illustrations of the technology. This document describes the strategy, the logic, the execution, and the future projection of this program of potentially global impact with attendant benefits to the health and economy of society at large through managed processing of aromatic waste to value-added substances. The length of a synthesis and the weight of all reagents and solvents used play a direct role in the attendant accumulated waste mass for the process.

A new definition of efficiency, "Effective Mass Yield," is provided as the ratio of the weight of desired product and the weight of all non-benign mass requiring treatment or disposal that is used in the process. Several syntheses of a cyclitol are compared by this criterion in terms of reduced pollution at the source of manufacturing-this indeed is one of the central themes of our design.

These projects have been developed in the last five years, and several patents have already been granted on more efficient synthesis of pharmaceutical entities. Several inositols, manufactured by this method, have been marketed by Aldrich Chemical Company since . Since , several diols of type 1 and certain cyclitol intermediates are also catalog items at Aldrich. The overall strategy of this project takes advantage of the best combinations of enzymatic trans-formations, electrochemical methods, as well as traditional chemistry to achieve unprecedented efficiency in the syntheses of natural as well as unnatural compounds.

Tandem Reactions, Cascade Sequences and Biomimetic Strategies in Chemical Synthesis: Tandem reactions, cascade sequences, and biomimetic strategies are being increasingly applied to the construction of natural and designed molecules. Such processes, in which ideally a single event triggers the conversion of a starting material to a product which then becomes a substrate for the next reaction until termination leads to a stable final product, are highly desirable not only due to their elegance, but also because of their efficiency and economy in terms of reagent consumption and purification.

Often, these multistep, one-pot procedures are accompanied by dramatic increases in molecular complexity and impressive selectivity. The discovery of new molecular diversity from Nature and the demand for more efficient and environmentally benign chemical processes dictates and invites the further development of such synthetic strategies and tactics as we move into a new age of chemical synthesis and green chemistry. The nominated work responds to these needs through the design and development of biomimetic cascade sequences, photo-induced reactions and other alternative, tandem-type synthetic pathways for the construction of molecular complexity. Central to a number of these cascade technologies is the venerable Diels-Alder reaction. Often requiring only thermal- or photo-initiation, this reaction delivers its downstream products with ideal (100%) atom economy.

Tasphox Water Treatment System: TASPHOX stands for Turbo-aspirated Photochemical Oxidizer an innovative edge photolysis based oxidation water treatment process that generates hydroxyl free radicals using hydrogen peroxide and deep ultraviolet light to destroy organic chemicals and pathogens in aqueous fluids.

Contaminated water is pumped through a two-chambered Peroxide Photolysis Ionizer (PPI) reactor constructed of 316-L stainless steel. Design flow rates from 3.0 to 500.0 gallons per minute are possible. Units linked in parallel can treat millions of gallons of water per day.

The fluid is initially irradiated by high intensity UV light and microwave energy. Then directed in the second chamber to a point where concentrated hydrogen peroxide (up to 50%) and additional UV light produces the transient univalent OH* radical. This is immediately followed by turbo-aspiration through an eductor jet. The resulting ebullition drives additional oxygen into the fluid and residual gaseous waste products such as carbon dioxide, nitrogen, argon etc. out of solution.

This process can be used to pre-treat any organically contaminated water source for drinking or other potable use. And consequently has wide application in emergency response during natural disasters, terrorist attacks and battlefield water purification.

Technology of Safe, Biodegradable, and Non-Polluting Products as Alternatives to Toxic Microbicidal Chemicals: Almost all traditional, widely used disinfecting and sanitizing products contain ingredients that are toxic or potentially toxic, are environmentally hazardous, or have a high potential for accidents. For example, oxidizing chemicals, such as hypochlorite, peracetic acid, hydrogen peroxide, ozone, and chlorine dioxide, kill microorganisms by indiscriminate oxidation of organic matter, potentially destroying antioxidants, nutrients, and vitamins while forming unknown or toxic byproducts, including cancer causing free radicals. The non-oxidizing microbicidal quaternary ammonium compounds (QACs; other traditional disinfectants) inhibit butyl cholinesterase in blood plasma, liver, pancreas, and the white matter and are unsafe for use on fruits and vegetables because they leave large residues.

Microcide uses ingredients listed by the FDA and EPA in volumes 21 and 40 of the Code of Federal Regulations (CFR) as biodegradable, generally recognized as safe (GRAS), food additives, safe, and/or nonpolluting. With these ingredients, Microcide develops broad-spectrum microbicidal products as alternatives to toxic and oxidizing chemicals for the food processing, personal care, and health industries. Their products use surface-active agents at low pH. Raising the pH diminishes the microbicidal properties, allowing safe environmental disposal and biodegradation of the products after use. These products selectively kill microorganisms on food contact surfaces, on fresh fruits and vegetables, and on body parts (including mucosal and skin surfaces) without covalent chemical reactions. The technology presents alternative products safe for manufacturing, transportation, and use without accident potential. Two of Microcide&#;s products, PRO-SAN and PRO-SAN L, are EPA-registered pesticides.

Template-Controlled Reactivity in the Organic Solid State: Subtle changes in molecular structure can profoundly influence the solid-state packing and, thus, reactivity of molecules. Problematic crystal packing can prevent closely related molecules from exhibiting homologous, solid-state structures and reactivity patterns.

Professor MacGillivray has developed a general method to control organic chemical reactivity in the solid state. He uses small organic molecules as templates to assemble olefins into position for chemical reactions. The templates, not long-range crystal packing, control the solid-state arrangements of the olefins. The templates assemble the olefins via hydrogen bonds within stoichiometric solids known as co-crystals. The olefins then undergo intermolecular [2+2] photodimerizations. This pioneering work has the potential to open new avenues of organic synthesis because the solid-state medium allows molecules to react in geometries and orientations that can be inaccessible in solution.

Professor MacGillivray has used his solid-state method to synthesize molecules known as ladderanes with regiospecificity, 100-percent yield, and no byproducts. Ladderane structures are building blocks for many natural products that previously had presented a major synthetic challenge for chemists. Recently, Professor MacGillivray received a patent for his solid-state preparation of ladderanes; he and the University of Iowa Research Foundation are working toward commercialization.

In , Professor MacGillivray discovered that the co-crystals used for his solid-state reactions can form via solvent-free, mortar-and-pestle dry grinding. Previously, co-crystal formation had required solvent. In addition to synthesizing unique organic molecules, he has used his methods to synthesize ligands in inorganic chemistry. Specifically, his molecules can be used as building blocks for self-assembled metal&#;organic architectures and porous materials with structures akin to zeolites. His work opens the solid state as a general solvent-free medium in synthetic organic chemistry with applications in inorganic chemistry and materials science. Professor MacGillivray received the highly prestigious Arthur C. Cope Scholar Award of the American Chemical Society in in recognition of his solid-state methodology.

Terephthalic Acid Synthesis at High Concentrations in High-Temperature Liquid Water: Acetic acid is the traditional solvent used to synthesize terephthalic acid commercially, but it has several drawbacks. First, acetic acid is flammable. Second, the commercial terephthalate process requires an expensive, energy-intensive distillation to separate acetic acid from water, which is a byproduct of terephthalic acid synthesis, and allow acetic acid recycling. Third, acetic acid oxidizes during the reaction.

At current terephthalate production levels, replacement of oxidized acetic acid requires approximately 4 billion pounds of makeup acetic acid worldwide every year. Manufacturing this makeup acetic acid not only requires substantial raw materials and energy but also creates pollutant emissions. Finally, acetic acid reacts with the bromide catalyst to produce high levels of methyl bromide emissions. According to EPA&#;s Toxics Release Inventory, a single terephthalic acid plant releases about 45,000 pounds of methyl bromide annually. Professor Savage has discovered reaction conditions and a reactor strategy for the catalyzed partial oxidation of p-xylene at high concentrations in high-temperature liquid water to synthesize terephthalic acid in high yields at nearly 100 percent selectivity.

As a replacement solvent, water eliminates the formation and emission of methyl bromide as well as oxidative solvent losses. As a result, this process eliminates the raw materials, energy, and pollutant emissions associated with producing 4 billion pounds of make-up acetic acid annually. Because the byproduct and solvent are both water, the distillation is eliminated, along with its associated costs and energy use.

Professor Savage and his group have developed and analyzed conceptual chemical process designs for this new reaction medium to show quantitatively that it is competitive in its economics, energy consumption, and environmental impacts. They have also developed processing strategies so that these greener reaction conditions can be used at the high concentrations required for commercial processes. In , University of Michigan filed a provisional patent application for this technology.

The Alternative Feedstocks and Biological and Chemical Technologies Research Programs: The Alternative Feedstocks (AF) program supports development work that employs alternative, renewable feedstocks in the biological and/or chemical production of commodity or commodity-like chemicals. The Biological and Chemical Technologies Research (BCTR) program supports research and development efforts that provide evidence of the technical and economic feasibility of advanced chemical and biological concepts that improve energy utilization, operational efficiencies, and environmental soundness of current U.S. industry process operations.

These two programs involve both the specific and broad utilization of green chemistry in the fulfillment of their missions. By definition, the AF program is green chemistry since it promotes the use of renewables in producing subsidy-free chemicals from feedstocks such as corn, lignocellulosics, and oil seed crops on scales that are or could be commodity chemicals. Many of the technology hurdles needed to employ biocatalysts as tools or biomass as a feedstock resource for the chemical processing industry have been addressed by the BCTR program. For example, efforts ranging from the development of molecular modeling tools to new, less toxic electrochemical hydrogenation processes have been undertaken and demonstrated for use in current processes. Within the federal sector, these two programs have an exceptional history of applying green chemistry to industrial needs.

The Application of Ultrasound to Catalyze Reactions in Some Industrial Processes: Ultrasound has potential as a safe and clean method to catalyze reactions. It uses high-frequency sound waves to change reaction paths and speed up reactions, thus reducing or eliminating added chemicals. The methodology has so far not been scaled up for industrial application to any great extent. Dr. MacRitchie and his collaborators are working to apply ultrasound to three areas that have the potential to lead to industrial processes.

These are:

(1) the modification of wheat gluten to create value-added products;

(2) the clarification of fruit juices; and

(3) the purification of potable water. Dr. MacRitchie is using ultrasound to produce value-added products from gluten by enhancing functional properties such as solubility, gelling, foaming, and emulsifying. F

or example, ultrasound can increase the solubility of gluten, making it suitable for use in fortified beverages. Previous methods have used concentrated acids or enzymes, but these are not environmentally friendly. Dr. MacRitchie and his colleagues are collaborating closely with Midwest Grain Products in Atchison, Kansas, one of the major manufacturers of gluten. Presently, manufacturers mainly use enzymes to clarify fruit juices. Ultrasound offers the possibility of clarification without additional chemicals. Water contamination by microorganisms or by chemical pollutants such as pesticides is another problem to which Dr. MacRitchie will apply ultrasonics to replace traditional hazardous chemicals.

The CerOx Process: A Non-Thermal Alternative for Hazardous Waste Destruction: The release and subsequent presence of persistent, bioaccumulative, and toxic (PBT) materials in the environment have recently come to the forefront of the public consciousness. The adverse health effects of PBTs, such as dioxins, have been well documented and have led to the placement of very strict limits on the releases of these materials to the environment by industrial processes, particularly from waste disposal by incineration. The chemistry and physics of the thermal process, particularly with incineration, are such that the production of dioxin-type materials is obligatory given the process conditions. Materials pass through the high temperature zone without being completely combusted and continue to "burn" at lower temperatures. It is here that the dioxin-type materials are synthesized.

The CerOx Process is a cerium-catalyzed chemical process for the destruction of organic hazardous materials under mild reaction conditions, atmospheric pressure, and temperatures less than 100 °C. The CerOx Technology is an alternative to incineration that does not produce the products of incomplete combustion that have plagued high temperature destruction methods. The process uses the high oxidizing power of Ce(IV) in a closed liquid solution to destroy the organic compounds. Upon reaction, the Ce(IV) is reduced to a nonreactive Ce(III) that, in turn, is recycled to the active Ce(IV) oxidation state via an electrochemical oxidation. The cerium ion is a true (electro)catalyst and is not consumed in the reaction.

Virtually all organic materials can be processed and destroyed by the CerOx Process, including PCBs, dioxins, pesticides, chlorocarbon wastes, and chemical weapons agents. The organic materials are converted to carbon dioxide and water; the other reaction products are chlorine from chlorocarbons, sulfate from organosulfur compounds, phosphate from organophosphates, and nitric acid from amines. Comparison of the process conditions and economics of the CerOx Process to standard incineration indicates that this new nonthermal technology is economically competitive with existing technologies and, in many cases, is more economical that the incinerator alternative.

The Chemical Kinetics Simulator Program: Computer simulators offer a powerful means of minimizing waste generated through physical experimentation during process development and optimization, a waste stream not usually addressed in green chemistry programs. The potential impact of simulations will not be realized, however, unless they are widely accessible in an organization. The Chemical Kinetics Simulator (CKS) Program, developed at the IBM Almaden Research Center to meet this need, is a general purpose, easy-to-use package that allows outcomes of reactions to be predicted for a large variety of gas, solution, and solid phase systems in static and flowing reactors. Its basic computational method is well-founded in theory and has been significantly enhanced through new algorithms that have been awarded U.S. patents. CKS has been in use at IBM for three years for process research and development. Since May , the package has been available globally for a no-cost license through the World Wide Web and is used in many other industries for process research and development because of its exceptional ease-of-use and functionality. It also has been frequently licensed by environmental researchers in universities, corporate and government laboratories, and environmental regulatory agencies to develop models and evaluate hazards.

The Development and Commercialization of a Low-pH, Lactic Acid Process for Renewable Plastics: Lactic acid is a commodity-scale fermentation product, ranking among the highest-volume chemicals produced by fermentation. Greater than 95 percent of the world&#;s 370,000 metric tons of lactic acid is produced by submerged fermentation of sugar. This fermentation has traditionally been carried out by lactic acid bacteria maintained near neutral pH (pH 5&#;7). At this pH, however, the fermentation product is a lactic acid salt that requires neutralization. One of the primary limitations of the bacterial lactic acid process is the cost and environmental footprint of the recovery and subsequent disposal of the waste salt caused by the neutralizing agent used during purification.

Cargill, in an effort cofunded by the Department of Energy (DOE), has developed and commercialized a metabolically engineered yeast biocatalyst that efficiently produces free lactic acid at low pH (significantly below the pKa of lactic acid). The lactic acid production attributes (rate, titer, and yield) of this yeast biocatalyst are near those of a bacterial lactic acid producer, but the low pH of the fermentation produces free lactic acid as the product, not a lactate salt. This technology improves product quality and reduces production costs by roughly 50 percent. It also reduces the use of sulfuric acid and calcium hydroxide and formation of the calcium sulfate byproduct by approximately 85 percent. Finally, it leads to a 35-percent reduction in greenhouse gas emissions (GHG) over the bacterial process.

Cargill uses lactic acid as the monomer to produce NatureWorks LLC IngeoTM poly(lactic acid) (PLA). IngeoTM biopolymer is the world&#;s first and only performance plastic made from 100-percent annually renewable resources. IngeoTM biopolymer is clear and strong like petroleum-based plastic, yet can be commercially composted. Plant-based IngeoTM biopolymer offers the cost and performance necessary to compete with traditional petroleum-based materials in the packaging and serviceware markets. Cargill commercialized its new yeast-based process in .

The Discovery and Development of an Environmentally Benign Commercial Route to Sildenafil Citrate: Pfizer has emphasized green chemistry objectives during the discovery and development of the commercial route to sildenafil citrate, the active ingredient in the important medicine ViagraTM. The commercial synthesis generates only 4 kg of organic waste per kg of sildenafil, substantially less than is typical for pharmaceutical products. The key breakthrough in achieving this exceptional result was the discovery of a new, convergent synthetic route with a clean cyclization reaction as the final step, eliminating purification operations. Subsequent careful chemical development and diligent solvent recovery have optimized the environmental performance. Achievements include a nine-fold yield increase from the starting pyrazole to sildenafil citrate. The commercial route reduces organic waste by 14-fold, eliminating 4,000 tons of organic waste; it also reduces aqueous waste by 5-fold, eliminating over 3,900 tons of aqueous waste. An environmentally benign catalytic hydrogenation reaction replaces a reduction using tin chloride (tin is a toxic heavy metal). Hydrogen peroxide (a worker safety issue) has been eliminated. Three chemical steps are combined, using a single solvent that is recovered. None of the reactions in eight chemical steps requires a work-up involving extraction, again leading to low organic waste. Pfizer has implemented many technological achievements at the outset of commercial manufacture.

The DUCARE 'Zero Effluent" Recycle Chemistry System: The printing and publishing pre-press industry is undergoing a revolutionary change driven by advances in imaging technology from a craft-based industry to one relying far more on digital imaging and printing technology. From a user perspective, this new technology is more environmentally benign than the process it replaces. Several iterations of improvements in hardware and software will be required before digital imaging completely replaces conventional chemical imaging. The DUCARE system is a 'bridge" between the current and developing systems. It is designed as a 'drop in" for conventional processing and enables the customer to continue utilizing their current equipment, thus avoiding a financial burden while still eliminating the adverse environmental impact.

DUCARE is an environmentally proactive way for customers to prevent any film processor effluent from going down their drain. Typically, customers discharge the effluent to the drain, pay to have it hauled away and disposed, or use expensive high maintenance equipment for on-site treatment. The effluent contains hazardous chemicals (as defined by SARA Title III), very high BOD and COD, and high silver and pH extremes. DUCARE, offered only by DuPont, solves these problems using several industry firsts. A new developer was invented which has no SARA Title III chemicals and is based on a vitamin C isomer. The chemistry is designed to use 25 to 40 percent less product than conventional chemistry and is recycled at its manufacturing sites to insure[sic] high quality and 'like new" performance. The washwater recirculating unit reduces water use up to 99 percent. This system can be used worldwide, wherever a cost effective reverse distribution system can be set up.

The Emission Quantification Model: In the semiconductor manufacturing process, liquid and gaseous chemical mixtures are used to manufacture submicron devices. These chemicals are categorized into four general groups: corrosives, organics, toxics, and fluorinated compounds. Local, state, and federal environmental regulations governing these materials are becoming more stringent and facilities must ensure protection of human health and the environment. To help accomplish this, AMD developed the Emissions Quantification Model (EQM) as a method to identify and quantify the chemicals used in manufacturing processes and incorporate them into a comprehensive environmental management system. Based on a modified mass balance model, pollution prevention and control outcomes were used to develop a real-time measurement method.

The EQM provides information such as toxicity, usage, and emission rates and is an invaluable tool for assessing human health and environmental impacts as well as identifying opportunities to optimize, reduce, reuse, recycle, and eliminate chemicals. The EQM has initiated many improvements at AMD&#;s Austin site. For example, chemicals with potential teratogenic properties were identified and replaced with less toxic chemicals that still meet the specifications required to produce semiconductors. Methyl ethyl ketone, a hazardous air pollutant as well as a SARA 313 reportable chemical, was replaced by methyl propyl ketone, a much less hazardous substitute.

Data from the EQM assessments identified chemicals used in large quantities, including sulfuric acid and isopropyl alcohol, that could be recycled. Currently, AMD is recycling 50 percent of the sulfuric acid used in these facilities and is evaluating isopropyl alcohol recycling. In the near future, all sulfuric acid used in these facilities will be recycled, and if the capital expenditure is justified, feasible, and approved, isopropyl alcohol reprocessing will be implemented.

The EVANS DE-TOX(TM) Process for the Detoxification of Ethylene Glycol: Approximately 4,500 humans are poisoned and 90,000 domestic animals die annually in the USA by the ingestion of ethylene glycol (EG). EG is not toxic until it becomes metabolized by alcohol dehydrogenase (ADH) to glycoaldehyde and then metabolized further to other toxic metabolites. The inventors discovered that propylene glycol (PG), when mixed with EG, acts as an ADH inhibitor, preventing the metabolism of EG and preventing the toxic metabolites that are the essence of EG poisoning. Laboratory testing during and demonstrated that only a small percentage of PG is needed.

By including a minor amount of PG in their EG-based products, producers can manufacture improved low-toxicity products at lower cost than was possible previously. All of the EG poisonings by ingestion are preventable. If the new technology were applied universally to EG-based products, all ingestion-related EG poisonings of humans and animals by these products could stop. Until revealed by Evans Cooling Systems, Inc. in , PG&#;s effect on the toxicity of EG was unknown. The many tests and the development of the theory that PG acts as an ADH inhibitor, so effective as to prevent the poisonous metabolites of EG from being produced, demonstrate scientific merit.

The INFINITY Process: The INFINITY dyeing process was developed as an alternative method to manage the dyeing cycle for nylon textiles. Over 8 billion pounds of nylon textiles are consumed each year and most are dyed to meet aesthetic and functional demands. In the United States alone, consumption of dyes for nylon exceeds 30 million pounds, much of which is left in the spent dye bath after the fabric is dyed. This waste must be treated to avoid pollution of downstream waterways. Mills are meeting regulatory requirements through conventional process control techniques and end-of-pipe treatment. The INFINITY dyeing process lets mills reduce their consumption of dyes and other chemicals by 25 percent, and, in some applications, water and steam use per dye cycle is cut in half. Conventional methods use up to 4,000 gallons of water, 20 pounds of dye, and 10 pounds of dye assist chemicals per 1,000 pounds of fabric.

The INFINITY dyeing process uses only 75 percent of the dye previously required, half the water, and less dye assist chemicals to get the same fabric color. In addition, dye discharge into mill effluent streams can be reduced as much as tenfold. A mill with a 90 percent exhaust rate may discharge 500 pounds of unused dye into the mill"s wastewater treatment stream each week. With INFINITY, the same mill can move to 99 percent exhaust, reducing the amount of dye discharged to 50 pounds per week; a significant step toward attacking waste at the source. The process is currently being used at nylon textile mills in the United States, and work has begun on the feasibility of using the process on wool, cotton, and polyester blend fabrics. Cost savings by most mills using this process could easily exceed $100,000 per year.

The Mcgyan Process: A Green Synthetic Route for Biodiesel Production: Fossil fuels have detrimental effects on the environment. Biobased fuels such as biodiesel are more environmentally friendly: their use recycles carbon through renewable biomass, and they burn cleaner than fossil fuels. Current manufacturing processes for biodiesel generate significant waste streams. They also require energy-intensive, high-purity, virgin oils (mostly soy oils), whose price accounts for over 80 percent of the price of biodiesel. As a result, the biodiesel industry is not commercially viable at present without government support.

Working with Professor Arlin E. Gyberg and his student Brian Krohn at Augsburg College, SarTec has developed a green synthetic route to produce biodiesel in a fixed-bed, flow-through catalytic reactor that could change how the industry produces this renewable fuel. The key to this new reactor is a highly efficient, heterogeneous catalyst that economically converts triglycerides and free fatty acids to biodiesel. The catalyst contains modified porous microspheres of zirconia, titania, or alumina.

SarTec&#;s Mcgyan process offers many environmental advantages over the current biodiesel production method, including the following: (1) The Mcgyan process uses less energy overall. (2) The process can make biodiesel from waste and byproduct lipid sources such as brown grease and corn oil reclaimed from ethanol production as well as virtually any plant oil because free fatty acids and water in the feedstocks do not interfere. (3) The zirconia-based catalyst is contained in a fixed-bed reactor and is not continuously consumed (washed out) in the production process. (4) The new technology reduces the amount of hazardous waste produced by eliminating unwanted side reactions that produce soap wastes from free fatty acids. (5) The Mcgyan process does not require large quantities of base (or acid) to covert feedstocks into biodiesel. During , SarTec neared completion of a three-million-gallon-per-year facility that will use this technology. The projected start date for the facility is February .

The MICARE Liquid CO2 Dry Cleaning Process: The commercial dry cleaning industry faces a tremendous burden of environmental liability due to reliance on chlorinated and organic solvents. Over 72 million pounds of perchloroethylene was sold to the industry in . This material ultimately ends up in the environment or in consumer clothes, impacting the health of communities and consumers. No one has previously been able to integrate an environmentally friendly technology with an effective cleaning process that alleviates this burden to our personal and environmental health.

The application of CO2 to the dry cleaning industry has been suggested since . However, commercial realization of this goal has been hindered by two main factors: the unavailability of an appropriate process and high-pressure equipment and the inability of unmodified CO2 to provide effective cleaning. Micell has overcome equipment barriers by designing a dry cleaning process and manufacturing equipment that use liquid CO2 just below ambient temperature (~18-22 °C) and vapor pressure (~50 bar).

As for the second factor, Micell has translated the fundamental discoveries of CO2 surfactants to create detergent packages appropriate for use in liquid CO2 at saturated vapor pressure. The end result is a system that cleans clothes effectively, substantially reduces garment damage due to linting from heat, substantially reduces dye and finish loss from aggressive organic solvents, and is friendly to the environment. The successful combination of these elements has led to the launch of the first national chain of dry cleaning stores to offer liquid CO2 garment care to the consumer.

The PIX Module Software: Combining Life Cycle Assessment with Activity-Based Costing to Reduce Global Environmental Impact and Sustain Industrial Profitability: The LCAPIX module is the first commercially available software package that simultaneously allows the user to perform both Activity Based Costing and Life Cycle Assessment (LCA). By using an industrial engineering approach employing drivers and driver values, the model and relational database provide a unique combination of two strategies that complement and enhance the implementation of an Environmental Management Strategy (EMS). This approach has strong appeal to those involved in any manufacturing sector &#; the point source for more than 50% of "undesirable effluents" affecting our global climate.

The conventional approach to LCA studies has been the application of "simple" mass and energy balances to manufacturing facilities. This approach is useful in providing guides for cost reduction and large-scale beneficial changes, but it requires difficult definitions of system boundaries, time-consuming data collection, and limits final inventory calculations. In contrast, the LCAPIX module provides a stand-alone software application that can analyze processes on a product basis, determine environmental load centers, and allow for development of a comprehensive database. The software package is a multifunctional tool in that it provides for inexpensive, rapid, and simple, strategic or environmental LCA comparisons of any product, process, or service.

The Process Greenness Scorecard: Design for Environmental Health and Safety Through Green Chemistry: The synthetic and semi-synthetic processes utilized in the manufacture of pharmaceuticals at Bristol-Myers Squibb are chemical-intensive and involve the use of many solvents and reagents. The organic chemistry developed at the earliest phases of research and development is essentially geared to producing complex organic molecules through convenient "building block" chemicals. Many of these building block materials are highly regulated chemicals. Process developers use these chemicals because they are widely available and may accelerate the development process and launch of critical life saving and enhancing drug products.

The Process Greenness Scorecard is a tool that helps Bristol-Myers Squibb research chemists and engineers to identify materials of concern and to evaluate potential substitution with environmentally preferable process materials. In addition, the scorecard enables users to consider process conditions that minimize the impact of using these materials. Controlling the use of reagents and solvents, increasing process yields, and reducing waste streams are a few of the factors measured in the scorecard.

The scorecard encourages early product pipeline work to dramatically improve the environmental impact of commercial-scale pharmaceutical operations. It is a means of driving green chemistry by directly measuring progress in designing processes that reduce hazardous solvent use, waste generation, employee exposure, and process hazards.

The Radiance Process: A Quantum Leap in Green Chemistry: The Radiance Process is a novel, dry, nontoxic cleaning technology for surface preparation. It employs the quantum mechanical effects of laser light in combination with an inert gas, ordinarily nitrogen, to clean surfaces. The light lifts the contaminant from the surface and the flowing gas sweeps it away without the pollution now associated with surface cleaning. The process has potential application in the manufacturing of semiconductors, photomasks, flat panel displays, storage media, and optics. Radiance cleans without emissions, discharges, or wastes, thus preventing pollution and conserving natural resources. It is designed to supplant the use of wet chemicals in surface cleaning and preparation.

The Removal of Oxides of Nitrogen by In Situ Addition of Hydrogen Peroxide to a Metal Dissolving Process: The removal of oxides of nitrogen (Ox) by in situ addition of hydrogen peroxide to a metal dissolving process was developed by Mallinckrodt Inc. Salts are produced by dissolving metals in nitric acid. During the dissolving process approximately 30 tons per year of Ox emissions are generated. A study was completed to determine the best method for reducing Ox emissions from the dissolving process. The literature states Ox is required to catalyze the dissolution reaction.

This theory was challenged; Mallinckrodt Inc. proposed to oxidize the Ox back to nitric acid by adding hydrogen peroxide directly to the process, thus completely eliminating Ox emissions. This proposal was demonstrated in the laboratory. Next, two trial runs using this technology were completed. In both cases the formation of Ox was completely eliminated. Based on the information from the trial runs, manufacturing, with help from research and development, designed a hydrogen peroxide addition process, which was successfully introduced. The new process has eliminated the generation of 30 tons per year of Ox while at the same time reducing nitric acid usage by approximately 109 tons per year. Also, 13 million gallons per year of scrubber waste water were eliminated since the scrubber is no longer needed.

The Replacement of Hazardous Organic Solvents with Water in the Manufacture of Chemicals and Pharmaceuticals: The use of water as the primary solvent is a realistic approach to green chemistry and is a very desirable approach for reducing hazardous organic solvents from plant inventories. Multiphase reactors have been developed at the New Jersey Institute of Technology and other universities that use water as the reaction medium in order to avoid the use of hazardous organic solvents in the manufacture of pharmaceuticals and specialty chemicals. This is the first technology to show that free radical bromination of organics can be carried out in aqueous systems. A unique semicontinuous droplet reactor also has been developed for epoxidations. Before pollution prevention became fashionable, organic chemists found that water-based reactions gave higher yields at faster rates under milder conditions than organic solvent-based reactions. This is incentive enough for process change. The fact that these methods offer a new 'non-end-of-pipe" method of eliminating volatile organic compounds adds a major incentive for process modification.

The SYNGEN Program for Generation of Alternative Syntheses: Thousands of organic chemicals are synthesized annually on an industrial scale, and their manufacture can often lead to environmental problems. If alternative syntheses that create fewer hazardous wastes and less pollution could be found, a number of these problems could be solved. No one would claim that the synthesis routes currently in use are the only ones possible, or even that they know them to be the best routes. Indeed it is easy to show that the number of possible synthesis routes to target molecules of even modest complexity is usually enormous. However, organic chemistry has traditionally not provided any logical protocol for the systematic design of synthesis routes to any target molecule. If there were such a protocol, other routes to any industrial synthesis target could be systematically explored, and their relative impacts on the environment examined.

Although a number of computer programs have been written, few have come out of their academic sources into the world of chemical industry for practical use, and essentially none have been viewed there as successful. The SYNGEN program developed by Professor James B. Hendrickson at Brandeis University is different from the others in conception and practice. It aims at surveying all possibilities and reduces the vast number of these possibilities quickly and stringently to focus on only the shortest and cheapest routes following a criterion of economy. It is self-consistent and not interactive, and so avoids skewing the results to favor operator"s preconceptions. On this base it now adds evaluation of environmental hazards to the best routes selected.

Earlier version of SYNGEN were also not successful in the practical world, partly because chemists did no fully understand its logic and also because the program too often generated reactions which the chemists regarded as chemically unworkable. To clarify the logic for chemists, the program first focuses on the criteria of the target skeleton from available starting skeletons. then it presents the ideal synthesis--of construction reactions only, to create the target just by sequential constructions uniting these starting skeletons. Finally the digital basis rigorously but compactly defines all possible molecular structures and their reactions.

This basis allows the new SYNGEN program to propose all the short alternative syntheses of any product from real starting materials in terms both of their cost and their environmental impact. This makes possible for the first time an unbiased collection of real benign synthesis routes for the production of commercial chemicals. With this tool we can truly explore alternatives for green chemistry.

The University of California, Santa Barbara Green Chemistry Initiative: The University of California, Santa Barbara Green Chemistry Initiative (UCSB GCI) addresses the challenges of reducing hazardous waste in UCSB research labs and laboratory-based courses. Focusing on the campus is essential, as it is the training ground for future chemists. These efforts started with programs beneficial to the Chemistry department. The first program dealt with replacing mercury thermometers with less-hazardous, alcohol-based thermometers. The second was the introduction of the UCSB Surplus Chemical Program and website, which allow researchers to exchange chemicals with each other. These programs helped the Student Intern LabRATS build trust with the faculty in the Chemistry Department.

With 1,100 undergraduate students in 130 laboratories each week at UCSB, there are huge potential savings. Although lab manuals already used some microchemistry, the LabRATS did research to see how much more waste they could reduce. For example, their manuals had an experiment with lead nitrate that might be replaced by less-hazardous zinc nitrate. To test this, they ran the regular experiment with lead nitrate alongside the revised experiment with zinc nitrate. Although this was unsuccessful, the model they developed allowed them to investigate alternative, less-hazardous substitutions in any learning laboratory. Currently, they are extending their efforts and model into organic chemistry with Professor Bruce H. Lipshutz and his ideas for aqueous alternatives to organic solvents.

Their multipronged approach to reducing hazardous waste has led faculty and students to interact on multiple levels to think about implementing green chemistry. Even after the failure of the zinc nitrate substitution, students and collaborators pushed forward with new ideas and approaches. This work has been supported by two grants from the Green Initiative Fund. The UCSB GCI has been leading efforts under the university&#;s Campus Sustainability Plan, which requires the university to achieve net zero waste by .

The Use of Chlorine Oxide, the Foundation of Elemental Chlorine-Free Bleaching for Pulp and Paper, as a Pollution Prevention Process: The use of chlorine dioxide as part of a pollution prevention process to substantially or completely replace chlorine in the first stage of chemical pulp bleaching is a unique implementation of chlorine dioxide chemistry. It can be applied to the entire bleached chemical pulp and paper industry, both in the United States and abroad. By employing raw material substitution and process modifications, this technology has allowed the pulp and paper industry to meet the source reduction objectives of the Pollution Prevention Act of . With this new application of sophisticated chlorine dioxide chemistry, the pulp and paper industry virtually eliminated dioxin from mill waste waters and our nation&#;s water bodies.

This technology has answered the industry&#;s calls for a more benign chemical pulp bleaching agent. Virtual elimination of dioxin from mill waste waters and continuing nationwide ecosystem recovery provide a strong measure of chlorine dioxide&#;s success and the industry&#;s environmental progress. In fact, downstream of U.S. pulp mills bleaching with chlorine dioxide, fish dioxin body burdens have declined rapidly and aquatic eco-systems continue to recover. For example, the Mead Paper Company&#;s Escanaba Mill in Michigan implemented pollution prevention strategies beginning with the use of low precursor defoamers in , followed by increased substitution of chlorine by chlorine dioxide in . In less than four years, downstream dioxin body burdens declined more than 90 percent. These indicators of progress toward broader eco-system integrity demonstrate the success of chlorine dioxide as "green chemistry."

The Use of Green Unikleen in Oil Spill Clean-Up, Both on Land and in Water: IPAX&#;s flagship product, Green Unikleen, will improve oil spill clean-up, both on land and at sea. Green Unikleen is a biodegradable, nontoxic, concentrated cleaner and degreaser that can be used with any manual or mechanical cleaning equipment. It is water-soluble and has no volatile organic compounds (VOCs). Its formula includes sodium silicate, Biosoft S-100, Neodole 23-5 (Shell Oil; includes a mixture of C12-13 alcohol ethoxylates), a tetrasodium salt, and Surco SXS (40&#;42 percent sodium xylene sulfonate and up to 2 percent sodium sulfate in water).

Green Unikleen has been used extensively for washing automotive parts; it replaces VOC solvents and reduces hazardous waste. IPAX has research results demonstrating that Green Unikleen is an improvement over current technologies to clean up oil spills on land. Green Unikleen is able both to return oil-saturated soil back to a state that will support plant growth and to allow recovery of the oil for its original use. Together with added biosupplementation, Green Unikleen can reduce residual petroleum in treated soil to 0.1 percent, the maximum concentration allowed for agriculture.

For oil spills at sea, Green Unikleen has been shown to be a very effective dispersing agent as well as a fire-preventive and -extinguishing additive. Green Unikleen breaks oil spills into small droplets, forming a thin emulsion that disperses in the water column. In dispersed form, the oil is subject to natural degradation by marine microorganisms. Green Unikleen can be effective in dispersing most liquid oils and liquid water-in-oil emulsions with viscosities below about 2,000 centistokes. In a fire-extinguishing demonstration, Green Unikleen and water (1:10) required less than 2 minutes to extinguish a fire of benzene, diesel fuel, and crude oil that had been allowed to heat up to over 2,000 degrees before treatment. Green Unikleen is available commercially, and IPAX has applied for a patent for its technology.

The Use of Soluble Polymers to Recover Catalysts and to Control Catalytic Reactions: New strategies for the use and recovery of homogeneous catalysts and for carrying out chemical processes are of increasing interest because of problems associated with the use of organic solvents and the costs associated with purification and the removal and disposal of byproducts. This nomination recognizes the work by Bergbreiter&#;s group at Texas A&M, which uses polymeric ligands and new separation strategies to facilitate homogeneous catalysis. This technology uses the well-known properties of polymers to recover and separate catalysts and ligands for reuse.

By employing relatively simple polymer chemistry, a wide variety of known homogeneous catalysts can be attached to such polymers without significant alteration of their reactivity or selectivity. Separation and recovery strategies that use solid/liq-uid separation of precipitate polymers or liquid/liquid separations of polymer solutions/product solutions have both been demonstrated. The utility of simple linear polymers in the formation of aqueous and fluorous phase soluble catalysts has also been demonstrated by this work. Finally, this technology has also demonstrated a unique approach to regulate and control reactions using soluble polymer-bound "smart" ligands that precipitate on heating.

The Use of Vitamin C To Neutralize Oxidants Such as Chlorine in Drinking Water Which Is Often Discharged to the Environment: The chlorination of public drinking water has proven to be a significant breakthrough in the prevention of disease in humans. However, chlorine, even in minute quantities, is toxic to fish and other aquatic life. The water (and wastewater) industry must use extreme caution when operating their systems so that chlorinous discharges do not adversely impact aquatic life downstream.

Industry has used specific sulfur-based compounds to neutralize chlorine. However, during dosing applications these sulfur-based chemicals can present distinct health hazards to the operator and/or fish that occupy nearby streams.

It was discovered that vitamin C in the form of ascorbic acid, is an effective and affordable neutralizer of oxidants such as chlorine. Vitamin C is safer than other chemicals which can cause serious respiratory problems in humans and deplete oxygen levels in the water. Vitamin C is the only dechlorination reagent with a NFPA rating of 0,0,0.

Vitamin C is just as effective, and in other ways it is better than all other chlorine neutralizers. However, vitamin C offers a unique advantage. It synergistically boosts the immune system of aquatic life while simultaneously removing toxic disinfectant dangers from their fragile habitat.

Both humans and fish benefit from this new technology.

The Zyvax "Watershield" Mold Release: Zyvax Watershield is a unique material for its intended purpose as a mold release for aerospace adhesively bonded parts or fiberglass and other composite aircraft/spacecraft structures. It contains no volatile organic compounds, ozone depleting chemicals, or other solvents and materials considered hazardous by EPA or state or local regulatory agencies. Furthermore, as a wiping agent, the Watershield could be used as a precleaner for molds for both initial and subsequent applications. And its residues could be easily removed with water or water soluble cleaners, therefore significantly reducing the need for solvents to remove Watershield residues prior to painting or sealing. It therefore avoids environmentally sensitive materials not only in its formulation, but also by its proper use.

Watershield was so effective a release agent that its use was enthusiastically adopted by a number of aerospace companies who found they could eliminate significant solvent use, satisfying environmental, health, and safety concerns. Watershield eliminated hazardous materials in an area of aerospace manufacturing that EPA had exempted from its regulation because of the absence of available replacement technology and the critical nature of the application. Therefore it allowed the elimination of hazardous material without an absolute regulatory requirement.

Tide Coldwater®: Energy Conservation through Residential Laundering Innovation and Commercialization: Procter & Gamble has recently commercialized a patented, breakthrough chemical innovation in environmentally friendly cleaning technology to provide superior cleaning and significant energy savings in low-temperature (60 °F) wash water. Over 7 million U.S. households have used Tide Coldwater® since its introduction in North America in January .

Tide Coldwater® uses surfactant systems designed to be more hydrophobic than other detergents. The liquid detergent formula uses an optimized combination of alcohol ether sulfate, linear alkyl benzene sulfonate, and ethoxylated zwitterionic and alkyl amine surfactants. In combination with a builder/chelant to sequester metals, soil suspension systems, enzymes (protease and amylase), and brightener systems, this proprietary surfactant system delivers superior cleaning performance in cold water. The powder detergent formula is based on high-solubility alkyl sulfate, a proprietary branched surfactant. It also contains sodium nonanoyl oxybenzene sulfonate, a proprietary bleach activator, along with other additives in common with the liquid version.

In blind consumer tests, Tide Coldwater® provides superior cleaning in cold water relative to detergents formulated for warm and hot water. Without sacrificing performance in stain removal or whitening, consumers can save up to $63 per year in home energy costs, reducing greenhouse gas emissions from fossil-fueled power plants. Using a peer-reviewed model for residential energy use, Procter & Gamble estimates that Tide Coldwater® will reduce the fraction of residential energy used to heat water by up to 26&#;36 percent, with an associated reduction in carbon dioxide (CO2) emissions of up to 1,259 pounds per household per year.

The potential benefits of this innovation are significant: if everyone in the United States switched to cold water for laundry, the potential energy savings would be 70&#;90 billion kilowatt-hours per year, representing up to 3 percent of the nation&#;s energy consumption. These savings are the equivalent of 26&#;34 million tons of CO2 per year, representing over 8 percent of the CO2 reduction target for the United States set in the Kyoto Protocol.

TimberSIL®: Toxic, waterborne chemical infusion processes are typically used to pressure-treat lumber and industrial wood products. The new TimberSIL® glass wood chemistry uses environmentally friendly, nontoxic, sustainable chemicals and processes to protect wood.

To produce TimberSIL® glass wood, Timber Treatment Technologies converts sodium silicate, a common industrial chemical, into amorphous glass in situ with a suitable substrate such as wood or another natural fiber. Amorphous glass forms as millions of microscopic ribbons become intimately attached to the wood fiber to make TimberSIL® lumber. Production of the proprietary TimberSIL® formulation uses no petroleum products. Most of the wood used comes from renewable, sustainable, southern yellow pine trees. In addition, the processing of recycled rice hulls to make sodium silicate, a primary component of the glass wood chemistry, requires no energy, has no greenhouse gas emissions, and produces two times more energy than the combustion of coal.

TimberSIL® glass wood can take any shape that can be milled by existing wood mills. It is stronger, more stable, and more resistant to fire, rot, and decay than pressure-treated wood. It can readily be used wherever long-lasting wood materials are the proper design and economic choice. The strength of TimberSIL® lumber means that less lumber is needed to achieve the same building integrity.

TimberSIL® technology can eliminate many toxic materials that are widely used in wood treatments. For example, every mile of TimberSIL® rail ties that replaces creosote rail ties eliminates 108,000 pounds of crude oil. Over its lifetime, one mile of TimberSIL® railroad ties displaces over 9,300,000 pounds of carbon dioxide (CO2). With no toxic mode of action and increased strength, TimberSIL® glass wood is an environmentally superior choice for residential, commercial, and industrial applications. Since , installations of TimberSIL® glass wood have totaled approximately 2.7 million board-feet in the United States.

Tin- and Copper-Compatible Conductive Adhesive for Lead-Free Electronic Circuit Assembly: Tin&#;lead eutectic solder is currently the most common product used to attach electronic components on circuit boards. Lead, however, is a known toxin. Because lead can leach into the environment, the European Commission in its Waste Electrical and Electronic Equipment Directive enacted legislation in July mandating recycling of consumer electronics containing lead. This has prompted electronic circuit assemblers to seek an alternative attachment product. Conductive adhesives have also been used for years, but their use has been limited to attaching palladium&#;silver-, silver-, and gold-terminated components on both ceramic hybrid boards and flexible polyester circuits. Previous conductive adhesives were not stable on low-cost tin- and tin&#;lead-terminated components.

Emerson & Cuming&#;s novel, patented chemistry allows it to achieve stable contact resistance and stable adhesion under damp-heat and high-temperature aging conditions with tin, tin&#;lead, and copper finishes. Compatibility with these finishes was not possible in the past. This compatibility was achieved by preventing galvanic corrosion on these less expensive, non-noble metal finishes. The incorporation of a corrosion inhibitor and a low-melting alloy into the adhesive formulation prevents oxidation on these finishes under extreme environmental conditions and leads to stable performance over time. About 40 major electronic circuit assembly companies currently purchase these Emerson & Cuming adhesives. These customers are from very demanding industry sectors including the automotive, medical, military, consumer electronics, and telecommunications sectors. Over the last 3 years, these adhesives have effectively eliminated the use of 12 metric tons of tin&#;lead eutectic solder. By , this conductive adhesive technology will be replacing about 40 metric tons of solder per year.

Total Impact Program - An Environmentally Preferable Program for Laundry: Anderson Chemical Company&#;s Total Impact Program® employs chemistry with a more positive environmental profile for human health and the environment than that used in conventional laundry systems. The TIP® program incorporates a neutral pH detergent enhanced with enzymes and surfactants that pose low environmental concerns, oxygen bleach, and biodegradable softeners. The program also saves water and energy and extends fabric life. The program targets three main impact areas: user safety and health, environmental impact for pollution prevention via source reduction, and efficiency through resource consumption reduction by decreasing processed pound costs (decrease in water consumption, energy costs, and reduced effluent costs resulting from volume and pH factors).

Totally Degradable Plastic Additives (TDPATM): In order to be considered environmentally degradable, a plastic must disintegrate by some mechanism to lower molecular weight fragments that are susceptible to microbial attack and, ultimately, elimination as biomass, gaseous byproducts, and water. Polyolefins are usually regarded as environmentally inert. To make them environmentally degradable, mechanisms must be identified to convert these hydrophobic and high molecular weight plastics into water-wettable, friable fragments of very low molecular weight to render them microbially susceptible. It is well established that abiotic oxidative degradation of polyolefin films produces oxidized molecular fragments of very low molecular weight in the range of a few hundred to a few thousand Daltons (Profs. A-C. Albertsson, C. David, and others). Such fragments are substantially biodegradable as measured by carbon dioxide evolution in a variety of aerobic environments.

EPI developed and introduced TDPA(TM) additives for use at low levels (< 10 weight percent), to specifically promote polyolefin oxidative degradation in the presence of heat and/or near-UV light. Adjusting the components in TDPA(TM) additives and the blend proportions with polyolefin, controls the rate and time for polyolefins to degrade to low molecular weight fragments and hence biodegrade. This control permits use in a wide range of applications and disposal sites.

TractionBack®: Alternative Green Adhesives Solutions for Textile Composites Used in Commercial Buildings: Poor indoor air quality is one of the top five environmental health risks associated with building interiors. Traditional modular carpet installation requires adhesives and sealants that contain such volatile organic compounds (VOCs) as formaldehyde and 2-ethyl-1-hexanol. Carpet installation may also require surface preparation including sanding and removal of old adhesive, which degrades air quality further.

Milliken&#;s TractionBack® antiskid, adhesive-free backing is a thin coating formulation applied to the felt on the bottom of carpet tile. The formulation is an amorphous ethylene&#;propylene copolymer that is tackified with a hydrocarbon resin and tall-oil rosin, a biobased component. The raw materials in the formulation have almost no measurable VOCs in the solid state. TractionBack® high-friction coating for modular carpet eliminates the need for onsite adhesive applications and repairs traditionally required for new and replacement installations, thus eliminating related VOCs. Milliken estimates that each year TractionBack® eliminates the use of 400 tons of sealants and adhesives as well as 16,000 five-gallon containers for the sealants and adhesives.

TractionBack® eliminates chemical pollutants such as adhesives, floor primers, sealants, and other VOCs; eliminates biological pollutants such as mold and bacteria; and reduces the particulate hazards of sanding and surface preparation. Additional environmental benefits include (1) energy reduction during production; (2) waste reduction during installation; (3) waste reduction to landfills by extending product life because individual tiles can be repositioned or replaced easily; (4) reduction of downtime for building spaces; (5) incorporation of biobased raw materials; and (6) removal of poly(vinyl chloride), PVC, which has environmental issues related to its production, installation, and eventual disposal. TractionBack® uses fewer resources in its manufacturing and installation, which reduces both its eco-footprint and its associated waste. TractionBack® has been on the market since . Milliken revised its formulation for TractionBack® to include biobased raw materials in .

Tru-Core® Protection System for Wood: Wood is the most widely used residential building material in the United States. Its environmentally positive characteristics include excellence as a carbon sink, low embodied energy, and high sustainability. Among its few shortcomings, however, is its relative lack of durability due to its susceptibility to decay and insect attack. Preservatives and insecticides can improve the durability of wood significantly, but methods to deliver these protectants into wood are largely based on old, environmentally damaging technologies. Kop-Coat developed Tru-Core® Protection System to treat wood in an environmentally positive manner.

The Tru-Core® system incorporates the principles of green chemistry in several ways. For example, most conventional treatments for wooden window frames and doors use petroleum-based solvent carriers, such as mineral spirits, that emit volatile organic compounds (VOCs). The Tru-Core® process uses water as the carrier, resulting in a significant reduction in organic solvent use. Because the Tru-Core® process uses only a small amount of water to carry the preservatives, it also eliminates the energy-intensive step of re-drying wood after treatment. The Tru-Core® system employs a unique chemical infusion process that includes nonvolatile, highly polar bonding carriers (amine oxides in water) that penetrate the cellular structure of wood to deposit and bind wood protection chemicals (preservatives and insecticides) within the substrate.

Buffers such as borates maintain a basic pH that inhibits the natural acids present in wood, allowing the amine oxides and preservatives to penetrate rapidly. Tru-Core® extends the service life of wood at a cost that is less than one quarter the cost of the closest competing treatment technology. In , EPA registered the patented Tru-Core® technology as a wood preservative. In , Tru-Core® technology was used in the dual treatment process for approximately two million railroad ties. Tru-Core® Type 1 is currently undergoing evaluation by ICC-ES (International Code Council Evaluation Service) for acceptance into the International Building Code.

Two-Stage Catalyst for Ox Reduction, CO Oxidation, and Hydrocarbon Combustion in Oxygen Containing Exhaust Mixtures: A unique catalyst system has been developed for removing oxides of nitrogen from automobile exhaust. These catalysts operate in a lean burn environment (excess oxygen in the engine) and represent a significant improvement over existing technologies. Automobile manufactures prefer to operate engines with excess oxygen to completely combust the fuel, improve efficiency, and reduce pollution. The principle impediment to designing such an engine is the inability of existing exhaust system catalysts to reduce oxides of nitrogen in the presence of oxygen.

Some progress has been made in resolving this problem, specifically, copper impregnated zeolites are found to reduce oxides of nitrogen in the presence of oxygen. This material is not, however, without problems, including, low conversion of the oxides of nitrogen. We have demonstrated a two stage catalyst system that significantly improves the conversion of oxides of nitrogen to environmentally acceptable gases. We have shown that a heterogeneous catalyst system consisting of two beds in sequence, each containing a different catalytic material, is superior for the removal of Ox from exhaust streams containing oxygen, to the current generation of single stage catalysts.

The character of each of the catalyst beds is fairly specific. The first bed consists of any high surface area refractory oxide such as silica, alumina, titania, zirconia, ceria, zeolite, etc. The second bed consists of any metal loaded catalytic material known to reduce Ox species in the presence of oxygen such as copper exchanged zeolite (e.g. Cu-ZSM-5). Many other materials, including zeolites exchanged with other metals, high surface area silica or alumina impregnated with metals, also are known to reduce Ox species in such environments, and thus also are candidates for second bed materials.

Ultrapure Carbon and Carbon&#;Nitride Nanomaterials Derived from Simple Pyrolyses of Nearly Chock-Full Nitrogen Compounds: Currently, carbon-based nanomaterials are manufactured primarily from residual oils or hydrocarbon precursors at extremely high temperatures and applied pressures. The toxic fumes and hazardous waste generated by these high-temperature, high-pressure reactions are detrimental to the environment and cause personal health risks.

Dr. Huynh has developed solventless pyrolytic conditions to prepare ultrapure carbon nanoparticles and diamond-hard carbon&#;nitride nano-architectures from novel high-nitrogen compounds, the so-called nearly chock-full nitrogen compounds. This requires simultaneous manipulation of melting points, heating patterns, and decomposition temperatures. Dr. Huynh&#;s solid-state pyrolyses can be tuned controllably to produce nanomaterials of the size, shape, morphology, density, dimension, and nitrogen content required for a wide variety of applications. S

ome of these applications include next-generation computer chips, kinetic-energy penetrators with enhanced lethality, better insulation materials, tougher and harder cutting tools, high-sensitivity sensors, automobiles with greater fuel efficiency, aerospace components with enhanced performance characteristics, and longer-lasting medical implants. Unlike hydrocarbon feedstocks that contain primarily C&#;H and C=C bonds, these high-nitrogen compounds contain multiple C=N bonds and N=N linkages that make their thermal decompositions downhill processes owing to the extrusion of nitrogen gas as the only byproduct. Multiple N=N linkages make these high-nitrogen compounds nonvolatile and viscous, so they are easy to handle.

With Dr. Huynh&#;s innovation, ultrapure carbon and carbon&#;nitride nanomaterials can be manufactured quantitatively with absolutely no hydrogen-incorporating byproducts. The manufacture of these carbon-based nanomaterials from high-nitrogen compounds is advantageous and cost-effective. This process abolishes specialized facilities and equipment, eliminates personal exposure to high-temperature and applied-pressure reaction conditions, eradicates lengthy preparation and complicated purification, and drastically reduces production costs associated with liability insurance and the removal of toxic fumes and hazardous waste. Essentially, Dr. Huynh has creatively applied high-nitrogen chemistry to solve environmental and nanotechnological problems. One patent has been granted for this technology; another is pending.

Unconventional High-Efficiency Green Synthesis: In the area of alternate reaction conditions, Professor Bose and his group have conducted microwave chemistry with limited amounts of solvents or even no solvents. Many useful synthetic reactions are exothermic and require only initiation by a short burst of microwave energy to go to completion. This "Microwave Jump Start", as devised by Professor Bose, would save energy and, thus, reduce the cost of producing pharmaceuticals. Second, Professor Bose has developed "Grindstone Chemistry" for conducting solvent-free exothermic reactions for pharmaceuticals on small and large scale by grinding reagents together.

Using friction-activating agents, he has extended this method to solid/liquid and even liquid/liquid reagents. Third, he has devised water-based biphasic media for exothermic synthetic reactions that are complete in approximately 20 minutes, as compared to several hours for classical methods. For these exothermic reactions, he stirs the reagents (no solvent) and a catalyst in a large volume of water. Solid products separate as crystalline material in good yield. These solvent-free techniques constitute energy-efficient green chemistry. Indofine Chemical Company has tested Professor Bose&#;s water-based biphasic media for the synthesis of coumarin-3-ester, obtaining excellent yield and high purity. In the area of alternate pathways, Professor Bose and his group have used nontoxic reagents and new oxidizing agents to develop an eco-friendly alternative synthesis of Dapsone, an anti-leprosy drug also used for AIDS patients.

Uncoupling Biochemical Processes for Enhanced Biological Efficiency: Advanced BioCatalytics developed and patented naturally produced chemicals using a protein-based system called C.O.D.E.TM. This led to a platform technology it calls Molecular KineticsTM, which uncouples oxidative phosphorylation in microbial metabolism such that the breakdown of organic compounds by microbes accelerates dramatically. The C.O.D.E.TM uncoupling factor signals microbes to view biofilms as nutrients and to digest them. C.O.D.E.TM products meet FDA guidelines for food contact, are approved by the National Science Foundation (NSF) for potable water use, are safe for the user, and improve the environment in many ways. In , the company commercialized this technology as Accell®.

In industrial and municipal wastewater treatment facilities, Accell® can consistently reduce sludge production and its associated costs by 30 percent or more. In addition, the treatment plants operate more efficiently, with improved effluent quality, better sludge settling, increased plant throughput capacity, and the opportunity to reduce aeration costs by over 30 percent in some cases. Aeration is the greatest user of energy in these facilities. Using Accell® in its wastewater treatment plant saved one industrial customer $5 million in capital equipment costs, reduced its operating costs, and saved over $200,000 per year in environmental surcharges.

The formation of biofilms in cooling systems contaminates heat exchange surfaces and fouls reverse osmosis filtration membranes drastically, corroding and degrading substrates and reducing energy efficiency. C.O.D.E.TM can reduce the toxic biocides typically used to control biofilm and biofouling by over 90 percent.

In seawater desalinization, the cost of energy to pump water through the membranes is the greatest operating expense. The process typically requires frequent cleaning cycles that can degrade the expensive membranes. C.O.D.E.TM treatment can save over 20 percent of energy use by reducing both operating pressures and cleaning cycles while increasing both throughput and salt rejection.

Use of Carbon Dioxide as an Alternative Green Solvent for the Synthesis of Energetic Thermoplastic Elastomers: Thermoplastic elastomers based on triblock oxetane copolymers containing azido functional groups offer an improved binding material for solid, high-energy formulations. Current technology uses chemically cross-linked energetic prepolymer mixes that introduce the problems of thermally labile chemical linkages, high end-of-mix viscosities, and vulnerability to premature detonation. These materials are also nonrecyclable and generate large amounts of pollution during disposal[.] The use of energetic thermoplastic elastomers eliminates the need for chemical cross-linking agents, makes processing easier due to their low melt viscosities, and eliminates the need for solvents during casting. Their superior processing qualities and the ease of demilitarization and recycling make these materials a much more environmentally sound choice for energetic binders.

However, their synthesis still involves the use of large quantities of toxic chemicals, such as methylene chloride, as solvents. Carbon dioxide has been proven to be a viable, environmentally responsible replacement solvent for many synthetic and processing applications. It is cheap, easily recyclable, and available from current sources. Research at the University of North Carolina has shown that carbon dioxide is a viable solvent for the polymerization of vinyl ether monomers. Furthermore, polyoxetanes can be polymerized in carbon dioxide with molecular weight, molecular weight distribution, and functionality maintained. The University of North Carolina has demonstrated the synthesis of both nonenergetic and energetic homopolymers and random copolymers.

Use of Solid Catalysts in Pollution Prevention in the Nitration of Aromatic Compounds: Nitration reactions of aromatic substrates are important for the industrial production of a wide variety of essential chemicals, chemical and pharmaceutical intermediates, and explosives. The most widely used practical nitrating agents are mixtures of concentrated nitric and sulfuric acids. These homogenous systems are very corrosive and present serious environmental problems caused by spent acid disposal. This traditional nitration process is a notoriously unselective reaction resulting in statistical distribution of ortho, meta, and para substituted nitro isomer products. Also, this process requires an aqueous washing stage to remove oxidized byproducts that result in a waste stream that is environmentally unsuitable and costly to treat.

Therefore, there is a great need for a new nitration method that can overcome problems associated with the current mixed-acid nitration process widely used in the industry. An attractive nitration process has been developed to provide para-nitro isomer with high regio-selectivity in alkyl and halo benzenes under mild conditions using concentrated nitric acid and a solid catalyst. Several aromatic substrates were nitrated using industrial grade nitric acid as the nitrating agent and commonly available, cheap zeolite solid acid catalyst to yield commercially valuable para-nitro isomer in good yield. The increase in the regioselectivity of the commercially more desirable para-isomer is due to the shape selective characteristics exerted by the solid catalyst.

This process has a number of practical advantages: significant improvements in regioselectivity favoring para-isomer in aromatic substitution in good yields, ease of separation and recovery of products, and low cost. The solid catalyst can be easily regenerated and reused by recalcination. It represents an attractive method for the clean synthesis of a range of nitroaromatic compounds. For example, this process eliminates the formation of unwanted meta-nitrotoluene isomer and other byproducts in the production of 2,4,6-trinitrotoluene (TNT) thus preventing the Red Water pollution problem. Regioselective formation of commercially more desirable p-nitro isomer has unique applications in the polyurethane and dye industry. In this respect, the polyurethane division of Bayer Corporation is currently evaluating this technology to implement in their polyurethane and dye production facilities.

Using Chemistry and Engineering Technology to Reduce Volatile Organic Compound (VOC) Emissions and Eliminate Hazardous Process Waste in the Printing Industry: Highland Supply Corporation (HSC) manufactures decorative packaging for the floral industry using flexographic and rotogravure printing presses as part of its production processes. Until , HSC used only solvent-based inks that contained 50% or more VOCs by weight.

During , however, the executive management of HSC accelerated its efforts to develop a viable water-based ink system and issued a corporate policy directing the reduction of VOC emissions and hazardous air pollutants (HAPs), which are harmful to human health and the environment. HSC researched installing air pollution control equipment, but chose to replace its solvent-based ink system with a cleaner water-based system. Commercially available water-based inks contained approximately 20% VOCs by weight, however, and had lower print quality. HSC elected to develop its own water-based ink system to reduce VOC content further and to increase print quality.

Within the last five years, HSC has refined its technology: now its water-based ink system contains less than 0.70% VOCs by weight. HSC continues aggressive research to lower this percentage. By switching from solvent-based to water-based printing inks in all of its facilities, HSC has reduced VOC emissions and eliminated HAPs and hazardous process waste. Water-based inks also cost about 40% less than solvent-based inks to print the same area. Its Highland, Illinois plant released 198.5 tons of VOCs in , but releases less than two tons per year today. I

n , HSC spent over $100,000 to dispose of hazardous process waste from that plant; today there are no such wastes, so it spends nothing. The company now recycles all of its water-based inks by reformulating excess inks into useful ones. HSC thoroughly reviews product information and controls all items that enter its facilities based on strict environmental, health, and safety criteria.

Utilization of High Performance, Environmentally Compliant Chemicals: GREEN LINE Adhesive, Sealant, and Coating Technologies: Astutely aware of the national strategy for protecting the environment and promoting energy efficiency in buildings, American Chemical Corporation developed the GREEN LINE, a complete stock of specialty adhesives, sealants, and coatings that utilize environmentally compliant polyvinyl acetate (PVA), acrylic, latex, and epoxy resins technologies. All methodologies meet Best Available Technology (BAT) standards for minimizing VOC exposure, health risks, and hazardous handling practices.

Concurrent with the technical development of GREEN LINE products was the conceptualization of Cost Benefit Algorithms and Dynamic Labeling, which permit federal managers to determine the degree of 'green&#; compliance of the core materials used to manufacture the products and of the environmental improvements intended by use of such materials. Federal managers and their staffs are provided with reliable information that can help them make energy-saving, water-conserving, and maintenance improvements that solve environmental problems and provide for worker safety. GREEN LINE products have been successfully used to (1) reduce both energy use and the environmental impacts of HVAC and air handling distribution system repairs and upgrades, (2) conserve potable water resources by facilitating the repair and rehabilitation of treatment, storage, and distribution systems, and (3) repair U.S. Naval ship structures.

Utilization of Neutral Cleaners for Reducing Environmental and Health Impacts: ESS neutral pH aqueous cleaners have replaced the environmental and safety hazards of solvent and aqueous alkaline cleaners in many industrial applications.

Unlike alkaline cleaners that are comprised mostly of high pH inorganic ingredients, ESS neutral biodegradeable cleaners are completely organic, comprising of highly specialized detergents and wetting agents. The pH of ESS neutral products is 7.0-7.9. The neutral pH of ESS cleaners makes them noncorrosive, enhancing worker safety while reducing mechanical wear and environmental impact. Unlike alkaline cleaners, there are no chelators in ESS neutral cleaners that can contribute to high heavy metals in wastewater.

The cleaning mechanism is very different between alkaline and neutral cleaners. Alkaline cleaners tend to saponify and emulsify process soils during the cleaning. This soap/soil interaction makes it difficult to remove oils from solution and leads to short wash bath life and water contamination. Thus, much wastewater can be generated. These hazardous cleaners historically leach heavy metals into solution to produce regulated waste.

ESS solutions wet the process soil so there is no strong soap/soil interaction. This allows oils to split out of solution for easy recovery. With the oils removed, the wash bath life lasts longer and wastewater generation is significantly reduced.

UV-Curable Pressure Sensitive Adhesive: UV-curable Pressure Sensitive Adhesives (PSAs) have attracted the attention of the PSA market due to their major advantages over the traditional waterborne and solventborne products. These advantages include

(1) lower conversion costs because less energy is required,

(2) smaller space requirements due to the compact equipment necessary for processing,

(3) lower shipping costs and inventory needed because UV-curable PSAs are 100-percent active,

(4) more efficient processing because a thick film can be made in a single pass, and

(5) environmental friendliness because these products have low volatile organic compounds (VOCs).

UV-cured products are attractive to PSA coaters seeking lower capital investment and operational costs as well as those facing footprint constraints. Although UV-curable PSA 36 formulations have been studied since the s, problems with their performance and cost have hindered their acceptance by the market.

Through numerous experiments with synthesis and formulation, Cytec has created new UV-curable PSA polymers with reasonable raw material costs, specially designed blocks of microstructure domains, optimized molecular weights, and efficient UV-curing properties. Cytec&#;s UV-curable PSA technology involves the formation of a unique, acrylated urethane hybrid that combines soft segments to provide flexibility and adhesion with hard segments to give the film cohesive strength, high temperature resistance, and chemical resistance. Cytec&#;s technology solves the five performance challenges faced by other UV-curable PSA technologies.

This acrylated urethane hybrid provides good adhesion to substrates of both low and high surface energy coupled with excellent high-temperature shear performance. In addition, Cytec&#;s technology achieves consistent performance over a broad UV curing range and good through-cure for thick PSA films at a reasonable cost to the general PSA market. It is a 100-percent-active PSA with no solvent or water, requiring much less energy for curing than traditional waterborne or solventborne PSA formulations. Currently, nine locations globally are evaluating this technology.

Vegetable Oil Based Macromonomers in Emulsion Polymers for High-Performance, Zero-VOC Architectural Coatings: Most waterborne coatings contain significant levels of volatile organic compounds (VOCs) as cosolvents to facilitate efficient film formation of high-glass-transition-termperature polymers. Vegetable oil based macromonomers (VOMMs) are a series of vegetable oil derivatives functionalized for efficient incorporation into emulsions by copolymerization with conventional monomers. The synergistic combination of vegetable oil derivatives and an acrylic backbone provides storage-stable, self-cross-linking systems for architectural and industrial coatings with reduced- or zero-VOC emissions. Professors Thames and Rawlins developed a series of VOMMs including soybean oil amide acrylate (SoyAA-1), a monomer that imparts flexibility to emulsion polymers and can replace butyl acetate.

Professors Thames and Rawlins have successfully formulated emulsions synthesized with up to 80 percent by weight of SoyAA-1 into zero-VOC, waterborne architectural coatings that perform competitively against commercial zero-VOC coatings. They have also formulated SoyAA-1 into low-VOC, waterborne Navy Haze Gray (NHG) coatings as a potential replacement for current NHG coatings formulated with solvent-based, silicone-modified alkyds that contain high levels of VOCs (336 g/L). Their SoyAA-1-based NHG coatings contain very low levels of VOCs (less than 15 g/L), have fast drying rates, and meet military specifications MIL-PRF-C and MIL-PRF-A. Additional advantages include easy clean-up, reduced fire hazards, and low toxicity to Navy personnel. Their coatings have passed initial trials at the Naval Research Laboratory in Washington, DC and are scheduled for evaluation onboard naval ships to simulate and characterize the coatings in actual use.

If one percent of the production of flat, water-thinned coatings had incorporated 20 weight-percent of SoyAA-1, almost 300,000 pounds of soybean oil would have been used and 2.1 million pounds of VOC emissions would have been eliminated. Upon commercialization, VOMM technology will have the ability to transform the marketplace: the resulting high-value-added monomers, polymers, and finished products would reduce the VOC emissions of coatings significantly without affecting their performance.

Vegetable Oil Based Printing Inks and Their Environmental Advantages: The current United States market for news inks is greater than 500 million pounds, for sheetfed inks is greater than 100 million pounds, and for heatset inks greater than 400 million pounds. Conventional printing inks used in these applications are multicomponent systems comprising a hydrocarbon and/or alkyd resin, a hydrocarbon solvent, a pigment, and optional additives. The large amount of petrochemical resins and solvents, used in these formulations, are presenting environmental problems and pollution during the production and disposal of these inks.

In recent years, the industry has been able to substitute soybean oil for a portion of the petroleum fraction, although news ink can contain as little as 40% vegetable oil (including soybean oil), sheetfed ink as little as 20% vegetable oil, and heatset ink as little as 7% vegetable oil of total formula weight. A technology has been developed for preparing ink vehicles using vegetable oils, in the complete absence of petroleum products. Ink vehicles were prepared by the polymerization of vegetable oils. By controlling the polymerization conditions, the desired viscosity, color and molecular weight could be achieved for a variety of vegetable oils having a broad range of iodine value and fatty acid composition.

These vehicles were used to formulate news inks in four primary colors (black, cyan, magenta, and yellow). For sheetfed and heatset ink vehicles heat polymerized vegetable oil was mixed with monoester of an unsaturated fatty acid or a blend of unsaturated fatty acid monoesters. In the formulation of the vehicle, unmodified vegetable oil was used as a third component. Esters were incorporated at a relatively low level, that is on the order of about 0.5-3.0% by weight of the vehicle. Heat polymerized and unmodified oil constitutes the major fraction of the vehicle, and thereby primarily is responsible for the rheological properties of the formulated ink. Physical properties (i.e, viscosity, tack, drying time, printability) and performance of these inks meet or exceed the industry standards. Biodegradation and volatile organic chemical tests once again showed the superiority of our inks over commercial inks.

Vegetable Oil Insulating Fluid for Improved High Voltage Transformer Capability: Polychlorinated biphenyls (PCBs) form the basis for traditional dielectric coolant fluids, but they present environmental problems and liabilities for the electric power industry. Cooper Power Systems has developed a replacement insulating fluid, EnvirotempTM FR3TM fluid, to provide the electric power industry with a sustainable dielectric coolant that has an innocuous environmental and health profile. EnvirotempTM FR3TM fluid contains approximately 97 percent food-grade soy oil blended with small amounts of additives for long-term performance.

The National Institute of Standards and Technology (NIST) directly compared FR3TM fluid to mineral oil in its total lifecycle assessment called BEES® 4.0, Building for Environmental and Economic Sustainability. Using the carbon dioxide equivalent (CO2 eq.) amount of greenhouse gas (GHG) generated from raw materials through end of life, FR3TM fluid has reduced GHG emissions by over 98 percent (or over 102,000 tons of CO2 eq.) to date compared to mineral oil. This essentially carbon-neutral result assumes that FR3TM fluid or mineral oil would be placed in equivalent transformers. Roughly 450,000 transformers now contain over 25 million gallons of EnvirotempTM FR3TM fluid instead of petroleum-based mineral oil.

In , Cooper combined the chemistries of FR3TM fluid and solid insulating paper with advanced high voltage transformer design to produce a new generation of even greener biotransformers. The chemical interactions between FR3TM fluid and the solid insulating structure create greater thermal capacity that allows an optimized biotransformer design. With this increased capacity, Cooper removed 3&#;15 percent of the fluid volume and 3 percent of the construction materials from the biotransformers. Using the BEES analysis on 25 million gallons of FR3TM fluid, the new generation of biotransformers could save an additional 2,000 tons of GHG emissions. Other advantages include improved fire safety, remediation of accidental spills, and sustainable supply benefitting U.S. farmers. New transformer designs with FR3TM fluid will be available in .

Vibrating Fluidized Bed Combustion Nitridation Processing Using Concentrated Solar Energy: The best way of managing pollution from industrial processes is to devise ways to minimize its production. This is especially true in the synthesis of chemical compounds. New concepts developed at the University of Colorado attack the problem on four levels: maximizing yields, avoidance of post processing, use of nontoxic precursors, and minimizing energy consumption. Professor Weimer and his students have demonstrated model ceramic synthesis systems that have high yield, avoid needle-like particle growth induced by thermophoresis, use metal powders and nitrogen as precursor material, and use sunlight as the source of energy for synthesis reactions. High-quality powders of silicon nitride and of aluminum nitride, both technologically important materials, have been produced as proof of concept. The use of a directed energy source for the synthesis produces higher quality materials and reduces the energy budget, thus reducing the pollution associated with conventional heating. The use of concentrated sunlight, instead of a laser beam or arc lamp, further reduces the consumption of fossil fuels to provide the energy for the beam.

VigorOx® Biocide: Advancing Environmentally Responsible Energy Production: Recent advances in horizontal drilling and hydraulic fracturing have unlocked significant reserves of natural gas in the United States, providing opportunities to increase the nation&#;s energy independence. Because microbes present in well treatment fluids can foul wells, the oil and gas industries must use biocides. Some of these biocides could contaminate ground water and drinking water wells, however, so the industry has been seeking biocides with minimal environmental impact. Glutaraldehyde, the most commonly used biocide in the oilfield industry, is an effective biocide but is also toxic to aquatic organisms and requires high rates of application. Historically, oxidizing biocides have not been practical because they may interact negatively with other chemicals in well treatment fluids.

FMC Corporation has met this challenge with VigorOx® biocide. FMC&#;s research team took peracetic acid (PAA), a safe chemical that was already established in the healthcare and food processing industries, and reformulated it for energy-production applications. VigorOx® biocide is a mixture of high-purity hydrogen peroxide and acetic acid treated with a proprietary purification process and a small amount of chemical stabilizer.

PAA is an oxidizing biocide that rapidly destroys aerobic and sulfate reducing bacteria (SRB) while decomposing into environmentally benign oxygen, water, and acetic acid, thus minimizing risk to the environment and human health. VigorOx® peracetic acid formulations contain lower levels of hydrogen peroxide than standard PAA blends, so they do not inhibit the polyacrylamide friction reducers commonly used in "slick water" fracturing. Field trials confirm that PAA does not persist in the environment or pose chronic toxicity risks. Moreover, the oxidizing power of peracetic acid can be used to clarify produced water, allowing greater water reuse in hydraulic fracturing operations. The low rates of use can also provide an economic advantage.

In , FMC&#;s patent-pending formulation received EPA pesticide registration #-3 for oil and gas applications.

Volatile Methyl Siloxanes: Environmentally Sound Solvent Systems: Linear Volatile Methyl Siloxanes (VMS) are a class of mild solvents having an unusual combination of environmentally benign qualities. They are low in toxicity, make little contribution to global warming, do not contribute to urban ozone pollution, and do not attack the stratospheric ozone layer. They do not accumulate in the atmosphere, but rather are rapidly transformed to naturally found species, and they have received SNAP approval and VOC exemption from the EPA.

VMS solvency can be tailored to specific applications by use of cosolvents and surfactants. Eleven U.S. patents, 26 new azeotropes, 5 commercial solvents, and several formulated products have resulted. The underlying phenomena related to their use to replace less benign solvents in coating formulations or to remove particulates, oils, fluxes, and aqueous contaminants have been extensively studied. Their mild but selectable solvency, environmental benignancy, and odorless character commend them for many uses. Highly purified grades leave no surface residue, and many of their applications require such purities. They have potential value for precision Water Displacement Drying during the many aqueous processing steps of Flat Panel Display and semiconductor manufacturing.

VORANOL* VORACTIV* Polyols for Flexible Polyurethane Foams: Polyurethane is the material of choice for cushioning materials in automotive seating, mattresses, and furniture. Its performance is unrivaled by competitive materials. Global production of flexible polyurethane foam is over 2 million metric tons (4.4 billion pounds) each year. Foam producers blend a polyether polyol, an isocyanate, water, a surfactant, and a fugitive tertiary amine catalyst together in a mix-head to form a reacting mixture that generates the foam. Most foams use either bis(dimethylaminoethyl)ether or triethylenediamine as the fugitive amine catalyst.

These amines are undesirable for a number of reasons. First, they may be hazardous to the skin or eyes and, hence, require careful handling. Second, workers could be exposed to them during handling and processing of polyurethane chemicals. And third, they are released slowly from the foam during use and, hence, can provide odor and degrade indoor air quality.

VORANOL VORACTIV polyols embed the amine catalyst covalently into the polyol structure, eliminating amine catalyst emissions both during the foaming process and from the finished product. This technology results in performance that exceeds current industry standards, provides greater yields, and makes smoother, more consistent foam block shapes, reducing waste from trimming. Dow Chemical has been selling its VORANOL VORACTIV polyols in the U.S. since ; in , its global sales exceeded $25 million.

Wash &#;n WalkTM Floor Care System: Foodservice operations can be dangerous places for employees because grease and other food soils fall onto floors throughout the work day. Grease creates slippery floors, leading to slips and falls that impact employee safety and the bottom line for Ecolab&#;s customers. Traditional floor cleaning and maintenance systems include surfactants to emulsify grease, highly alkaline chemicals to hydrolyze grease, hydrofluoric acid to etch floor tiles for greater traction, and EDTA (ethylenediaminetetraacetic acid; not readily biodegradable) for water conditioning.

Ecolab has designed a revolutionary floor care system that both results in cleaner floors and increases the coefficient of friction (the primary measure of slipperiness of floors). The formula is unique in exhibiting superior performance and providing environmental and human health benefits. Ecolab&#;s floor care system incorporates three innovative platforms. First is a proprietary blend of surfactants, including a silicon surfactant uniquely capable of removing complex organic or greasy soils from a variety of substrates. Second is a suite of stabilized enzymes, including lipases, that are stable at alkaline pH values and in the presence of high concentrations of water. Third is an optional suite of stabilized bacterial spores that germinate and then decompose proteins, starches, and fatty acids. The Wash 'n WalkTM formula also includes Trilon M water conditioner that is composed of amino carboxylates and is readily biodegradable. Wash 'n WalkTM can be used with cold water. It uses a no-rinse procedure that leaves enzymes and spores on the floor to break down grease and other soils that accumulate over time.

The Wash &#;n WalkTM formula received Green Seal Certification in under the GS 37 standard. To achieve this certification, the formula passed a rigorous review to demonstrate both superior environmental and human health benefits. Between and , Wash 'n WalkTM saved Ecolab&#;s customers 546 million gallons of water annually.

Washington State Pollution Prevention, Health, and Safety Initiative in Academic Chemistry Laboratories: In , the Washington State Department of Ecology and the Educational Service District 101 began planning workshops to educate chemistry teachers on green chemistry techniques, health and safety issues, and proper hazardous waste management. The workshops included detailed information on better laboratory practices that reduce the risk of accidents, maintain employee and student health and safety, and reduce the use of hazardous substances and generation of hazardous waste.

Green chemistry techniques such as microscale chemistry and conducting experiments that use only non-toxic substances or less toxic chemicals were also taught. The workshops also included environmental, health and safety regulations that schools must observe in the state of Washington. A Step-by Step Guide to Better Laboratory Management was produced and used as part of the workshops.

A coordinated multi-agency team was formed to plan and implement the workshops. Six workshops were held throughout the state of Washington in the spring of . Ecology, ESDs, OSPI, Washington State Department of Health (DOH) and Washington State Department of Labor and Industries (L&I) developed and implemented the workshops. Over 300 chemistry instructors attended throughout the state.

Ecology trained six staff members and King County Hazardous Waste Program (Metro) staff to conduct site visits at middle and high schools throughout the state of Washington. The lab team was trained to: 1) Organize chemicals in compatible storage system; 2) Tag or remove chemicals of concern that are extremely hazardous, unstable, in poor condition or in excess; 3) Sort waste chemicals into Department of Transportation shipping categories; 4) Labpack waste chemicals for shipping and disposal; 5) Explain proper hazardous waste management and disposal; 6) Assist with preparing a chemical hygiene plan for laboratory; 7) Assist with creating a complete and up-to-date chemical inventory. To date, about 100 schools have been visited.

Waste Biomass Utilization in the Production of a Biodegradable Road Deicer: The effective utilization of biomass and the residuals from agricultural and food processing operations in the production of fuels and chemicals is one of the cornerstones of policies aimed at energy conservation and sound environmental management. Biomass wastes such as liquid whey effluents from the dairy industry are an undue burden on the environment due to the high biochemical oxygen demand (BOD) of such wastes. Whey is a byproduct from cheese and casein production operations and contains about 5% lactose and 0.1 to 0.8% lactic acid. About 50% of the total U.S. milk production is used in the production of cheese, resulting in the generation of approximately 57 billion pounds of liquid whey per year. Acid whey containing lactose and lactic acid has a very high BOD of about 40,000 mg/L.

As such, this waste can be a tremendous burden to the environment if it is discharged without controls. Treatment of the high BOD waste is both capital and energy intensive. Thus any viable reuse option is likely to offer large savings in cost and energy utilization. The work of Alexander P. Mathews at Kansas State University is aimed at examining the use of whey permeate in the production of a road deicer substitute for sodium chloride. Each year, about $2 billion are spent on U.S. highways alone to maintain driveable conditions during winter. The bulk of this expenditure is on the application of chemical deicers, principally sodium chloride (NaCl). The annual use of NaCl has increased rapidly from 0.5 million tons in to about 30 million tons in .

Many roads and highways in the snowbelt may receive up to 60 tons of salt per km during the winter season. Currently used deicers, such as NaCl, cause extensive corrosion-related damage to the highway infrastructure and environmental damage by contaminating water supplies and soils. The main objectives of Mathews&#; work were to examine the use of biomass wastes in the production of deicers, calcium magnesium acetate (CMA), and calcium magnesium propionate (CMP). A novel two-stage fermentation process was developed to utilize and convert inexpensive substrates such as whey permeate to acetic and propionic acids for use in the production of the deicer.

The two-stage process has a substrate conversion efficiency of about 9% compared to 53% for a single-stage process. Acid concentrations up to 60 gm/l were obtained in batch and fed-batch fermentations. In addition, the source of calcium and magnesium in the CMA/CMP deicer was obtained from water plant treatment sludges (water treatment operations such as coagulation, flocculation, and chemical softening result in the production of large quantities of solid byproducts containing calcium and magnesium that can be used in the production of CMA/CMP deicer).

Waste Minimization and Pollution Prevention Programs for the Production of Films & Chemicals in the Graphic Arts Industry: Ulano Corporation, with 90 employees in Brooklyn, New York, is a graphic arts supply manufacturer specializing in film and liquid stencil-making products for screen process printing. Ulano dramatically improved its film and chemical manufacturing process at Sites I and II in the following manner:

By replacing hazardous solvent-based coating solutions with non-hazardous water-based emulsions in its film coating operation at Site I, Ulano reduced hazardous waste from 50,000 pounds in to 200 pounds in (a 99.6% decrease).

By recycling organic solvent blends from tank and pipe rinsings instead of disposing of them in its blending operation at Site II, Ulano reduced hazardous waste from 102,000 pounds in to pounds in (a 94.7% decrease).

By redesigning coating cement formulas, Ulano reduced toluene processed during production at Site I, from 68,000 pounds in to pounds in (an 87.1% decrease}. During the same period, toluene released to the environment was reduced from pounds to 393 pounds (an 80.4% decrease).

Environmental and Economic Benefits of Ulano"s Green Chemistry Program: Dramatically reduced hazardous waste, reduced disposal costs, reduced raw material costs, reduced emissions to the environment, and dramatically improved both worker and environmental safety.

Waste Minimization in the Manufacture of an Antibiotic Produced by Chemical Synthesis: PRIMAXIN is an injectable, broad-spectrum antibiotic commercialized in . Development and implementation of an effective manufacturing process for PRIMAXIN was an immense challenge due in part to the complexity of the imipenem molecule and instability. The manufacturing process initially proposed for PRIMAXIN involved 18 steps and would have created one ton of waste for every pound of product. While still in the development lab, however, Merck&#;s chemists and engineers found a way to eliminate 500,000 gallons of annual toxic waste.

After production began, Merck continued to improve the process by eliminating a mixture that prevented solvents from being reused, developing an innovative extractive hydrolysis technology that improved yield, and reducing use of another solvent. For example, one of the process steps involved the use of methyl isobutyl ketone (MIBK) and acetonitrile. Process development work indicated that MIBK could be eliminated. This allowed acetonitrile to be recycled, which previously was sent off-site for disposal. In a separation step, the number of cycles between regeneration of a chromatographic column using acetone/sulfuric acid was increased tenfold. These solvent recovery opportunities resulted in an annual savings of $50,000. Even after PRIMAXIN was in full scale manufacturing, several waste minimization process modifications were implemented that resulted in dramatic waste load reductions.

The most significant is the 82 percent reduction in the use of methylene chloride by eliminating materials that made methylene chloride recovery impractical, modifying processes to allow the use of recovered material, and improving recovery techniques. This dramatic waste reduction resulted in an annual savings of over $1 million, and the process is still undergoing modification in order to further reduce waste generation. Development, implementation, and ongoing improvement of the process to manufacture PRIMAXIN (imipenem) is a prime example of Merck&#;s contribution to the promotion of environmentally benign technology.

Waste Oil Source Reduction Through Extended Oil Service Life: According to National Petroleum Refiners Association estimates, 1.1 billion gallons of oil were used in passenger vehicles and 916 million gallons were used in diesel engine vehicles in the United States in . Much of the motor oil changed by passenger vehicle owners is improperly introduced into the environment. The management of used oil is a major environmental issue because of its hazardous nature. Used oil contains toxins such as lead, benzene, cadmium, chromium, and other heavy metals. These contaminants can cause illness in plants and animals and can contaminate drinking water.

Waste oil has been granted special regulatory status, exempting its management from conventional hazardous waste rules in an attempt to encourage its beneficial use as a source of energy. Overall, this has had some success in the management of used oil in the business sector. Used oil generated by households, however, is currently disposed of improperly at an alarming rate nationally&#;220 million gallons per year as estimated by the U.S. Department of Energy. In , AMSOIL, Inc. introduced the first 100% synthetic motor oil to meet American Petroleum Institute service requirements, passing performance testing for gasoline-fueled consumer passenger vehicles. AMSOIL, Inc. has since developed synthetic oil formulas that extend oil service life up to 11 times that of conventional petroleum lubricants in consumer and commercial automobile and truck service and that work much longer when used with an oil analysis program.

AMSOIL, Inc. also manufactures extended life, premium-grade lubrication and related products for commercial and industrial applications, including hydraulics, compressors, gears, and diesel-engine power plants. The scope of AMSOIL lubricating products&#; ability to provide uncompromising engine and machine wear protection, while reducing the volume of waste oil generation at the source, benefits the consumer, the commercial goods and services provider, and the upstream industrial entity. Synthetic oil basestocks are comprised of well-defined particular molecule types that can be designed for specific performance characteristics. One distinct advantage over crude petroleum is that they can be tailored to fit the requirements of the application. The uniform molecular structure of synthetic oil base-stocks reduces the lubricant volatility (aromatic boil off ) in extreme heat, which in turn reduces oil consumption. With long drain synthetics, the average American can use 75% less oil, reducing the volume and the potential for accidental environmental contamination.

Waste Reduction and Recycling of Magnesite-Chrome Refractory into the Steelmaking Process: The primary objective of the work of Dr. Claudia Lage Nassaralla at Michigan Technological University is to develop the technological basis to minimize the formation of hexavalent chromium (Cr6+), a well-known carcinogen, within magnesite-chrome refractory during its production and use in industrial processes. Magnesite-chrome is a high-temperature refractory used in the steel, copper, cement, and glass industries because of its excellent resistance to thermal shock and chemical attack. The spent magnesite-chrome refractory is classified as a hazardous material by EPA when it contains high levels of Cr6+.

Of all the chromium ions, Cr6+ is the only one soluble in water, and as such, can give rise to detrimental effects on the environment and food chain because it is strongly oxidizing and easily penetrates human tissue. The origin of Cr6+ in the refractory is due to the reaction between CaO and Cr2O3. No other oxide present in the refractory is known to form Cr6+. Until recently, spent magnesite-chrome refractory was normally disposed of in authorized landfills. Currently, spent magnesite-chrome refractories with a Cr6+ content above 5 ppm must be treated before disposal. The technology being developed by Dr. Nassaralla has the potential to minimize the formation of Cr6+ by carefully controlling the brickmaking and steelmaking practices. It will also allow for the reduction of hexavalent to trivalent, and to chromium metal, di- and trivalent chromium by recycling the brick into the steelmaking converter and the electric arc furnace, respectively.

No type of preprocessing of the solid waste or installation of additional equipment will be necessary. The waste material can be treated on site, and the contaminated bricks can also be recycled as part of the flux that has to be added in the steelmaking converter to absorb the oxides generated in the production of steel or in the electric arc furnace as a source of chromium in the production of ferro-chromium. The information generated from this project can also be used by the copper, cement, and glass industries to design their practices to minimize the formation of Cr6+. Besides the savings associated with the costs of disposing spent chrome-magnesite brick, the recycling of Cr6+ in the production process and its conversion to chromium metal, di- and trivalent chromium will avoid contamination of the environment by possible leaching of Cr6+ after dumping.

Waste Reduction During Development of a New Process for Manufacture of Pharmaceutical Products: Evista® is the first of a new class of selective estrogen receptor modulators, or SERMs, that was approved in December for the prevention of osteoporosis in postmenopausal women. Waste reduction and minimization of overall environmental impact were key elements in development and commercialization of a process for manufacture of Evista®. To identify, address, and track environmental issues and opportunities early in the development and commercialization of manufacturing processes, Eli Lilly and Company has developed a new management system called New Product Environmental Requirements Tracking (NPERT). Development and commercialization of the manufacturing process for Evista® served as a pilot for this program. The initial process proposed for manufacture of Evista® would have generated over 3.1 pounds of solid hazardous aluminum chloride waste per pound of product. In addition, the manufacture required the use of 114 liters of organic solvents for each pound of product produced.

Of the total solvent used, 85 percent was composed of Superfund Amendment and Reauthorization Act (SARA) Title III listed material. While the process was still in development, Lilly chemists and engineers found a way to eliminate the use of aluminum chloride and the need for disposal of the corresponding hazardous solid waste. This eliminated the generation and disposal of more than 371,000 pounds of hazardous solid waste during the first year of commercial production. During process development, the NPERT process focused attention on reducing total solvent usage and particular attention on the reduction in the use of all SARA Title III solvents. For example, one of the processing steps initially used methylene chloride. Evaluation of 26 alternative solvents resulted in the ability to completely eliminate the use of methylene chloride. Another process step used methyl isobutyl ketone (MIBK) and generated a waste stream that could not be solvent recovered and required incineration. Process development work resulted in a modification of the process that allowed the use of amyl acetate rather than MIBK.

The revised process was more efficient and economical, generating an amyl acetate waste stream that could be easily recovered. By the time the Evista® process was in full scale manufacturing, process modifications and improvements in efficiency during development and scale-up had reduced the total volume of solvent required to produce a pound of product by 61 percent. These improvements also reduce the use of SARA Title III solvents by 67 percent. Currently, on-going efforts are underway to further decrease waste, reduce volatile emissions and increase the recovery and recycle of solvent. The NPERT process and the example of its use on Evista®, show that focused efforts early in development and scale-up can dramatically reduce the environmental impacts of a new chemical manufacturing process. This effort highlights Lilly"s commitment to minimizing the worldwide environmental impact of its manufacturing operations.

Waste Reduction in the Production of an Energetic Material by Development of an Alternative Synthesis: 1,3,3-Trinitroazetidine (TNAZ) is a promising new melt-castable explosive that has significant potential for providing environmental benefits and capability improvements in a wide variety of defense and industrial applications. Initial lifecycle pollution burden was associated with the demilitarization of the munitions, and in particular, the use of thermoset polymeric binders that require removal with water jet cutting. TNAZ is the only energetic material other than trinitrotoluene (TNT) that can be melt-cast in existing TNT loading plants. Demilitarization of TNAZ simply requires heating the device above the melting point and pouring the liquid out, rather than the complicated and destructive methods used for RDX- and HMX-based plastic bonded explosives. The stability of TNAZ in the melt allows it to be easily recycled.

TNAZ has performance slightly better than that of HMX, the most powerful military explosive in current use. Thus, TNAZ might offer 30 to 40 percent improvements in performance as a replacement for TNT-based formulations such as Composition-B. The alternative synthesis of TNAZ, developed at the Los Alamos National Laboratory, allows TNAZ to be produced in a waste-free process that also eliminates the use of halogenated solvents. This alternative synthesis produces 5.3 pounds of waste per pound of product compared to the original synthesis of TNAZ, which produces 1,200 pounds of waster [sic] per pound of product. The alternate technology has been transferred to industry, where it has been scaled up to production-plant quantities. Further improvements in waste reduction have been demonstrated in the laboratory that might eventually lead to a process giving little more waste than one pound of salt per pound of TNAZ.

Waste to Renewable Diesel: Changing World Technologies, Inc. (CWT) has successfully developed and patented an energy-efficient process that converts organic waste into diesel oil. Their Thermal Conversion Process (TCP) is capable of breaking down waste material using water, heat, and pressure. The process can use a broad range of wastes including animal carcasses and byproducts; fats, greases, and oils; and municipal and industrial wastes including plastics, metals, and recycled automobiles. It does not require exotic chemicals or catalysts, and it includes screening and grinding of waste; depolymerization at 290 °F and 80 psi; hydrolysis at extreme temperature and pressure (480 °F and 600 psi); and separation of the oil, water, and solid products. Because the process relies on waste, which is typically generated near areas of high energy demand, the company will be able to supply its renewable diesel locally without having to use costly and constrained energy infrastructure.

TCP is being demonstrated in a commercial environment. In December , CWT opened a pilot plant at the Philadelphia Naval Business Center with the support of the Gas Technology Institute. CWT began construction of its Carthage, MI facility in , produced its first gallon of renewable diesel in , and commissioned the plant in February as a joint venture with ConAgra Foods, Inc. The company is currently selling its renewable diesel for use in industrial boilers. The efficacy, efficiency, and other key qualities of TCP have been reviewed and validated by a number of independent authoritative organizations such as the Brookhaven National Laboratory, the Massachusetts Institute of Technology, the U.S. Department of Energy, and the Vehicle Recycling Partnership. CWT believes it is the first company to successfully demonstrate the ability to commercialize the process of converting waste to oil in an energy-efficient manner.

Water and Energy Conservation in Denim Finishing: Traditionally, the processing and finishing of denim to achieve the popular, well-worn, soft look and feel requires large amounts of water and energy. To provide a faded look, processors traditionally use silicones, particularly amino-silicones, as softeners in wet finishing. Often the enzymes and other chemicals used in denim garment and fabric processing do not have good compatibility with silicones. Consequently, most processors use silicones and enzymes only in different processing steps when they desire a faded look. The conventional denim garment process requires from 7 to 10 steps and uses large quantities of water in each step. Typically, a basic denim wash that includes desizing and fading with enzymes can consume as much as 70 to 110 liters per kilogram of denim garments.

Dow Corning® GP Eco Softener is a granulated, modified polysiloxane textile enhancer. Its nonionic formulation contains four to five ingredients. It has the potential to reduce the amount of water consumption needed for traditional methods of denim processing by as much as 30&#;50 percent, to as little as 20 liters of water per garment containing 500 grams of denim. Used in different stages of denim garment or fabric wetfinish processing to achieve a natural, soft hand, this water-dilutable, ready-to-use granular silicone material has a unique formulation and delivery that provides good compatibility with fabric finishing enzymes and washing stones. This novel combination of properties enables previously incompatible steps to be combined, thus eliminating separate washing requirements and conserving significant amounts of water and energy. Combining processing steps using Dow Corning® GP Eco Softener also results in improved productivity, reduced utility costs and processing time, and improved environmental sustainability without sacrificing performance or fabric characteristics. Dow applied for a patent for this technology and expects the patent to be published in June .

Water Immiscible Room Temperature Ionic Liquids as Green Solvents for Extraction and In-Situ Photolytic Destruction of Environmental Organic Contaminants: The technology described herein concerns an innovative Green Chemistry and Engineering technology dealing with the use of a new generation of "Green Solvents" to solve environmental problems combined with the application of a novel and environmentally friendly method to achieve recyclability and sustainability of the solvents. These solvents concern a new generation of materials known as Room Temperature Ionic Liquids (RTILs). These are currently considered as "Neoteric Green Solvents" and have great potential to replace volatile organic solvents (VOCs) in chemical and engineering processes. VOCs are currently used extensively and are the source of major environmental pollution problems.

Water immiscible RTIL solvents have been employed in this study considering removal by extraction of organic contaminants from polluted environments such as contaminated soils and dredged sediments. The novel method investigated in this project concerns the use of ultraviolet (UV) radiation to destroy extracted organic contaminants in-situ in the ionic liquid phase with simultaneous regeneration of the ionic liquid. This approach ensures purification, recyclability, and sustainability of the ionic liquid solvents.

Alternatively, the photodegradation method can be utilized to destroy organic contaminants that are present in RTILs as undesirable byproducts in various chemical reactions utilizing RTILs as the solvent media. Finally the photodegradation method can be utilized to eliminate organic impurities present in the RTILs after their manufacturing for the production of extremely clean RTILs, which are required in electrochemical processes and liquid batteries.

Water Washable Flexo Photopolymer Plate "Flexceed" and Washout System: Flexography (Flexo) is a method of direct rotary printing that uses resilient relief image plates and the fastest growing printing process in the world. The conventional flexo photopolymer plates can be washed out only by using organic solvents to make relief images. Concerns for solvent use include the emission of VOCs, flammability because of lower flash point, hazardous waste, and influence on human health. Flexo photopolymer plate "Flexceed" is designed to be washed out by water to eliminate the use of any organic solvents.

Both "Flexceed" plate and its washout system are designed as a total system to make treatment of its washout solution pass waste management regulations at reasonable cost using a user-friendly concept. The newly developed washout system can provide wider latitude for developing new types of "Flexceed" plate, which can satisfy the requirements of new flexo market segments for "Flexceed," while maintaining this environmental benefit. It has been positively demonstrated that the total "Flexceed" system is acceptable for each market segment of flexo printing industry due to not only print performances but also economic benefits as compared with the conventional solvent washout flexo photopolymer plate systems.

Water-Based Refractory Coatings with Wet/Dry Color Change Indication: The use of refractory coatings in metal casting processes has been a common practice in the foundry industry for decades. These coatings are applied to dies, cores, and molds to provide a protective barrier facing the hot liquid metal. When applied to sand cores and molds, the coatings prevent casting defects like metal penetration and erosion, improve veining resistance and casting surface finish, or simply mitigate imperfections resulting from molding media and processes.

Traditionally, solvent-based refractory coatings have been widely preferred over water-based coatings. More recently, workplace health and safety concerns, environmental concerns, and economic considerations due to increasing costs of petrochemical-based materials such as solvents are spawning the development and use of water-based coating technologies. Although optimum drying of these water-based coatings is critical, the metal-casting market has not had a simple analytical method to determine whether the coating has completely dried. Incomplete drying can cause casting defects that could be expensive to fix or may require scrapping of the cast piece. Conversely, excessive drying wastes energy and may reduce productivity.

Ashland Performance Materials has developed a water-based refractory coating that undergoes a distinctive color change as it dries. The water-based refractory coating with wet/dry color change is an innovative approach that combines intended purpose, environmental considerations, and a high level of functionality within an otherwise ordinary product. Ashland successfully introduced this technology to the industry in ; it is now widely accepted among metal casters. Some customers have saved more than 10 percent overall, including a 50-percent reduction in gas used by the heaters to dry coated material. Ashland continues to develop technologies and innovative solutions that deliver performance to their customers and are environmentally responsible.

Water-Based Synthesis and Purification of Mannich Base Modified Polyphenols: Polyphenol copolymers are common in industrial and consumer products. Mannich reaction products of polyphenols with formaldehyde solutions and secondary amines produce unique chelating polymers. These have replaced many hexavalent chromium-containing treatments and continue as components in new and diverse non-heavy-metal-containing conversion-coating technologies. Originally, the precursor phenolic polymer was dissolved in an organic solvent before the reaction. Acidification of the newly acquired amine functionality allows dilution with water before application.

At this point, the organic solvent component serves no apparent useful purpose. Since phenols can be ionized and, thus, be solubilized in water by a strong base such as sodium hydroxide, a water-based synthesis process was developed. These reactions proceed with paraformaldehyde (eliminating methanol content) and amine at lower temperatures and higher yields than the solvent-based processes. Dilution and acidification, followed by deionization through a strong-acid type cation-exchange column, quantitatively removes the sodium, residual amine, monomeric Mannich reaction products (small ethylphenol content from the precursor polymer), and other cationic impurities C resulting in a highly purified 100% aqueous polymer solution.

Additional benefits realized include improved shelf-life and hot/cold stability of the concentrate; elimination of flash points; biological and chemical oxygen demand and residual formaldehyde reductions; and the elimination of worker exposure to organic volatiles during manufacture. The amount of organic solvent eliminated to date is greater than 500,000 lbs. This has been a great help to customers who need to meet ever-decreasing limits on the amount of volatile organic compounds emitted from their manufacturing plants. These products have been highly effective at reducing widespread heavy metal use in the past. The continued application of these new synthesis technologies today helps insure the continued development and wise use of these important polymers well into the future.

Waterborne Coating Formulations for Video Tape Manufacture: Magnetic tape technology is an important component of the information age and maintaining a domestic tape manufacturing capability is important to the U.S. economy. Magnetic tape is manufactured by a continuous web coating process that uses organic solvents, including tetrahydrofuran, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), toluene and cyclohexanone. MEK, MIBK, and toluene are on the list of 189 hazardous air pollutants and on the list of 18 chemicals for the EPA&#;s 33/50 voluntary pollution reduction program.

Waterborne magnetic tape coating formulations were designed at the University of Alabama and used to prepare experimental magnetic tape samples in a pilot coating trial. The formulations contained a blend of a water-dispersed polyester and an ethylene/vinyl chloride copolymer emulsion. The coatings were thermally cured with a melamine-formaldehyde cross-linker to give tensile properties that were comparable to a standard solvent-based binder composition.

The pilot tape trial used existing processing equipment, including calendering and slitting. The tape had good magnetic properties and excellent adhesion between the pigmented magnetic layer and the base film, easily exceeding the 8 mm helical scan tape standard of 0.96 N peel force. An economic impact analysis for the case of using the waterborne video tape coating process in a conventional tape manufacturing plant showed an 11 percent decrease in hourly operating costs. The solvent-based process generated almost 650 kg of organic solvent per hour operation, while the waterborne process generated less than 5 kg methanol (from the melamine-formaldehyde cross-linker) per hour. In addition to pollution prevention, there was a clear economic incentive to adopt the waterborne video tape manufacturing process.

Waterborne Refi nish Coatings Manufacture: Paints and solvents account for approximately 12 percent of all emissions of volatile organic compounds (VOCs). The traditional, solventborne paints that automobile body repair shops have used for automotive refinishing emit relatively large amounts of VOCs. The California Air Resources Board (CARB) enacted legislation in January to reduce VOCs for all automotive refinishing products. Most notably, it reduced the limit on VOCs in basecoat to 3.5 pounds per gallon (420 grams per liter). The rest of the United States is expected to adopt similar limits in the near future. Waterborne and solventborne paints perform similarly in color accuracy, smoothness, and chip resistance.

Although the main current motivators of market growth for waterborne coatings are VOC regulations in California and Canada, many automotive refinishers use PPG&#;s waterborne finish products solely for their perceived superior performance. PPG developed waterborne finish in Europe in the early s. In spring , PPG established an innovative waterborne manufacturing process and facility in Delaware, Ohio. This facility is designed such that all raw materials, production, filling, quality assurance, and utilities are located nearby. The design reduces product loss, contamination, and waste. The waterborne finish produced at this facility will contain approximately 0.15 pounds of VOCs per gallon.

The company&#;s expansion to the North American market allows PPG to create an additional 3 million liters per year of its high-quality, environmentally friendly waterborne refinish paint. During , this production volume will avoid the emission of 3,097 metric tons of carbon dioxide equivalents (CO2e). PPG expects the use of waterborne finish to double in the next five years. Any body shop that replaces solventborne finish with waterborne finish will release 80 percent fewer VOCs to the atmosphere. More than 25,000 auto body repair shops in 50 countries (nearly 5,000 in the United States) now use PPG&#;s waterborne refinish coatings.

Waterborne, Ambient-Cure, Stain-Blocking Primer: When red cedar and other tannin-rich woods are painted, their tannins can bleed into topcoat paints, producing undesirable discolorations. Solventborne, universal-stain-blocking primers reduce tannin bleed and discoloration. Typical solventborne primers are based on alkyd resins and contain volatile organic compounds (VOCs) at 350&#;450 grams per liter. During painting, these solvents are released directly into the air. Eco-friendly systems, such as waterborne systems, are needed to reduce VOCs, but existing commercially available waterborne primers, many of which are based on anionic alkyd resins, are generally less effective in blocking tannin bleed than are their solventborne counterparts. Cytec Industries has developed a family of cationic, waterborne, epoxy ester resins.

The new cationic polymer emulsions are synthesized by reactions of epoxy resins, fatty acids, and amines. The polymers are neutralized with organic acids such as acetic or lactic acid and then dispersed in water. To achieve the best film-forming properties, the emulsion is reacted with additional epoxy resin to increase its molecular weight. These low-VOC esters show excellent tannin-blocking performance. Their manufacturing uses a solvent-free process in which exothermic reactions heat the reaction mixture to processing temperature. They also provide better drying performance because they do not require oxidative cross-linking reactions, but only solvent evaporation for complete drying.

The primers cure at ambient or even low temperatures. Cytec&#;s new waterborne primers require very little cosolvent. Conventional stain-blocking primers can contain up to 40 percent solvent, whereas the new products need only 1&#;2 percent cosolvent. The VOC content of Cytec&#;s cationic, waterborne, stain-blocking primers is 20&#;45 grams per liter. In , Cytec produced its first technical-scale batch of primer and made its first commercial sales to U.S. paint manufacturers. These small, initial sales reduced VOC emissions by approximately 20 tons. Potential VOC reductions from low-VOC waterborne primers of equal performance are 35,000&#;49,000 tons annually.

Water-Dispersible Hot-Melt Adhesive Raw Material: Current technologies make recycling and disposal of paper products difficult. The hotmelt adhesive industry has been searching for an answer in the form of a water-dispersible raw material. Previous attempts to satisfy this need were often deficient in both critical performance requirements and cost. Government regulations are not yet directly mandating improved adhesive raw materials, but the needs are real and urgent just the same. The lack of regulatory changes does not encourage adhesive manufacturers to introduce products based on expensive raw materials. Eastman AQ water-dispersible hot-melt adhesive raw material represents the best of both worlds. The water dispersibility of Eastman AQ is due to the random incorporation of sodiosulfonate groups along with polymer backbone.

These ionic functionalities also facilitate the excellent adhesion of Eastman AQ to a variety of substrates. Some of the key features of Eastman"s new product are low cost, 100 percent water-dispersible in ordinary tap water, nondispersible in ionic solutions, superior adhesion to polyolefin films, and comparable key physical properties to conventional formulations. Eastman AQ is part of a new family of water-dispersible polymers that provide the hot-melt adhesive industry with an innovation that addresses long-standing needs in very large, applicable areas. These products not only overcome the lack of water-dispersibility inherent to the current generation of technology but also are differentiated from the competitive generation of technologies by their ability to be dispersed into water coupled with insolubility in saline solutions. This tunable solubility mechanism also can be employed as a method for product recovery; thus, it is legitimate to call Eastman AQ an advanced technology of a 'smart material.&#;

Water-Dispersible Sulfopolyester for Reduced VOC Consumer Products: The reduction of airborne emissions is a major focal point for legislation to safeguard public health. Volatile organic compounds (VOCs) are one of the major sources of air pollution that arise from both consumer and industrial products. Legislation proposed at the state level, particularly in California, is targeting consumer and personal care products for VOC content reductions.

One of the largest product areas is in hairsprays, which a very large, diverse segment of the population uses daily. Consumers, however, demand that green products have the same if not better performance characteristics. Eastman Chemical Company has developed a new product, known as EASTMAN AQ 48 Ultra, for this general need that not only reduces VOCs, but actually may improve performance. EASTMAN AQ 48 Ultra is a water-dispersible sulfopolyester that allows hairsprays to be formulated with 55 percent ethanol, which is significantly less than the current industry standard of 80 percent VOC. Switching all of the hairspray market from the current standard of 80 percent VOC to 55 percent VOC would result in a total reduction of VOC emissions around 55 million pounds per year.

In general, sulfopolyester dispersions may be used as low VOC film formers for a variety of cosmetic products in addition to hairsprays; therefore, an even larger potential for VOC emission reduction exists. Finally, the process chemistry is completed in the melt phase. There are no organic solvents used in the synthesis of sulfopolyesters at Eastman Chemical Company. The synthesis also does not release any toxic by-products.

Wolman® AG Metal-Free Wood Preservative: Wolman® AG is the first organic preservative for pressure-treating wood used in decks, fences, and residential projects. The active ingredients are carbon-based and contain no metals. This is a long-envisioned breakthrough in wood preservation. Wolman® AG preservative offers broad-spectrum protection against wood decay and termites yet does not contain copper, as do current alternatives. Just as an earlier transition replaced chromium and arsenate with copper in common wood preservatives, this advancement offers control of termites and fungal decay without copper.

Instead, Wolman® AG takes advantage of the synergistic qualities of three organic biocides: propiconazole, tebuconazole, and imidacloprid, which have long histories of residential and agricultural use. They readily undergo bacterial degradation in soil and groundwater, becoming nonhazardous materials. As a result, Wolman® AG is intended for use on outof- ground wood, which accounts for nearly 80 percent of all applications for pressure-treated wood. Proven efficacious in field and lab tests, wood treated with Wolman® AG is recyclable after use as decking. It can be burned for energy in commercial incinerators in accordance with state and local laws. It is safe for landfills because any runoff is biodegradable. Wolman® AG contains the three biocides blended with emulsifiers to produce a concentrated aqueous formulation. The formulation has a pH of 7.5, close to that of water. It is not regulated as a hazardous material for land, water, or air transport.

In addition, the amount of preservative needed is comparatively small, reducing total production and transportation requirements. The mammalian acute toxicity for Wolman® AG is 4,000 mg/kg, in contrast to that of copper-based alternatives, which have acute toxicities of 800 mg/kg or less. The price of Wolman® AG is comparable to or less than that of copper-based alternatives. In , the product was first used at a customer&#;s plant.

WOODSTALKTM Strawboard: Dow Chemical and Dow BioProducts have implemented a revolutionary process for manufacturing fiberboards using 100% waste straw as the fiber raw material. After harvesting wheat grain, the remaining stalks are typically burned in the fields or plowed into the topsoil. Historically, field burning has been the preferred method of disposal; however, CO and CO2 emissions from open-air field burning can be significant, especially in the wheat belt areas of Kansas, Iowa, and Manitoba. Smoke from these burning fields decreases visibility and poses health concerns.

In the WOODSTALKTM process, Dow BioProducts takes straw that would have been burned as waste in the fields and manufactures it into fiberboard composite panels. WOODSTALKTM fiberboard competes head-to-head with traditional fiberboard made from wood particles (i.e., particleboard, medium-density fiberboard, and plywood). WOODSTALKTM fiberboard uses polymeric methylene diphenyl diisocyanate (pMDI) instead of formaldehyde-based resins and, therefore, emits substantially less aldehyde than do traditional wood-based composite panels.

Overall, the WOODSTALKTM process uses waste from a renewable resource, reduces CO and CO2 emissions associated with the wheat harvest, and substantially reduces the aldehyde emissions from wood-based composite panels that are a growing concern with indoor air quality. Each year, Dow BioProducts uses over 255 million pounds of waste straw that would have generated 175,000 tons of CO2 had it been burned. Dow BioProducts does this today while being competitive with traditional indoor woodbased fiberboard products.

World-wide Elimination or Reduction of Solvent and Chemical Cleaning of Laboratory Glassware Using Thermal Pyrolysis-oxidation Chemistry: Pyro-clean® technology is a commercial system developed by Tempyrox Company to change the way chemists, technicians, scientists, and laboratory personnel clean their glassware. The technology is designed to eliminate or greatly reduce the current wide spread use of hazardous chemicals and solvents for cleaning of laboratory glassware.

Although sales are in its infancy (about $ 3,000,000), laboratories adopting Pyro-clean® technology have reported typical reduction of 40% in cleaning solvent use after purchase of the Tempyrox systems. The Federal Highway Administration purchased four units for evaluation by the DOT labs of four different states. After the year long study was done, each state adopted Pyro-clean® technology as the method of choice to reduce solvent usage. Since then, virtually all state DOT labs in the USA (46 out of 50 states) have switched to this new solvent free cleaning technology.

World wide adoption of Pyro-clean® technology for cleaning of lab glassware (where applicable) could significantly impact and reduce use of solvents and chemicals detrimental to human health and the environment.

WT-HSC13: A High-Strength, Low-VOC Aerosol Adhesive: Westech&#;s WT-HSC13 high-strength canister adhesive is formulated to limit volatile organic compounds (VOCs), dramatically reducing toxicity and air pollutants. WT-SC13 contains no chlorinated or cancer-causing solvents (e.g., methylene chloride). Methylene chloride is a concern in some geographical areas and Westech has excluded it from the formula. The South Coast Air Quality Management District (SCAQMD) for Los Angeles, Orange County, Riverside, and San Bernardino requires the VOC level to be less than 80 grams per liter. WT-HSC13 is the only solvent-based canister adhesive on the market that complies with this regulation.

Using an alternative solvent, cyclohexane, Westech&#;s new formula makes the manufacture of furniture, countertops, RVs, automotive headliners, manufactured homes, and many other products a safer process for workers, the environment, and the local population. This product provides a substantially high bonding strength and contains more than double the solids or rubber content of other adhesives currently on the market, resulting in double the coverage. This new technology in chemistry provides a much needed solvent-based adhesive. It is strong, affordable, environmentally safe, and adheres to even the strictest regulations with regard to emissions and pollutants.

Xerographic Dry Ink Resin Manufacturing Hazard & Emission Reduction : The process and material change described entails replacement of a hazardous, pollution generating solid free radical initiator, benzoyl peroxide, with a less hazardous liquid initiator, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, that generates far less pollution, to produce a low melt temperature cross-linked polyester resin for use in xerographic dry-ink formulations. Specifically, Xerox developed a proprietary process for cross-linking an unsaturated polyester resin by mixing a peroxide initiator with the polymer and then passing the polymer through a high shear melt mixer.

The process is termed "reactive extrusion" because the reaction occurs during the melt mix step. Desiccation of the benzoyl peroxide occurred in vessels and the nuisance dust collection system. Impact testing showed that the residual left in the equipment was shock sensitive, with potential for explosive decomposition. Benzoyl peroxide was also inefficient in the cross-linking of the polyester and large quantities of benzoic acid were generated as the major decomposition product, necessitating manual steam cleaning of the sublimed benzoic acid from piping and generating aqueous hazardous waste. The alternate liquid initiator eliminated the risk of explosion and generated only neat tertiary butyl alcohol as a by-product.

Xerox&#;s Emulsion Aggregation Toner Technology: Toner is the dry ink for laser printers and copiers. Xerox&#;s Emulsion Aggregation (EA) toner technology represents a breakthrough in the chemistry and chemical processing of toner materials. It is a unique, environmentally friendly technology that allows customers to print in color more accurately and affordably. There are over 400 patents protecting this Xerox innovation.

Toners are a mixture of plastic resin, colorant, and other ingredients. The conventional method of making toners uses a top-down approach: a mechanical mechanism physically grinds composite polymeric materials into micron-sized particles, which are then sorted by size. The EA technology uses sophisticated chemical design- and control-based nanotechnology methods to generate toner particles of about 3&#;5 microns in diameter from nanoscale components in a bottoms-up approach. The process includes a semicontinuous emulsion polymerization in water to generate nanometer-scale polymer particles.

The key advantages of EA technology are its ability to control the size, shape, and structure of the particles. This technology improves print quality, uses less toner, wastes less toner, and decreases energy use, both for manufacturing toner and for using it in printing. Xerox can now produce toner using 25&#;35 percent less energy per pound of toner. Combined with 40&#;50 percent less toner needed during printing, EA technology offers an estimated 60&#;70 percent energy savings per printed page. EA technology produces less waste and increases the life of machine parts. EA is an environmentally friendly, water-based process.

The Xerox Research Centre of Canada and its Xerox partners in the United States and Japan jointly developed this technology. Xerox introduced its EA technology in in its DocuColor / color copier/printers; currently, several other Xerox products also use this technology. In June , Xerox announced plans to build a second EA toner plant on the company&#;s property in Webster, NY.

Zero Discharge System For Cooling Towers: The Zero Discharge system is a complete packaged water treatment system to control corrosion deposition and biological fouling with no water discharge (commonly known as 'bleed-off") from the system. This bleed-off is widely used by conventional water treatment programs to dilute the concentration of natural minerals in the water to prevent precipitation. In the Zero Discharge system, the recirculating cooling tower water is filtered by a side-stream filtration system to remove suspended solids. A microprocessor control monitors the prescribed characteristic of the recirculating water through sensors installed in a sample stream.

The control maintains a programmed pH in the recirculating water along with prescribed levels of chemical treatment through actuation of chemical feed pumps. With these levels being maintained and monitored, the microprocessor, using stored tabular data, calculates the calcium content necessary to maintain a zero Langelier Saturation Index. The level of calcium is adjusted accordingly by regulating the flow of untreated raw water supplied to the tower as make-up through a bypass of a calcium removal (e.g., water softener or deionizer) system on the make-up water line. The health and environmental benefits of the Zero Discharge system are the result of the water saved and the significant reduction of chemicals discharged to the environment. The Zero Discharge system was patented in the early s and has since been extensively applied in the metropolitan Philadelphia area. In total, about 30,000 tons of cooling water are being treated by the Zero Discharge system, which saves about 132 million gallons of water in the Philadelphia area annually.

Zero Effluent Photographic Processing in the Printing Industry: In its pre-press operations, the printing industry consumes about 1.5 billion square feet of silver halide photographic film annually. Processing the film consumes enormous amounts of water and chemicals and produces an equally large amount of liquid waste which is primarily disposed of in POTWs. The process also produces millions of waste plastic containers. Virtually none of this material is recycled and the environmental burden is very large. Some 400,000,000 gallons of fresh water is consumed each year and, after washing contaminant from the processed film, is sent to local POTWs for treatment.

In addition to that, 15,000,000 gallons of photographic developer containing thousands of tons of obnoxious chemicals like hydroquinone is similarly dumped on the POTWs. Further, 15,000,000 gallons of photographic fixer containing high levels of ammonia and silver is also sent to the POTWs for treatment. Although some of the silver is removed by various processes, these are not very efficient and recovery of this precious metal is only on the order of 50 percent. The limited environmental efforts have been directed primarily at silver recovery because of the value of the silver, or, where water prices are high, to reduction in wash water use. The wastes generated in the pre-press printing industry are complex and require a coordinated effort to eliminate them. The Dupont DuCareTM Photochemical Film Processing System is such a coordinated effort.

It attacks the largest volume piece of the problem, the wash water, by developing novel technology that reduces the amount of wash water required by 99 percent and completely eliminates the wash water effluent by sending used wash water into the fixer. The DuCareTM system also includes a novel, recyclable developer based on erythorbic acid instead of hydroquinone in a process that allows about 75 percent of returned developer to be used in making fresh recycled developer. Finally, the DuCareTM system also includes a recycled fixer. Although the technology used is not new, it is made much more effective and efficient than in the past. The fixer is returned to a central recycling center, much like the developer is, where the silver is recovered with an efficiency of 99 percent. In addition, the analytical capability and control at a recycling center allow about 90 percent of the returned fixer to be used in making fresh recycled fixer.

The net effect of this coordinated approach would virtually eliminate the liquid waste generated if it was applied across the industry. Fresh water savings would be over 395,000,000 gallons annually. No liquid waste would be sent to POTWs. All liquids would be returned for recycling. Those that could not be recycled would be disposed of at commercial, licensed TSDFs. Packaging waste would drop significantly. The efficient recycling and reuse of the spent chemical stream would eliminate the need for thousands of tons of raw materials as well.

Zero VOC Protective Coatings for Aerospace Applications: The Zero VOC protective coatings developed by Deft include an epoxy resin based primer and a polyurethane topcoat based on polyester polyol-polyisocyanate resins. Each has a design organic solvent content of zero confirmed through measurements as specified in EPA Method 24. Neither uses exempt solvents to achieve zero VOC. The primer, AquapoxTM, was listed as qualified to military waterborne primer specification MIL-PRF-, Type I (standard pigments), Class C2 (strontium chromate) on July 11, .

It is based on emulsified epoxy resin and polyamine curing agents. Coatings qualified to the specification have an intended use as corrosion inhibiting, chemical resistant coatings for use on most aircraft substrates. The topcoat product line, Defthane® Z-VOCTM, is qualified to military specification MIL-PRF-, Type III (aircraft and ground support equipment, 50 g/L VOC maximum), Class W (waterborne). It was qualified in July . Coatings qualified to this specification, based on the range of requirements for application, appearance, fluid resistance, corrosion resistance, and weathering resistance, are intended for use in naval aviation environments and other less severe environments.

Zero-Emission Production of the Green Lithium Ion SuperPolymer® Battery: The lithium ion cell and battery industry is a multibillion-dollar business that also pollutes the environment. The manufacturing process for lithium ion electrodes includes coating the electrodes with the toxic solvent N-methyl pyrrolidone (NMP), then removing NMP by slow evaporation in a furnace up to 100 meters long. Although manufacturers attempt to recover NMP, some escapes. NMP is listed as potentially causing birth defects by environmental agencies in California, Japan, the European Union (EU), and elsewhere.

The large quantities of toxic solvents in cell and battery manufacturing also lead to high costs for capital equipment and plant operations as well as uncertain future liabilities. Electrovaya&#;s SuperPolymer® batteries are based on a nanostructured lithiated manganese oxide material that allows more energy to be stored in a smaller space, making applications smaller, lighter, and more powerful. They also produce approximately 25 percent less carbon dioxide (CO2) over their lifecycle than do NMP batteries. Electrovaya developed a unique, nontoxic process to manufacture its fuel cells that eliminates all solvents including NMP. Electrovaya has also eliminated some energy-intensive drying and solvent-recovery processes. Electrovaya&#;s SuperPolymer® batteries address the problem of energy generation and storage.

Advanced energy storage for plug-in hybrid electric vehicles and e-bikes can provide an alternative to nonrenewable resources and reduce greenhouse gas emissions. Currently, Electrovaya is testing its battery technology nationwide in a fleet of plug-in hybrid electric versions of Chrysler&#;s RAM pickup trucks and Minivans. High-capacity energy-storage systems are essential if renewable sources are to supply a significant portion of a grid&#;s energy. Electrovaya&#;s technology is useful for grid energy storage systems to solve the power stability and energy storage problems associated with electricity generated by renewable resources. Electrovaya recently delivered a 1.5 MW energy-storage system to an electric utility in the Southwest United States for use with its photovoltaic operations.

Zero-to-Landfill Fuel Cell Systems: Plug Power produces fuel cell-based products that are environmentally friendly; however, the concepts of sustainability do not end with this contribution. Plug Power is striving to ensure that the product lifecycle is effectively managed and to achieve minimal waste generation from its operation and maintenance. The goal is zero-to-landfill, meaning that no part of either the product, its operation, or its maintenance finds its way to the trash. During , Plug Power was able to reduce the fraction of its GenSysTM systems that are thrown away to 10% by weight. This achievement is due in part to efforts to recycle or reuse fuel cell stack plates. The plates represented the largest item, by weight, being sent to landfills at the beginning of . Recycling and reuse methods were developed and proven in the laboratory; both are now being scaled up to support production volumes.

Zero-VOC Cleaning and Remediation Technology: The pollutants in indoor environments can actually reach higher levels than those found outdoors. Although several factors contribute to indoor air quality, fumes and residues from the cleaning chemicals currently used in our homes, offices, and schools have a significant negative effect on the quality of the air we breathe. Many common cleaners contain dangerous and harmful chemicals that are carcinogens, neurotoxins, hormone disruptors, and reproductive toxins. RPS Environmental Solutions has developed products without volatile organic compounds (VOCs) or harsh chemicals that it is currently using in a wide range of cleaning products from degreasers and odor eliminators to adhesive removers and pet care products.

These products are hypoallergenic, rapidly biodegradable, and have undergone rigorous testing to ensure the greatest possible safety and efficacy. RPS carefully manages the entire lifecycle of its products from manufacturing in a zero-discharge facility to using minimal-impact packaging. Independent laboratory testing with the American Society for Testing and Materials International (ASTM) D protocol for cleaning efficacy shows RPS&#;s products to be 3.5 times more effective than those of the leading "green" competitor, over twice as effective as those of the most-recognizable name-brand competitors, and over 30 percent more effective than those of the most powerful competitor.

Although many competitive products compromise safety for effectiveness, RPS cleaning products are both safer and more effective than those of their competitors. RPS technology has leveraged hydration&#;dehydration, metal ion reaction, surface charge modification, and the mechanics of conversion to provide cleaning and remediation products that are safer for use near people, pets, and plants. RPS technology not only eliminates the need to produce many dangerous chemicals, but can actually remediate environmental damage caused by many harmful substances and improve human health by improving indoor air quality. RPS expanded and launched several product lines during ; RPS products have been recognized by EPA&#;s Design for the Environment partnership program.

Zero-VOC, BioBased HiOmega® Linseed Oil Epoxies, Adhesives, and Alkyd Resins as Replacements for Epichlorohydrin&#;Epoxy Resins and Other VOC-containing Coatings, Paints, Adhesives, and Epoxies: Of the two billion pounds of epichlorohydrin manufactured worldwide each year, 76 percent is used in epoxy resins. Epichlorohydrin is both a probable human carcinogen and a deadly poison at high levels.

Polar Industries is commercializing products from HiOmega® linseed, a flax plant developed by conventional breeding that is an annual, renewable crop grown in the United States and Canada. HiOmega® linseed oil is highly suitable for epoxidation because it has 20&#;40 percent more a-linolenic acid than does conventional linseed oil. Environmentally friendly epoxidation methods at moderate temperatures yield epoxidized HiOmega® linseed oil with high oxirane values (11.0&#;13.0) that exceed the highest values of epoxidized conventional linseed oil (9.0&#;10.0). Epoxy and alkyd resins made from HiOmega® linseed oil contain no volatile organic compounds (VOCs).

They are biodegradable and require no special handling or disposal. The entire lifecycle of HiOmega® linseed oil epoxy resins, from crop growth and harvest to oil extraction, epoxidation, industrial use, and final disposal, is nonhazardous and follows environmentally sound practices. In initial testing, the performance of HiOmega® epoxy resins and alkyd resins met or exceeded the performance of other linseed oil epoxy resins in bonding strength, moisture resistance, and resistance to fatigue. HiOmega® linseed oil epoxy resins are suitable replacements for epoxy resins made from epichlorohydrin. HiOmega® epoxy resins can be used in conventional two-part epoxy systems (i.e., resin and amine hardener) or one-part, UV-photoinitiated systems.

Biobased, environmentally friendly, nontoxic epoxy resins and adhesives synthesized with epoxidized HiOmega® linseed oil could potentially reduce epichlorohydrin production by approximately 1.5 billion pounds per year. Polar Industries has successfully commercialized nontoxic epoxy coatings, epoxy adhesives, and alkyd resins made from HiOmega® components. The California Department of Transportation is currently using Green Graffiti Coat, an antigraffiti clear coating based on HiOmega® epoxidized linseed oil, to protect road signs.

Zero-VOC, Zero-HAP, No-Odor Industrial Coatings: Sierra Performance Coatings by Rust-Oleum have eliminated the traditional use of solvents to manufacture and apply industrial coatings. Through a number of patented and trade secret processes, Sierra has developed a way to combine uniquely designed resins and resin systems into a line of industrial coatings that contains zero volatile organic compounds (VOCs), zero hazardous air pollutants (HAPs), and no odor. As a commercial product line, these coatings are reducing VOC and HAP emissions, which have in return translated into broad-based benefits for end-users (paint applicators, workers, and building occupants) and the macro-scale environment. Sierra Performance products range from single component (1K) acrylic and acrylic-urethanes to two-component (2K) epoxies and acrylic-epoxies.

The 1K compositions are unique resin systems that achieve application and finished properties by manipulating particle size, molecular weight distributions, and chemical composition without solvents. These compositions, combined with other traditional raw materials for paints and coatings, activate upon the evaporation of water. The principal component of the 2K products is a proprietary, advanced molecular-weight epoxy polymer with a unique distribution of molecular weight; it produces high-performance coatings that cure quickly without requiring solvents to reduce viscosity or aid coalescence. Rust-Oleum&#;s development of alternative processes and material compositions, both patented and trade-secret, have made possible new designs for waterborne resins, coatings, and paint products that meet the demanding performance of institutional and industrial environments, while not contributing any airborne environmental emissions or worker safety issues.

Zero-Waste Dry Plating of Cadmium: Electroplated cadmium is widely used in the defense and aerospace industries for the corrosion protection of steel. Cadmium, however, is a known toxic material. In addition, the electroplating process generates large quantities of toxic sludge and effluents. A typical, medi-um-sized electroplating shop, for example, discharges well over 100,000 gallons of effluents daily and disposes of 15 to 20 tons of hazardous sludge per week. As an alternative to this conventional process, IonEdge Corporation has developed and commercialized a novel "zero-waste" dry plating technology.

The dry plating does not use liquid chemicals and recycles solid materials in situ, resulting in elimination of waste. In this dry plating technique, a vapor-bath concept has been used in vacuum as opposed to the liquid bath of electroplating. This vapor bath allows for multidirectional and economical plating of cadmium only in the intended parts, resulting in a green technology. In addition, the amount of water used, filtered, and deionized on the line is reduced by at least one order of magnitude, and the energy consumption in the dry plating process is only 35% of that in electroplating. Estimated water treatment and disposal cost savings on the dry plating line are greater than $1,000 per day, and the capital costs in setting up the line are substantially lower.

At IonEdge Corporation&#;s facility in Fort Collins, Colorado, a complete dry plating line has been set up for production. The plating line consists of only four processes and a quality inspection as opposed to more than a dozen baths and related operations in electroplating. This plating line has been certified by a major aerospace parts supplier, and two dry plating machines are in service for plating cadmium on aerospace components.

ZircobondTM Pretreatment: Pretreatments protect metal substrates against corrosion and improve adhesion of paints. Conventional zinc phosphate pretreatment forms a sludge byproduct containing suspected carcinogens and heavy metals such as zinc, nickel, and manganese that are hazardous and subject to environmental regulations. These heavy metals also create challenges in wastewater management. Increasing demand for the raw materials used for zinc phosphate pretreatment is also rapidly outpacing the capacity of suppliers worldwide.

PPG has developed ZircobondTM pretreatment as an alternative to conventional pretreatment technologies. The ZircobondTM process is based on dilute, aqueous fluorozirconic acid. It contains no regulated heavy metals, phosphates, or volatile organic compounds (VOCs). With its zirconium-based chemistry, ZircobondTM pretreatment uses a more stable supply chain and alleviates some of the strain on supplies of zinc, manganese, nickel, and phosphoric acid, which are used by other industries such as farming and steel. It can be used in existing equipment and is safe for the conventional waste treatment systems in most manufacturing facilities following a simple pH adjustment.

ZircobondTM pretreatment provides manufacturers with a new, environmentally friendly option with greener chemicals and reaction conditions. It generates at least 80-percent less sludge than do conventional processes; this translates to significant savings on waste disposal costs, as well as fewer stage cleanings and boil-outs. In addition to savings on maintenance, PPG&#;s new chemistry operates in an ambient temperature bath that requires minimal agitation and fewer water rinses than do current processes. The result is substantial operating savings from reductions in energy use, water consumption, and wastewater treatment. Brownfield automotive plants that have converted to ZircobondTM pretreatment demonstrate potential annual operating savings of almost $600,000. The savings in greenfield facilities are more than double: there, the smaller process footprint can save millions on new capital costs. In , the first commercial launch took place in Canada.

Changing the Nature of Surfactants: Protein-Surfactant Synergists With Enhanced Cleaning Power and Bioremediation Abilities: DRAFT: Research on the interaction between proteins and surfactants has focused on the ways surfactants change the properties and behavior of proteins including folding/unfolding, solubilization, and effects on enzymatic activity. While the effects of surfactants on proteins have been studied, some small proteins, acting as hydrotropes, can also affect the behavior and performance of surfactants.

Yeast responds to stress conditions, such as elevated, but non-lethal, temperatures by releasing small non-enzymatic stress exo-proteins. Advanced BioCatalytics Corporation (ABC) discovered that these proteins form tight protein-surfactant complexes (PSCs) and enhance the surface activity of a broad range of surfactants as manifested by reduced interfacial tension (IFT) and critical micelle concentration (CMC). These PSCs were also found to improve wetting, spreading, and uptake of actives by various surfaces.

In addition, PSCs activate the biooxidation of organic contaminants by naturally present microflora, such as in wastewater treatment, by uncoupling this process from biosynthesis and hence from bacterial proliferation, thus reducing accumulation of solid sludge by 30-50 percent. PSCs also assist natural microflora in converting hydrophobic contaminants, such as fat, oil, and grease, into soap-like surfactants, thereby rendering the process of degreasing autocatalytic in its nature, and thus converting sewer lines into wastewater preprocessing reactors. PSCs enhance the activity of interfacial enzymes, such as lipase, and improve the uptake of actives (as herbicides, micronutrients, etc.) by green leaves of plants and fertilizers by plant roots. ABC incorporated PSCs into cost-effective, water-based, nearly neutral products that do not contain any harsh chemicals, ozone-depleting, volatile organic compounds, active enzymes, or living cells. The key benefits include decreasing the use of surfactants, organic solvents, and/or petroleum-based chemicals, needed for various industrial applications. ABC is creating a new paradigm of performance enhancement and cost reduction agents with many actual and potential end uses including enhanced oil recovery, degreasing, cleaning, wastewater processing, odor and biofilm control, as adjuvants in agricultural chemicals, and elsewhere.

Hybrid Polymers: DRAFT: AkzoNobel has developed a new, biodegradable biopolymer technology for the fabric and cleaning marketplace. Based upon the combination of selected polysaccharides and synthetic monomers, the 2nd generation Hybrid Polymer technology (Alcoguard® H and Alcoguard® H ) readily biodegrades in the environment, offers a preferable carbon footprint, and is effective in replacing synthetic polymers in formulations such as automatic dishwash (ADW) and laundry detergents. This 2nd generation technology provides a sustainable and cost-effective alternative to existing synthetic options. Compared to synthetic (acrylic acid) polymers, the Hybrid Polymers provide: 40 percent lower CO2 evolution; 44 percent lower energy use; 10% percent lower acidification; 43 percent lower resource depletion; and 40 percent lower ground level ozone depletion.

Conductive Polymer Nanodispersion (CPND) and the Environmentally Friendly Heavy-Duty Anti-Corrosion Coating Platform Technology: DRAFT: Every year direct corrosion cost is estimated at trillions of dollars worldwide and nearly every industry sector is affected. Current coating technologies utilize anti-corrosion pigments in the primer to protect metals from corrosion. Hexavalent chromium has been the strongest anti-corrosion pigment on the market but it is facing regulation due to its high toxicity and carcinogenicity. Zinc pigments are environmentally preferable chromium alternatives, however, they are increasing in price and zinc cannot protect aluminum (a major material for the aerospace industries) or galvanized steel. Zinc is also less effective than chromium in severe corrosive environments.

AnCatt Inc. has discovered a high-performance anti-corrosion coating platform technology utilizing novel conductive polymer nanodispersion (CPND) as the anti-corrosion pigment instead of traditional toxic heavy-metal pigments. CPND-based coatings show superior performance to the current zinc alternatives, and CPND can also outperform traditional hexavalent chromate. In independent tests with 13,740 hours of salt fog test (ASTM B117), a CPND-based coating outperformed chromate, zinc, and other commercial anti-corrosion coatings. The test results indicate that AnCatt's next generation anti-corrosion coating platform may be used in a wide range of anti-corrosion applications to protect all sorts of metals with improved performance without using toxic heavy metal anti-corrosion pigments.

Accelerated corrosion test results indicate that CPND technology can also extend the performance life of anti-corrosion coating systems and therefore the performance life of the metal structures they protect. CPND coatings may therefore result in reduction of waste metal; repaint and coating maintenance costs; as well as corrosion related accidents, injuries, fires, and delays. CPND technology can also prevent toxic heavy-metals contamination and sidestep the zinc reserve depletion issue.

The CPND pigments and coating formulation have been filed for patent protections and are readily manufactured in scalable processes. They are cost competitive with other alternative anti-corrosion systems and AnCatt is working with paint manufacturers, government, and private companies for licensing negotiation.

Breakthrough Coating for Ceiling Tiles: DRAFT: Armstrong World Industries has developed a formaldehyde-free coating which can be applied to the surface of any fibrous panel such as a ceiling tile to prevent product sagging. This invention is the result of an extensive research effort to develop a new coating technology with the following four performance parameters: (1) capable of hydroscopic expansion at high humidity to resist sag; (2) can maintain a high modulus even at high humidity; (3) is compatible with other coatings and/or fillers; and (4) a waterborne coating system. Currently, three out of four of Armstrong's U.S. plants fully utilize the coating technology. Approximately 2.7 million pounds of formaldehyde resin and approximately 36,000 pounds of triethylamine were eliminated from U.S. plants in . The U.S. plants will complete the conversion to the new coating system in early . When this partially renewable biobased coating is implemented worldwide, Armstrong globally will eliminate the use of approximately 8,300,000 pounds of formaldehyde resins, approximately 416,000 pounds of formaldehyde emissions to the air, and approximately 134,000 pounds of triethylamine emissions annually.

Formaldehyde is a classified as a "known" carcinogen by International Agency for Research on Cancer and as "reasonably anticipated to be a human carcinogen" by the National Toxicology Program. Formaldehyde is a key ingredient in a wide variety of building products including pressed-wood products, such as particleboard, plywood, and fiberboard; glues and adhesives; permanent-press fabrics; paper product coatings; and certain insulation materials. Historically, Armstrong and other ceiling tile manufacturers have applied a formaldehyde-resin-based back coat to prevent ceiling tiles from sagging, because of formaldehyde resin's unique hydroscopic properties.

Armstrong has been using this newly invented coating technology to replace all formaldehyde resin ceiling tile applications as the new coating provides for hydroscopic expansion at high humidity while maintaining a high modulus to prevent sag. The new coating is compatible with other coatings and/or fillers and is a water-borne coating. The benefits of eliminating the use of formaldehyde resin include the:

1. Avoidance of employee formaldehyde and triethylamine exposure risk at four Armstrong manufacturing facilities in the U.S. and five international facilities;
2. Elimination of formaldehyde and triethylamine stack emissions associated with the ceiling tile back coat that resulted from the melamine formaldehyde cross linking process;
3. Removal of potential formaldehyde emissions from finished products after they are installed;
4. Reduction in life cycle assessment impacts associated with upstream production of formaldehyde and triethylamine.

An Order of Magnitude Improvement in Sustainability through Core Application of Green Chemistry Principles: The Process Development of Avibactam: DRAFT: Avibactam is a novel Beta-lactamase inhibitor which seeks to reinvigorate a co-administered antibiotic by sacrificially binding to β-lactamase enzymes produced by drug resistant bacteria. A combination of out-sourcing the synthesis and a fast track clinical program led to many challenges in meeting the clinical and manufacturing demands for a new product launch, not least the inheritance of a synthetic route with many inefficiencies in yields and reagent/solvent use, but also lack of environmental consideration in selection.

Within Forest and AstraZeneca laboratories, a focus was placed on improving the synthesis of Avibactam. The current process has been redefined with considerable sustainability benefits compared to previous through selection of greener solvents and reagents, and process optimization resulting in a subtle but effective route change.

This improved synthesis of Avibactam introduces several sustainability elements. The efficiency of the synthesis has been improved 92 percent compared to the traditional technology as evidenced by the reduction of the process' PMI (Process Mass Intensity) from to 526. Organic solvents have been reduced from kg per kg of API to160 kg per kg (20 to 1 reduction in volumes). Water consumption has also been reduced from kg per kg of API to 61 kg. The improved synthesis reduces annual waste reduction by 89,310 tonnes (based on predicted peak sales). The technology avoids hazardous chemicals by switching from dimethylformamide (DMF) and dichloromethane (DCM) to less impacting alternatives, and eliminating the use of a sulphur-trioxide DMF complex and triphosgene. The improved synthesis of Avibactam introduces considerable energy savings by avoiding distillation of 11 ml/g DMF and 120 ml/g Xylene. It also avoids environmental and hazard issues by eliminating need for distillation of DCM, reducing catalyst loadings by 90 percent and using a safer "wet" catalyst, and telescoping stages to avoid isolation and associated energy intensive processing.

INFUSETM Olefin Block Copolymers: DRAFT: INFUSETM Olefin Block Copolymers (OBCs) are produced via a novel catalytic shuttling process, creating a unique block architecture which enables customers to expand into a wide range of innovative market applications currently served by styrene- or vinyl chloride-containing polymers. OBCs have highly differentiated material properties that break the traditional relationship of flexibility and heat resistance while providing significantly improved compression set and elastic recovery properties. Importantly, OBCs also maintain the ease of formulation and low energy to process that is expected from a polyolefin.

Sustainable chemistry benefits include: atom efficiency; reduced toxicity/risk; source reduction; reduced energy requirements; and improved eco-profiles. INFUSETM OBCs are created with more efficient chemistry with less by-products, fewer extractables, and less volatiles. The formulation of other OBCs requires significant resources to strip initiator residues after polymerization. The unique block architecture of INFUSETM OBCs allows high performance from a polyolefin and reduces toxicity/risk by enabling customers to substitute for materials like PVC and styrene-butadiene-based polymers with regulatory or de-selection issues. Greenpeace lists polyolefins as among the most Earth-friendly polymers, and the materials OBCs are replacing as among the least. INFUSETM OBCs introduce source reduction through complete elimination of emissions of styrene, butadiene, aromatic solvents, or vinyl chloride compared to incumbent competitive styrene-ethylene/butylene-styrene (SEBS) or f-PVC technology. Their manufacture also has reduced energy requirements compared to incumbent polymer technology because OBCs are produced in existing polyethylene plants with an energy-efficient process, as processing steps like catalyst and volatiles stripping are eliminated. The molecular weight distribution of OBCs affords lower processing temperatures for the plastic fabricator, and reduced energy usage during fabrication versus competitive resins. Overall, INFUSETM OBCs have superior eco-profiles compared to competitive styrenic-based block copolymers. The production of OBCs has significant environmental advantages in total energy use, global warming potential, acidification potential, photochemical ozone creation potential, eutrophication potential, and water consumption. The cumulative energy demand and GWP100a ("carbon footprint") for producing OBCs are 23-38 percent less than for SEBS or SEBS compounds.

Sugar to Diesel (Bio-Diesel from Microbial Oil) -- A Sustainable, Scalable and Affordable Option to Petroleum Diesel: DRAFT: According to the BP Energy Outlook (published January ), the demand for liquid transport fuels is expected to continue to rise. Approximately an extra 16 million barrels a day will be required by . Replacing fossil-derived diesel is a worldwide priority. Producing a low-cost fuel for heavy goods transportation via biological means while also reducing carbon emissions is a viable response to this need.

Biobased/renewable diesel options do exist, but most are produced from vegetable oils such as palm, soy bean, and rapeseed oil. These routes face major concerns about sustainability, availability, and, in the case of photosynthetic algae, fundamental technical and engineering challenges.

DSM and BP have just completed the third year of a pioneering research program to demonstrate that heterotrophic-derived microbial oil can be developed as a sustainable, scalable and cost-effective alternative to fossil-based diesel. The technology uses microorganisms that convert sugars into lipids through fermentation (heterotrophic conversion), which does not require sunlight or a source of carbon dioxide (CO2).

Heterotrophic-derived diesel offers the potential to deliver significant lifecycle greenhouse gas emission reductions (estimated at >60 percent) when compared to traditional fossil fuels and therefore is less harmful to the environment. This pathway allows access to a wide variety of "greener" biomass feedstocks such as sugarcane, sugarcane waste, and woodchips, which can be produced at scale and with high yields, offering a "greener" synthetic pathway for diesel fuel.

The program seeks to utilize novel, low-cost, solvent-free, extraction processes that have the potential to deliver lower cost oil via greener reaction conditions. Further, this platform has the potential to enable the conformity of fuel providers worldwide with biofuel blending mandates. To summarize, the technology being developed by BP and DSM offers an alternative to the current biodiesel and other renewable diesel options and is a viable, practical route to low-cost, sustainable bio-diesel.

An Innovative Cell Factory and Bioprocess for Production of BiolsopreneTM Monomer: DRAFT: DuPont and Goodyear are involved in a highly collaborative effort to develop an integrated process to make isoprene (BioIsopreneTM monomer) from renewable raw materials. Currently, the two companies are in a joint research stage of the platform's development. The technology is an innovative production system for isoprene based on microbial fermentation of renewable sugars. The production system includes an engineered E. coli cell factory, a fermentation-based bioprocess, and continuous recovery and purification from the fermentation of gas that results in 99.95 percent product purity even from cellulosic residue sugar streams. BioIsopreneTM monomer yields approaching commercial targets have been demonstrated and rate and titer metrics are at or greater than those needed for commercialization. A further significant step towards commercialization has been demonstrated by the integration of unit operations at research and development scale, producing over 20 kilograms of purified BioIsopreneTM monomer, some of which has been chemically polymerized to cis-polyisoprene, a rubber component of passenger car tires. Concept tires produced from the BioIsopreneTM monomer validate completing the supply line from renewable feedstock to consumer product. The technology will help mitigate a number of problems associated with the incumbent supply chains of natural and synthetic rubbers. An investment in a dedicated pilot plant for the production of renewably sourced BioIsopreneTM product will address the growing demand for isoprene, which is utilized for a wide range of industrial applications, including synthetic rubber, specialty elastomers, and in adhesive applications.

Polymeric, Non-Halogenated Flame Retardants with Broad Applicability in Multiple Industries: DRAFT: Halogenated, small-molecule flame retardant (FR) additives readily migrate out of their host plastic, exposing humans to toxic chemicals and diminishing the application's flame retardant function. Electronic device manufacturers have instituted voluntary bans on plastic formulations with halogen-containing FR additives. Other industries are also moving away from halogenated FR additives. Consequently, the plastics industry is searching for cost-effective, non-migrating, non-halogenated alternatives.

FRX POLYMERS® Inc. (FRXP) developed halogen-free polymers based on phosphorus for use as non-migrating FR additives. These unique polymers have been commercialized under the brand name NOFIA® and have the highest limited oxygen index measured for any thermoplastic material, highlighting their FR functionality. The polymers can be used as standalone, inherently FR materials. They can also deliver FR performance and additional properties when blended with polycarbonate, polyesters, (thermoplastic) polyurethane, unsaturated polyesters, and epoxies.

Sustainable developments led to processes to make these new innovative monomer and polymers that are based on Green Chemistry principles. No solvents are used and the atom economy of the reactions is 100 percent. A minimum amount of waste is produced from FRXP's polymer production. NOFIA® products can readily be converted into useful products via normally difficult melt processes like melt spinning or blown film processing, giving NOFIA® a distinct advantage verses other types of FR additives.

NOFIA® is commercial in applications including electronic housings, industrial textiles, printed circuit boards, transparent laminates and structural panels in high speed trains, and synthetic leather. Multiple toxicology studies have shown a low risk profile and FRXP's monomers and polymers are now globally registered. FRXP is currently constructing a several thousands of metric tons commercial plant. In September , FRXP broke ground on the facility and the first-of-its-kind plant is on track to start up by mid-October .

GeoSprayTM Geopolymer Mortar System for Structural Rehabilitation of Sewer and Storm Water Infrastructure: DRAFT: Asset owners throughout the U.S. and the world are in search of cost-effective and environmentally-friendly solutions to severe infrastructure degradation problems such as aging pipes. GeoSprayTM is a revolutionary geopolymer mortar system that is an environmentally-preferred solution for trenchless storm and sewer water pipe repair. GeoSprayTM allows a contractor to perform an on-site reconstruction of new structural storm or sewer pipe using a patented spray technology resulting in improved strength and flow characteristics within the old pipe. GeoSprayTM is a styrene-free, easy-to-install pipe within a pipe. It fits within the old pipe regardless of the original pipe condition. The GeoSprayTM system offers a cost advantaged solution to both contractors and asset owners.

The environmental benefits of the GeoSprayTM system include: (1) use of industrial waste materials that would otherwise be landfilled; (2) substantial reduction in environmental disruption from the use of a trenchless technology; (3) significantly reduced CO2 emissions when compared to standard cement materials; and (4) replacement of styrene-based resin alternative solutions of cure-in-place-pipe (CIPP). The mix of a proprietary geopolymer formulation containing at least 80 percent post-industrial waste streams and biobased components has significant environmental advantages as compared to dig and replace, CIPP, and Portland cement. These advantages include preservation of current sensitive environments, greater than 80 percent postindustrial recycled content, and reduced carbon dioxide emissions. For example, CO2 emissions are reduced up to 90 percent compared to dig and replace solutions with an additional 90 percent reduction over standard Portland cement &#; all with a styrene-free chemistry.

To date, more than 10,000 linear feet and 5 million pounds of GeoSprayTM have been installed in 10 states. This constitutes over 150 individual structures. In addition, on-going and scheduled projects in amount to more than $8 million in material sales. GeoSprayTM is the environmentally friendly trenchless solution to sewer and storm water infrastructure decay.

Infinite Enzymes: Low-Cost, Plant-Based Enzymes for Converting Cellulosic Biomass into Biofuels and Other Biobased Products: DRAFT: Infinite Enzymes (IE), established in , is a plant biotechnology company with a novel genetic technology for producing low-cost, industrial, and reagent enzymes.

The company's plant genetic technology enables the production of cellulase enzymes in the germ of the corn kernel. Using genetically-engineered corn as a "plant factory" for producing cellulase enzymes, Infinite Enzymes can deliver high-quality, cost-competitive cellulase enzymes on a commercial scale without the capital intensive requirements and environmental costs associated with existing enzyme production through microbial/fungal fermentation processes.

The enzymes produced by IE are used in industries from textile production to renewable fuels. IE's first products are cellulases. Cellulases are a group of enzymes that degrade plant stems and leaves and thus are able to convert plant bodies into sugars. These sugars can be used for fermentation into biobased products such as fuels, plastics, and chemicals.

Biobased products are referred to as the "third wave of biotechnology". Industrial biotechnology employs developed and new technologies to transform agricultural and forestry materials into consumer products. The advantages of plants include being biodegradable, endlessly renewable, and environmentally friendly.

IE aims to produce enzymes for the biofuel industry. Two hundred 35 million dry tonnes of biomass would be needed to produce 20 billion gallons of biofuel, the Renewable Fuel Standard goal. The amount of enzyme needed to convert this volume of feedstock has been estimated to be approximately 0.6 million tonnes.

The agricultural bio-production system offers the potential for a viable and scalable alternative to lower the cost of enzymes for biomass deconstruction. IE's technology offers a cleaner and more environmentally friendly alternative to current production methods.

Temporary Assembly Lubricants for Rubber and Plastic Articles Using Renewable Oil-in-Water Emulsion Technology: DRAFT: Rubber, plastic, and articles thereof intrinsically manifest significant friction during their manipulation and assembly to other materials. The assembly of a hose onto a manifold requires strenuous exertion, particularly when the mated components are designed with tight tolerances for a permanent union.

Historically, the assembly friction is mitigated by using chemicals conveniently found throughout the manufacturing facility; these include transmission oil, motor oil, coolants, gasoline, and metalworking fluids. In the domestic automotive industry alone, International Products Corporation (IPC) estimates the misapplication of these chemicals generates over ten thousand gallons of hazardous waste annually from spills, drips, and overuse. Other detrimental consequences include fugitive emissions, unnecessary exposure, and housekeeping hazards. This problem spans into many other industries, including aerospace, appliance, recreational equipment, marine, pump, and after-market maintenance and repair needs.

IPC is providing an innovative product line to overcome these problems. By using emulsion technology, superior lubrication is achieved with no adverse environmental or health hazards. Unlike petroleum products, P-80 lubricants provide a thin lubricating film on the elastomer. After assembly, the water evaporates, the negligible synthetic esters absorb into the porous elastomers, and the lubrication ceases.

In the last 10 years, non-porous elastomers with longer lives and a burgeoning use of plastics penetrated manufacturing industries. IPC responded with Grip-It and RediLube. Grip-It offers both adequate lubrication and a tacky residue that promotes adhesion of the mated components. In , the low-solids RediLube emulsion was launched with enhanced lubrication and no interfering residue. Like the rest of the product line, RediLube is solvent-free, water-based and non-hazardous. Plus, P-80 Emulsion, THIX, RediLube, and the incidental food contact lubricants are biodegradable. All products are non-irritating to eyes and skin and non-toxic, based on an independent laboratory's evaluation.

The P-80 lubricants have a global presence in many industries that use or manipulate rubber or plastic.

Dantogard Preservative: An Antimicrobial Technology with Reduced Environmental Impact for Hydraulic Fracturing of Shale Gas Plays: DRAFT: The development of shale gas plays within the U.S. is growing. In order to effectively produce the gas, hydraulic fracturing techniques are required. Such techniques have been under significant scrutiny, particularly with regard to the potential for contamination of drinking water aquifers. Specific concern has focused on the use of biocides in hydraulic fracturing fluids. Commercially launched at the World Shale Gas Conference® in November , Dantogard® Preservative provides antimicrobial protection while reducing worker and operational risks associated with handling biocides since it ships as a non-hazardous product, is readily biodegradable, and exhibits up to 300 times lower environmental toxicity than alternate biocide technologies currently being used on the market for this application. Further, its extended antimicrobial protection and improved interaction with fluid additives provides the ability to reduce the amount of biocide utilized by 50 percent and the potential to eliminate carbon dioxide emissions by over 16,000 MT per year.

Vistive® Gold Soybeans and Biosynthetic Technologies Enable Biodegradable, Non-Toxic, Renewable, and Economical Industrial Bio-Lubricants: DRAFT: Lubricant manufacturers have tried for years to use vegetable oil as a base stock to meet the growing demand for biodegradable, non-toxic, and renewable products, thereby reducing the world's reliance on limited petroleum-based oils. However, vegetable oils' poor oxidative stabilites and insufficient cold temperatures properties limit their usefulness in the lubricant market.

Monsanto scientists combined cutting edge RNAi biotechnology and molecular breeding to create Vistive Gold® soybeans, setting a new performance standard for vegetable oil. These soybeans produce 60 percent less saturated and polyunsaturated fats and three times more monounsaturates than commodity soybeans. The reduced saturates improve cold temperature properties, while increased monounsaturates (high oleic) and reduced polyunsaturates improve oxidative stability, making the oil better suited for industrial and automotive use.

Vistive Gold® soybean oil can be a feedstock for a new class of bio-based synthetic oils that meet or exceed the performance characteristics of the highest quality petroleum-based oils currently used in the automotive and industrial lubricant sectors. In , U.S. consumption of lubricants was estimated at 2.4 billion gallons.

Biosynthetic Technologies developed this new class of biosynthetic oils in collaboration with the U.S. Department of Agriculture (USDA). The most significant benefit is that these lubricants are biodegradable. Since one gallon of used engine oil can contaminate over one million gallons of fresh water, 40 percent of freshwater pollution comes from used motor oil, and over 500 million gallons of petroleum oil is released into the ocean annually, the global impact of these technologies is yet to be realized.

Biosynthetic Technologies is in the final stages of fleet testing LubriGreen® biosynthetic motor oils and several major oil companies are formulating their first-ever biosynthetic motor oils from these bio-based oils. Pilot plant production will begin in .

The Use of Nitrate and Selected Live Strains of Nitrate Reducing Bacteria to Replace the Use of Biocide in Hydraulic Fracturing Operations: DRAFT: Hydraulic fracturing in shale formations to enhance extraction of hydrocarbons is a relatively new technique in the oil and gas industry. Concerns have arisen regarding the potential environmental impact of fracturing due in part to the use of large volumes of chemicals used for each well. Biocides are used during fracturing to prevent biogenic production of toxic and corrosive H2S. The technology was developed to completely eliminate the use of biocides during fracturing and replace them with a technology that employs relatively benign components. This technology relies on the use of live strains of nitrate reducing bacteria (NRB) that have been selected to grow in reservoir conditions of the given oil or gas field. The NRB, in addition to a nutrient (sodium nitrate), are injected into the formation during the fracturing operation. NRB are able to consume the nutrients that deleterious bacteria, such as sulfate reducing bacteria, would otherwise use, thus preventing corrosion and production of H2S. This technology has been fully tested in both the laboratory and the field. To date, 20 wells have been successfully treated. Treatment results from each of the test wells have been equal or superior to conventional biocide treatments (bacteria concentrations, sulfide concentration, and water clarity). Multi-Chem expects to fully commercialize manufacturing and application by the 3rd quarter of . Multi-Chem estimated that this technology will be suitable to treat 15,146 wells per year based on estimates of wells to be completed in formations with temperature less than 180°F (upper temperature limit of NRB strains). Biocide types and volumes used in fracturing vary somewhat, but based on typical use patterns it is estimated that 15,903,300 gallons of 50 percent glutaradehyde/quat biocide (or other equivalent biocide) may be eliminated annually due to this technology.

Expanding the Renewable Polymers "Tool Kit" with Bio-Succinic Acid: DRAFT: In the second quarter of , Myriant Corporation will be the first in the U.S. to commercially produce bio-succinic acid at its flagship facility in Lake Providence, Louisiana. Bio-succinic acid is an organic acid with the potential to be used as a raw material for the production of numerous industrial and consumer applications. Myriant's high purity bio-succinic acid is made from renewable feedstocks and is chemically equivalent to petroleum-based succinic acid while significantly reducing harmful greenhouse gas emissions. Polyester polyols are mainly produced using adipic acid, a petroleum-based chemical that can be replaced with Myriant's bio-succinic acid without compromising the final product quality or performance. Myriant, Piedmont Chemical Industries, and Dupont Tate & Lyle have partnered to produce 100 percent renewable polyester polyols formulations for the production of polyurethanes.

Bio-based Chemicals from Low-cost Lignocellulosic Sugars: DRAFT: Myriant successfully developed its proprietary process for the production of drop-in chemicals and replacement chemicals, including succinic acid and lactic acid, from low-cost, non-food, lignocellulosic feedstocks. Myriant currently has several E. coli platforms capable of generating high titers of organic acids from clean sugars and most importantly from lignocellulosic hydrolysate sugars. Life cycle studies performed on Myriant's bio-succinic acid technology as compared to petroleum-derived succinic acid showed a potential of 94 percent reduction in greenhouse gases. Myriant's bio-succinic acid, a four-carbon molecule, and biobased lactic acid, a three-carbon molecule, will be used as drop-in and replacement chemicals in their current petroleum-based markets. In the second quarter of , Myriant's flagship commercial facility that utilizes a multi-feedstock technology platform will produce annually 30 million pounds of bio-succinic acid.

eVerified ASP560: An Environmentally Friendly Corrosion Inhibitor: DRAFT: The discovery of shale plays across the U.S. has caused an unprecedented growth of oil and gas production. Hydraulic fracturing has become widely used to access these unconventional oil and gas reservoirs. However, public debates over the safety of hydraulic fracturing and state-government regulations have increased the demand for the use of environmentally friendly hydraulic fracturing fluids.

To meet this challenge, Nalco has developed environmentally friendly hydraulic fracturing fluids additives--called eVerified products--to replace more hazardous conventional technologies. Specifically, Nalco focused on acid corrosion inhibitors (ACIs). ACIs are an integral part of the acidizing segment in a hydraulic fracturing and acid fracturing application and considered to be one of the most hazardous components in these applications. Conventional ACI chemistries often contain Clean Water Act and Clean Air Act contaminants; may be toxic, persistent, bioaccumulative (PBT); and may be carcinogens, mutagens, or reproductive toxicants (CMR). The goals of eVerified are: to improve the overall hazard profile, meet key performance attributes, and be cost-competitive.

The eVerified ACI ASP® 560 is based on a patent-pending chemistry that used EPA predictive modeling for the design of the active component. The formulation was developed using a hazard profile screening tool, called eVerified, to make environmental, ecological, and human health improvements. Specifically, ASP® 560 removed priority pollutants; removed CMRs, Drinking Water, and Clean Air Act contaminants; enhanced biodegradability; reduced aquatic and mammalian toxicity; and reduced the flammability/combustibility when compared with current technologies. Assuming that the hazard profiles of Nalco ACIs for this market segment are typical, replacing all ACIs currently being used from all suppliers with ASP® 560 could remove an estimated 18 million pounds per year of hazardous substances.

Sustainable Soda Ash for the Glass Industry: DRAFT: New Sky Energy is a clean chemistry company dedicated to source reduction of carbon dioxide pollution in the air as well as salt brine pollution in fresh water. New Sky's technology offers a novel approach to making high-purity, commodity chemicals (acids, bases, carbonates, and bicarbonates) that are key inputs for many industrial processes and building materials. Instead of mining, processing, and transporting virgin materials, New Sky's technology uses the carbon dioxide and salt brine waste products from industrial processes as low-cost, renewable feed-stocks for generating high-value, clean chemicals. Using New Sky's technology, carbonates and bicarbonates for glass, cement, paper, plastics, and food processing can be produced on-site, minimizing transportation costs and emissions while using reaction conditions that are entirely compatible with renewable energy and a smart grid.

The environmental benefits of New Sky's technology are numerous and include power plant emission controls, wastewater from biofuels and oil and gas, and recycling of acid or salt wastes from semiconductor manufacturing, mining, and other industrial activities. There are also lifecycle benefits of using the process to make sodium carbonate (soda ash) for the glass industry.

New Sky is currently working with one of the world's largest glass companies toward the goal of deploying the New Sky process on an industrial scale within three years. Based on estimates by New Sky's glass industry partners, use of the New Sky process to replace traditional sources of soda ash (i.e., trona mining and synthetic (Solvay Process) soda ash) would reduce the industry's direct CO2 emissions by 15-20 percent. Furthermore, when powered by zero-carbon energy, New Sky's process could eliminate almost all of the glass industry's upstream emissions from soda ash production, resulting in total CO2 reductions of up to 35 percent.

Enzymes for the Production of Economical Sugars: A Linchpin of the Carbohydrate Economy: DRAFT: With the introduction of CTec3, Novozymes has catalyzed the commercial plans of major biofuel and renewable chemical producers globally. Plant cell walls are a complex matrix of cellulose, hemicellulose, and lignin. Efficiently hydrolyzing this recalcitrant lignocellulosic material is a critical step towards providing high-quality sugar streams as a feedstock for the production of fuels and chemicals via fermentative or chemical pathways. Novozymes' technology employs biological catalysts (enzymes) to achieve high sugar yields from a variety of feedstocks (e.g., corn stover, wheat straw, perennial grasses). A key breakthrough in Novozymes' development was the discovery of a previously uncharacterized family of proteins (GH61), which utilize a redox mechanism to synergize with classical hydrolases in lowering the enzyme dose needed to hydrolyze lignocellulose. Novozymes pioneered this novel technology, and holds several patents covering the use of these important cellulolytic enhancers. A highly active GH61 protein has been incorporated into the CTec3 enzyme cocktail. CTec3 allows a significant improvement in biomass conversion efficiency over previous enzymatic cocktails, enabling the production of cellulosic biofuels whose utilization reduce greenhouse gases by 90-115 percent in comparison with gasoline. Novozymes is supporting its key partners in commercializing proven technologies for producing these biofuels, including the world's first commercial cellulosic ethanol production facility (13 million gallons per year) currently being commissioned by the Mossi & Ghisolfi Group (M&G) in Crescentino, Italy. A subsidiary of M&G (Chemtex) announced that it has received a $99 million loan guarantee from USDA for the engineering and construction of a biofuels plant in North Carolina utilizing dedicated energy crops as the biomass feedstock. Other major companies (POET, Abengoa, DuPont) are also proceeding with biorefinery construction plans.

Sustainability and Owens Corning's EcoTouchTM Insulation Conversion: DRAFT: Sustainability is a core business strategy at Owens Corning (OC). OC is committed to driving sustainability by delivering solutions, transforming markets and enhancing lives. From a baseline, OC set aggressive 10-year footprint reduction goals across seven key areas of resource consumption, waste, and air emissions. Six of the seven goals were achieved by the end of . OC's goals target significant reductions in energy, greenhouse gas, water, toxic air emissions, particulate matter, and waste-to-landfill. In addition to footprint reduction goals, OC has expanded its goals to drive and track the sustainability of its products and their applications, and to accelerate its supplier sustainability initiatives.

OC's insulation product is comprised of 95 percent glass fibers and 5 percent binder. The binder is a chemical adhesive that is required to hold the glass fibers together. EcoTouchTM insulation is a new fiberglass wool insulation product that is 99 percent natural and certified to have a minimum of 58 percent recycled content. OC has used a formaldehyde-based binder for over 70 years and its customers were increasingly requesting a product made with more sustainable materials. In addition to satisfying the customers, the substitution of the starch-based binder for the phenolic/formaldehyde binder eliminated or significantly reduced the hazardous air pollution (phenol, formaldehyde and methanol) along with ammonia emissions associated with the old resin formula. Reducing the environmental footprint of OC's manufacturing plants is consistent with the sustainability strategy initiated by the company while delivering the productperformance attributes that the customers expect.

EcoTouchTM is the first fiberglass insulation to be certified by the U.S. Department of Agriculture (USDA), as a biobased product. In addition to the USDA renewable plant material certification, EcoTouchTM was recently certified by Scientific Certifications Systems for new recycled content figures, total recycled content rose from 50 percent to 58 percent for faced batts and rolls, to 65 percent for unfaced batts, rolls, MBI and loosefill. EcoTouchTM insulation has achieved GREENGUARD Children & Schools Certification, is verified to be formaldehyde-free, and carries the UL Environment Ecologo CCD016 preferable product designation.

A Greener Hydroformylation Technology: DRAFT: Hydroformylation for producing chemical intermediates such as aldehydes and alcohols from olefinic substrates is a 15 billion pound per year industry. It also can be a route for producing longer chain olefins. Hydroformylation technologies with tunable selectivity are of particular interest. During conventional hydroformylation with 1:1 syngas (molar H2/CO =1), the H2/CO ratio in the liquid phase is ~0.6, which is not only sub-optimal for rate/selectivity but also non-tunable without adding extra H2 in the feed.

Dr. Subramaniam demonstrated continuous hydroformylation of olefins in carbon dioxide-expanded liquids (CXLs) at unprecedented rates and selectivities. This was accomplished in a stirred reactor equipped with a nanofiltration membrane that effectively retains a dissolved rhodium complex in the reactor, allowing only lighter components to pass through. This technology uses benign solvents, intensifies the process at mild conditions, and eliminates toxic reagents. Additionally, comparative economic analyses demonstrate practical viability. Environmental analysis shows that the CXL process produces 50 percent less waste and is 33 percent less toxic than the conventional cobalt-based process. The technology has been successfully extended to several olefinic substrates demonstrating its versatility.

Remarkably, when the conventional solvent is partly replaced by dense CO2 to create a CXL phase, the H2/CO ratio in the CXL phase is significantly increased at mild syngas pressures (~6 bar) and neither syngas starvation nor CO inhibition is observed. The increased free volume in CXLs apparently enhances H2 solubility beyond what is possible by Henry's law. Consequently, 1-olefin hydroformylation in a CXL phase with a simple rhodium catalyst complex [Rh[(CO)2(acac) and triphenylphosphine (TPP)], results in impressive turnover frequency (~340 h-1) and regioselectivity (linear/branched aldehydes ~ 8) at mild pressure (~38 bar) and temperatures (30-60°C). A nearly quantitative rhodium recovery is accomplished by using the bulky JanaPhos ligand (molecular weight: 12,000 g/mol) which is effectively retained in solution by nanofiltration. This technology has been extended successfully to produce 1,4-butanediol via the hydroformylation of allyl alcohol. Based on lab-scale demonstration data, a major U.S. company has licensed the issued patent and the patent application for defined fields of use and industry partners are also evaluating the technology for licensing.

Easy (1-Reagent) Nitrate Method: A Green Alternative to Traditional USEPA Approved Nitrate Methods: DRAFT: Several methods exist for determining nitrate in aqueous solutions. However, the traditional USEPA approved methods 353.1 (Nitrate Hydrazine Reduction) and 353.2 (Nitrate Cadmium Reduction) are problematic, frequently unreliable, and utilize carcinogenic and highly toxic chemicals. Thousands of laboratories in the U.S. and worldwide use these methods, or variations of them. The alternative methods performed by ion chromatography and ion selective electrode are slow and unreliable when performing analysis on samples with high ionic strength, such as wastewater, ground water, and soil extracts. The new Easy (1-Reagent) Nitrate Method was developed by Systea Scientific, LLC to eliminate the problems associated with these traditional methods and improve performance.

The Easy (1-Reagent) Nitrate Method utilizes a reaction in which nitrate is reduced to nitrite by a proprietary reagent "R1"&#;a non-hazardous, non-enzymatic reducing agent. The method protects laboratory personnel from hydrazine and cadmium exposure and eliminates hazardous waste, significantly reducing potential liability associated with waste handling and disposal.

The Easy (1-Reagent) Nitrate Method eliminates analytical problems associated with nitrate analysis, such as poor reproducibility, recovery, and matrix interferences. With the Easy (1-Reagent) Nitrate Method, the nitrate to nitrite reduction is consistently between 95 and 105 percent, which is a dramatic improvement over traditional nitrate methods. In the cadmium reduction method and hydrazine methods, efficiency of the reduction depends on the matrix. After extensive testing on various matrices, no matrix interference problems have been observed when using the Easy (1-Reagent) Nitrate Method. Furthermore, the reagent costs dramatically less than other non-hazardous methods for nitrate, such as enzymatic tests. Depending on how the method is performed, the reagent costs approximately four cents or less per test. Laboratories also save time on analytical runs, since the overall performance of the new method is better and matrix interference problems are not present. The Easy (1-Reagent) was EPA approved in for analysis of both drinking water and wastewater. It was listed in the Federal Register as an approved method for nitrate, nitrite, and combined nitrate/nitrite analysis under 40 CFR Part 136.3 on May 18, .

Formaldehyde-Free Commercial-Grade Particleboards Based Solely on Soybean Protein Adhesive: DRAFT: Decreasing forest cover and an increase in consumption of wood-based materials have generated strong demand for particleboard and other engineered wood composites made from wood wastes. Commercial particleboards use urea-formaldehyde (UF) resin as an adhesive and are known to emit formaldehyde during manufacture use. Formaldehyde causes adverse health reactions in humans, even at low concentrations, and the International Agency for Research on Cancer has classified formaldehyde as a human carcinogen.

The occupational exposure of formaldehyde during particleboard production and the slow liberation of formaldehyde during the service life of particleboards pose serious health concerns. Alternative particleboards have been derived from wheat straw blended with methylene diphenyl diisocyanate, corn stalk pith, and sodium hydroxide-modified soy protein isolate. However, isocyanates present toxicity issues of their own with respect to handling and processing. There are no existing commercially viable technologies that totally replace the UF resin without adversely affecting particleboard properties, increasing production costs, and/or using another toxic chemical.

Drs. Thames and Rawlins have developed particleboards that are free of synthetic formaldehyde precursors by employing a soybean protein adhesive (SPA) as the sole binder. The SPA particleboards match, and in some instances, exceed the performance properties of commercial particleboards. Their research generated two U.S. patents and recent discoveries have been included in another patent application. Trials at a particleboard manufacturing plant in Texas have validated the scalability and feasibility of commercializing the SPA.

The adhesive synthesis involving mechanical blending of commercial grade soybean protein with water and raw materials to open the protein chains thereby making them amenable to flow and wetting. The process is energy efficient and does not involve toxic chemicals. The adhesive blends easily with wood furnish at wood to resin ratios similar to those employed for commercial particleboard manufacture. Particleboards manufactured with SPA technology meet the American National Standards Institute (ANSI) performance specifications for M-1, M-2, M-3, and M-S grade particleboards and completely avoid synthetic formaldehyde precursors. A full plant trial adoption of SPA at just one plant would lower the consumption of UF resin by ~35,000 metric tons and toxic formaldehyde by ~17,500 metric tons.

Upcycling Process That Converts Unsorted Plastic Waste into Functional Carbon Materials: DRAFT: Environmentally harmful plastic waste is a major concern throughout the world. Argonne's novel autogenic process completely destroys unsorted plastic waste in a technologically eneficial, environmentally responsible manner before the plastic enters the waste stream. The one-step, low-energy, solventless process is called "upcycling" because it produces products having greater value than the original plastics, particularly hard carbon microspheres that have important tribological and battery technology applications and carbon nanotubes that may prove preferable to the carbon microspheres for some tribological uses.

Current automotive engine lubricants contain anti-friction and anti-wear additives that poison catalysts in catalytic converters, thus increasing harmful emissions from such vehicles. To meet the increasingly stringent emission targets of the EPA and other regulators, lubricant manufacturers have sought, yet unsuccessfully, to replace these damaging additives. Dispersing small amounts of Argonne's carbon microspheres or nanotubes in engine oils yields great reductions in both friction and wear, thus potentially permitting discontinuation or reduced use of the harmful additives, thereby boosting catalytic converter effectiveness in reducing emissions.

Graphite is universally used in the negative electrodes (anodes) of commercial lithium-ion batteries, even though graphite anodes can cause the batteries to rapidly overheat and catch fire, as perhaps recently occurred aboard the Boeing Dreamliner aircraft. Anodes made with Argonne's hard carbon microspheres cycle lithium much more safely than flake-like graphite anodes. Also, upon being briefly heat-treated to &#;°C and sonochemically coated with a lithium-alloying element, the microspheres can deliver an electrode energy capacity (>400 mAh/g) that exceeds the capacity of every commercial graphite anode in use today. Both capabilities are crucial to the increased use of lithium-ion batteries in transportation applications. Numerous other applications exist for the carbon microspheres and nanotubes as well, ensuring that the technology can potentially prevent large amounts of unwanted plastic from ever entering the waste stream.

Converting Plant Sugars into Paraxylene for 100% Renewable, 100% Recyclable Packaging and Fibers: DRAFT: Volatile costs of fossil fuels, concerns for the environment, and focus on sustainability and domestic energy security have sparked worldwide interest in developing alternatives to petroleum-based chemicals and fuels. Virent has discovered an innovative technology that catalytically transforms 100 percent renewable sources into paraxylene. Traditionally sourced from petroleum, paraxylene is a chemical highly useful in the production of packaging and fibers.

Compared to other biomass conversion systems, Virent's technology broadens the range of viable renewable feedstocks as a variety of cellulosic and conventional sugars can be utilized. Virent's bio&#;based paraxylene, BioFormPX, is molecularly identical to petroleum&#;based paraxylene and is compatible in today's chemical supply chains. PET made with BioFormPX paraxylene can also seamlessly enter into already established recycling streams and infrastructure. This retains the majority of the energy used to manufacture the material in contrast to biodegradable molecules.

Across its supply chain, from sustainable feedstock through manufacturing to final highly useful products, bio&#;based paraxylene is more environmentally friendly and less threatening to human health compared to petroleum as a feedstock. Not only are biobased feedstocks safer than petroleum to handle, Virent's production of paraxylene incorporates CO2 from the atmosphere into materials, thereby reducing greenhouses gases by up to 55 percent with conventional sugars.

Virent currently produces biobased hydrocarbons &#; including the basis for its BioFormPX product &#; at its 30,000 kg/year demonstration plant. In , Virent and The Coca&#;Cola Company formed a strategic partnership to accelerate commercial production of Virent's BioFormPX paraxylene. Coca&#;Cola's PlantBottle is currently made with up to 30 percent biobased material. Virent's BioFormPX is the missing ingredient needed to make 100 percent biobased PET.

This will enable The Coca&#;Cola Company to launch commercial scale 100 percent biobased PET bottles, providing its customers with 100 percent renewable and recyclable PET beverage packaging made from biobased materials.

Pure Solutions Chemical Line for Laundries: DRAFT: Since , Washing Systems has made the commitment to develop washing chemistry for industrial laundries across the U.S. that would enable customers to improve their environmental profile and financial well-being. After two years of developmental work and field testing, the Pure Solutions Chemical Line for detergents was developed which is entirely nonylphenol ethoxylate free. As of April , 100 percent of Washing Systems' customers have converted to these green DfE (USEPA Design for the Environment) detergents. From the projects inception, the Pure Solutions Chemical Line has reduced over 21.6 million pounds (an average of 3.6 million pounds per year) of NPE discharged into the environment from wastewater discharge, which is toxic and an endocrine disruptor.

Washing Systems also introduced a new builder (Structure) which is based on natural, sustainable, and biodegradable chelating agents for lowering water hardness within the washer. This builder eliminates the use of phosphates and ethylenediaminetetraacetic acid which is a persistent organic chemical with hazardous degradation products. This product was developed in , and distributed in . Currently, 100 percent of Washing Systems' customers have converted to this more environmentally friendly chemistry which has reduced the level of tetrapotassium pyrophosphate by 1.5 million pounds and 104,000 pounds of tetrasodium ethylendiamine tetraacetate within one year.

Another Washing Systems project initiative was to eliminate the petroleum solvents from its solvent/detergent formulas. Washing Systems has also replaced two of its core products that contained aromatic hydrocarbons and aliphatic hydrocarbons, which easily bioaccumulate, with a nonhazardous, biodegradable, biobased product. In just a few months of distribution, this product has reduced over 100,000 pounds of petroleum solvents into the environment; and as of , its use has reduced petroleum solvents close to 400,000 pounds per year, 50 percent of our customers.

A Greener, Safer and More Efficient Antifreeze: DRAFT: Ethylene glycol, the main ingredient in antifreeze, smells and tastes sweet, attracting both children and pets to consume it. Ethylene glycol should not be confused with propylene glycol, a common food additive. Drinking ethylene glycol antifreeze will cause heart and breathing difficulties, kidney failure, brain damage, and even death. The major cause of toxicity is not the ethylene glycol antifreeze itself but its metabolites. The American Association of Poison Control Centers reported that there were 5,784 poisonings due to ethylene glycol antifreeze in . There were 431 reported cases of children under the age of 5 years old and some of these cases were fatal.

ACTA&#;s product improves the heat transfer capability of propylene glycol and is 58 percent better than ethylene glycol antifreeze in a circulating cooling system. Therefore, heat transfer performance and cost should no longer be reasons to use the potential lethal ethylene glycol antifreeze.

ACTA&#;s additive to propylene glycol antifreeze can reduce dependence on foreign oil and reduce greenhouse gas emissions because of improved energy efficiency. ACTA&#;s product covers a greener and non&#;toxic chemical.

The eVOLVTM System, a Clean, Sustainable Solution to Electronic Waste: DRAFT: The eVOLVTM system was created to help solve the global issue of electronic waste (e&#;waste). While laws in developed nations have been pushing to regulate or eliminate dirty, harmful e&#;cycling practices and scrap piling, underdeveloped nations are seeing their lands being used as dumping sites. These sites host opportunities for people, including children, to use dangerous open burning techniques and toxic chemicals to extract metals for resale. While these conditions are deplorable, the piles themselves are growing and are polluting the soil and groundwater.

A United Nations report states that e&#;waste will grow by one&#;third by the year to total about 65.5 million metric tons. According to the report, the United States produced 9.4 million metric tons in &#;the most of any country. In all, e&#;waste is the fastest&#;growing municipal waste stream in the world.

The eVOLVTM process is the first of its kind to safely reclaim base and precious metals at a large scale with a 98 percent recovery rate and virtually zero waste. The system consists of three process tools and a series of chemistries. It operates at or near room temperature and uses very little energy. It processes printed wiring boards, cell phones, and integrated circuits, or computer chips. Traditional shredding or grinding of boards, which leads to the loss of precious metals and/or the formation of dangerous contaminants, is eliminated. The chemistries are engineered for selectivity to dissolve different metals for easy recovery. Each chemistry was designed using the 12 Principles of Green Chemistry and is less toxic than common orange juice. In addition, each chemistry &#; and all process water &#; can be infinitely reused, generating no waste. All metals recovered are at a purity of 98 percent or better and can be re&#;inserted into manufacturing processes.

Improved Performance and HSE Profile of a Novel Stimulation Fluid for Oil and Natural Gas Wells: DRAFT: Well stimulation is a process to improve oil or gas well productivity as the well&#;s output naturally declines. Stimulation typically involves the injection of hydrochloric acid (HCl) or hydrofluoric acid (HF) based fluids at high pressure into the well. These corrosive acids dissolve portions of the rock near the well bore and allow more oil or gas to freely flow. While stimulation can significantly improve the productivity of a well, safely handling these corrosive acids is a significant challenge &#; e.g., HF is a contact poison. Additionally, additives needed to mitigate the corrosive impact of HCl further aggravate the safe handling and environmental impact due to these additives&#; poor ecotoxicological profiles. Wells at high temperature and pressure require a greater number and concentration of these additives, further emphasizing the need for both safe handling and ecotoxicological profiles of the treatments. As wells trend toward off&#;shore with higher temperatures and pressures, there are greater health, safety and environmental considerations and safer stimulation fluids are desired.

Recent lab studies and field applications with a new stimulation fluid based on the chelating agent Glutamic Diacetic Acid (GLDA) has shown that GLDA can improve oil and gas flow in carbonate and sandstone petroleum reservoirs. Even at high temperature and pressure, additives are not needed with GLDA to prevent corrosion of carbon steel or chrome&#;based well pipes. Contrary to conventional stimulation fluids used in the industry, GLDA is a biodegradable, non&#;toxic and non&#;hazardous chemical. GLDA was recently recognized by EPA&#;s Design for the Environment (DfE) program as a safer chemical ingredient and is certified as 58 percent bio&#;based by the USDA&#;s Bio&#;Preferred Procurement Program. The successful application of GLDA in four high temperature gas wells in the Gulf of Mexico resulted in a doubling of production using this safe and environmentally friendly stimulation fluid based on GLDA.

Earthcolors Technology: DRAFT: Nowadays, all raw materials currently used for the production of textile dyestuff at commercial scale are derived from petroleum via a complex process of oil extraction, refining, and synthesis. Archroma is using a key raw material derived from biomass to produce soluble dyestuffs that are capable of dyeing cellulosic fibers such as cotton, viscose, paper, and Tencel with high strength and color fastness properties. For this purpose, the term "biomass" is defined as the residual product obtained from the usual human crop activities in agricultural and forestry sectors.

Archroma R&D has been working for the past five years on the technology resulting in two patents: EP 2 527 407 (WO ) & EP (WO ) (patent pending). Abundant, globally available, and renewable, the different agriculture crop waste is directly used as raw material and 100 percent transformed to final dyestuffs. A range of six dyes have been developed at this stage: two dyes are synthetized using 100 percent biomass while the other four dyes are 90 percent biomass + 10 percent petrol due to the limitation of color range when using 100 percent biomass. The first bulk batches were produced in , and the full range will be available at the end of May . The recent implementation of these dyes showed equal performance to the conventional dyes using standard and the best available wet processing techniques.

There are two main benefits for the new technology:

• The massive reduction of the use of aromatic toxic compounds and of the generation of CO2 in comparison with present known procedures of the petroleum aromatic chemistry. The technology also eliminates the high environmental risks of oil extraction and further processing; and
• The use of waste from another industry (circular economy).

SYLVAROADTM RP Performance Additive: A Sustainable, Pine&#;Based Additive to Enable High Re&#;Use of Reclaimed Asphalt Pavement: DRAFT: In January , Arizona Chemical Company, LLC commercially launched the SYLVAROADTM RP performance additive for asphalt pavement. Arizona Chemical produces this new, bio&#;based additive from pine trees using a green production process. This product enables Arizona Chemical&#;s customers in the paving industry to incorporate significantly higher percentages of reclaimed asphalt pavement in their hot mix asphalt, thus preventing waste and reducing the use of virgin materials such as aggregate and binder while still maintaining the specified performance of the pavement. Enabling higher aged pavement recycling not only saves virgin raw materials, but also makes economic sense due to reduced raw material costs. Arizona Chemical&#;s technology upgrades a byproduct from the paper pulping industry into a value&#;added specialty chemical for improving infrastructure in the United States.

Green Biological Production of Short and Medium Chain Esters: DRAFT: Increasing global demand and reliance on petroleum&#;derived chemicals will necessitate alternative sources for chemicals and all the products made possible by them. Currently, 99 percent of chemicals are derived from petroleum and natural gas. The ester classes of small molecules are used for fragrances and cosmetics due to their fruity and floral aromas but are also heavily used in paints, coatings, and solvents. In , the global market for flavors and fragrances was $16 billion. Small esters are commonly produced by acid&#;catalyzed esterification synthesis of an organic acid and alcohol substrate that are usually sourced from petroleum under harsh conditions. Synthetic biology and metabolic engineering enables the renewable production of fuels and chemicals from microorganisms by constructing unique metabolic pathways. Professor Atsumi and his team developed a new strategy for ester production that is cleaner and more sustainable. The alcohol O&#;acyltransferase (ATF) class of enzyme utilizes acyl&#;CoA units for ester formation, which takes advantage of the stored energy in the thioester bond of the acyl&#;CoA molecule. The release of free CoA upon esterification with an alcohol provides the free energy to facilitate ester formation under green conditions. Thus, Professor Atsumi and his team engineered the industrial production host, Escherichia coli, to produce various esters under green conditions (water and ambient temperatures) and from a renewable carbon source (glucose). They achieved high&#;yield and titer production of isobutyl acetate, which demonstrates the commercial potential of this platform. Ultimately, Professor Atsumi and his team demonstrated production of 13 different ester compounds using the strategy. This renewable technology can potentially replace petroleum&#;derived ester synthesis, greatly reducing carbon emissions and the associated health hazards.

Consumer Viable and Environmentally Friendly Solvent Replacements Developed From Food Grade Compounds: DRAFT: The BODYGUARD is a new, water&#;based and environmentally friendly, multi&#;surface treating emulsion developed to replace solvents, degreasing agents, and cleaning agents that use chlorofluorocarbons, specifically methylchloroform, CFC&#;13, and HCFC&#;225. The BODYGUARD uses cavitation, capillary attraction, and encapsulation to protect and clean surfaces from bonding materials such as epoxies, frozen loads, wet soils, clays, wet concrete, ice, asphalt, and biofouling. The patented formula controls surfaces and creates a bridge across the millions of micropores on surfaces that allow bonding.

In , Bay State Tech, LLC completed its 12&#;month field testing of the BODYGUARD and secured manufacturing of the product. In , Bay State Tech, LLC began responding to procurement opportunities from different municipalities across the United States. The BODYGUARD is a USDA certified Bio&#;Preferred product and tested to be 96 percent bio&#;based. The technology is a combination of water with food grade additives including a boron compound, a gelling compound, and an inorganic alkali compound.

The Scalable Production of Edge Functionalized Few Layer Graphene Oxide: DRAFT: Edge&#;functionalized few layer graphene oxide (EFGO) can be rapidly prepared in large quantities by mechanochemical means. Grinding graphite with urea hydrogen peroxide adduct produces a highly delaminated product with an oxygen content of 5&#;20 percentage by weight. The only byproducts of this synthesis are water and urea. This process does not require toxic reagents and it produces byproducts generally considered safe. The edge&#;functionalized graphene produced by this method is hydrophilic and easily suspended in water, allowing for convenient processing of films and epoxy composites. It can also be electrodeposited to form uniformly smooth coatings. This material is electrically conductive and free from manganese impurities that often plague graphite oxides prepared by Hummers&#;&#;type methods. Analyses show that the graphite is fully oxidized to &#;COOH groups along the edges of individual graphene sheets. This approach offers a scalable, environmentally benign route to large quantities of EFGO.

Boegel Surface Activation Technology Suite: DRAFT: The Boegel Surface Activation Technology Suite is an environmentally friendly alternative to hazardous surface preparation methods for metallic structures. Invented by a team of Boeing chemists, the process is based on sol&#;gel condensation polymerization and utilizes tailored molecules which link metals to resins by covalently bonding with both surfaces and resins in order to create a strong, durable chemical bond between critical layers. The Boegel Suite includes a number of related sol&#;gel formulations that can be used on aluminum, titanium, stainless steel, nickel, tungsten, and many other alloys. It has been leveraged for painting, bonding, and sealing surface preparations across the Boeing Enterprise, including commercial, military, and space vehicles. Hazardous materials that Boegel successfully replaces include acidic and hexavalent chromium &#; containing conversion coatings such as Alodine, Phosphate Fluoride, Pasajel 105 and 107, and Chromic Acid Anodizing. In addition to ridding Boeing manufacturing processes of many major environmental concerns, Boegel has also simplified work and increased efficiencies in numerous paint operations, increased performance and durability, reduced chemical inventories, and has become a key enabling technology for metal bonding and sealing, with improved adhesion and durability performance.

Novel, Effective, Safe Delivery System for Antimicrobial Agents Derived from Sustainable Vegetable Monoglycerides: DRAFT: Biopolysan® is a novel antimicrobial composition derived from coconut oil. The patented manufacturing process is a relatively low temperature, single vessel reaction wherein monoglycerides are heated in the presence of a polyhydric alcohol and an alkaline catalyst. The result of processing is a liquid crystal mixture of glycerol and propylene glycol esters and salts thereof with drastically improved solubility, stability and efficacy. Biopolysan® is composed of generally recognized as safe (GRAS) food&#;grade ingredients. The active ingredient, glyceryl laurate, is derived from coconut oil, a renewable source. There is no waste stream and no harmful byproducts are produced by the process. Biopolysan® has applications in numerous industrial and medical settings including as a preservative and other anti&#;microbial applications.

Commercialization of Biopolysan® as a multifunctional ingredient for use in various formulations began in . The benefits to the formulator are many, and include green preservation, greener chemistry, emolliency, improved penetration and skin feel as well as cost savings and simplification of the manufacturing process when Biopolysan® replaces a plurality of ingredients in some products. Current products on the market formulated with Biopolysan® include both animal and human products. Once Biopolysan® 120 (Copperhead&#;s standard Biopolysan® formulation) receives its FIFRA registration, commercialization of Biopolysan® as a preservative is expected to replace a portion of the annual 40,000 metric ton traditional preservative market.

Cylinderized Phosphine as Safer, More Environmentally Friendly Alternatives to Traditional Stored Product Fumigants: DRAFT: Cytec Industries Inc. has developed and commercialized technology for the stored product fumigation market. Traditional fumigants such as methyl bromide and metallic phosphides have significant safety and environmental shortcomings in their use, application, and disposal. Methyl bromide is an ozone depleting chemical and is partially being phased out under the Montreal Protocol. Metallic phosphide suffers from worker safety and environmental issues created by the residues. Cytec&#;s cylinderized phosphine products, ECO2FUME (a non&#;flammable blend of two percent phosphine and 98 percent CO2) and VAPORPH3OS® (phosphine fumigant), offer inherently safer alternatives as they involve less worker exposure and do not significantly impact the environment. The use of Cytec&#;s cylinderized products for fumigations in 24 hours allows for greatly expanded use of these products as drop&#;in replacements for methyl bromide and they are now being used commercially in a number of 24&#;hour applications across the United States. To date, this technology has resulted in an annual global waste reduction of 900,000 pounds of solid chemical residue and 600,000 aluminum flasks. In addition, this technology has annually eliminated 620,000 pounds of methyl bromide use and 1,500,000 pounds of metallic phosphide use globally.

FORMASHIELDTM Formaldehyde Abatement Technology: DRAFT: FORMASHIELDTM is a breakthrough polymeric binder technology that abates gaseous formaldehyde from the surrounding ambient environment. FORMASHIELDTM Binders incorporate novel technology that imparts smart functionality to interior architectural paints. The wall of homes and buildings painted with architectural paints incorporating FORMASHIELDTM are well positioned to abate a carcinogenic pollutant like formaldehyde thereby improving indoor air quality for occupants.

According to the United States Green Building Council, buildings in the United States consume 36 percent of the total energy usage and generate 30 percent of all waste. The green movement is motivated by the desire to conserve energy usage and reduce natural resources utilized by this market. Consequently, main building codes used in the United States have made energy codes the priority which increases "occupant risk of exposures to indoor generated contaminants." It is believed that this trend of reducing ventilation and sealing buildings has led to indoor air containing 2&#;5 times the levels of many outdoor pollutants.

FORMASHIELDTM Binder Technology seeks to address the growing concern over the most carcinogenic pollutants by enabling an indoor house paint to ameliorate the health and wellness of occupants in buildings. Additionally, FORMASHIELDTM Polymers help facilitate a more robust paint film with improved performance properties. This is achieved by means of reactive cross&#;linking technology that enhances adhesion and overall paint durability while further improving the sustainability profile. Commercial paints containing FORMASHIELDTM Binders are now sold in the United States and are expanding the credibility of green movement products. It is expected that FORMASHIELDTM Technology will become a standard feature in common commercial paints in the United States whereby formaldehyde reductions provide improved health and wellness benefits for residents in homes and offices.

Sustainable Microbial Control Treatments for Hydraulic Fracturing: DRAFT: The sustainability of hydraulic fracturing operations is of vital concern to the United States. Chemistry is a critical factor in the success of hydraulic fracturing, enabling technology breakthroughs and allowing energy producers to maximize well performance and hydrocarbon quality. To successfully advance sustainable hydraulic fracturing, enabling chemistries must be designed to not only improve performance, but also improve the safety and environmental impact of the fracturing operation.

The use of microbial control agents is critical for sustainable operations, ensuring the minimization of biogenic hydrogen sulfide and acid production. Hydrogen sulfide causes corrosion, hydrocarbon souring, and, most critically, is a human exposure health concern. Therefore, effective microbial control is required to ensure worker and public safety, asset integrity, and to preserve the quality of hydrocarbons, resulting in reductions in overall drilling, re&#;work, and re&#;fracturing.

The safety and environmental impact of chemicals used in hydraulic fracturing, including microbial control agents, are often of critical concern to the industry and public. To date, attempts to introduce chemistries or technologies perceived as less harmful have not proven to be effective. Therefore, the Dow Chemical Company purposely and systematically designed and developed a microbial control program that enables the advancement of sustainable hydraulic fracturing operations. This program is based on innovative, sustainable chemistry to dramatically reduce the environmental impact of current technologies, ensure worker safety, and improve overall effectiveness of microbial control. The new patent&#;pending treatment, utilizing glutaraldehyde and 4,4&#;dimethyloxazolidine in synergistic combination, provides enhanced microbial control at lower dosage with excellent biodegradability and low environmental toxicity to offer advanced treatment of fractured reservoirs. Proven performance in lab and field testing has been validated through rapid commercial adoption of this chemistry. The implementation of this technology enables improved asset integrity and improved quality of hydrocarbon production, thus reducing the overall environmental footprint of hydraulic fracturing.

BETAMATETM and BETAFORCE TM Structural Adhesives Improve Automotive Fuel Efficiency and Emissions: DRAFT: Environmental impact is a central consideration in vehicle development. Since the Kyoto Protocol, more countries and industries have committed to reducing their greenhouse gas footprint. In parallel, fuel economy regulations are becoming more stringent and increasing attention is being paid to vehicle safety. With strong growth in vehicle production projected in the coming years and a shift of vehicle ownership and road congestion towards emerging markets, these sustainability aspects are commanding ever increasing attention globally. Reducing vehicle weight by incorporating lightweight materials has become a key route to improving fuel economy and reducing greenhouse gas emissions. Automakers today face the additional challenge of producing lightweight vehicles that also meet consumer expectations and government standards for safety, comfort, and performance. One of the key requirements for successfully implementing lightweight materials in vehicles is the selection of effective joining technologies, especially for dissimilar, lightweight substrates such as high strength steel, aluminum, magnesium, and composites. BETAMATETM and BETAFORCETM structural adhesives enable joining of lightweight and dissimilar materials, where traditional joining techniques such as welding and riveting have limited applicability. These structural adhesives also increase load bearing capability, static and dynamic stiffness, driving and handling characteristics, and optimized ride, leading to improved safety and crash behavior, longer vehicle life span, and improved durability.

As a result, BETAMATETM and BETAFORCETM structural adhesives represent a breakthrough solution addressing energy and climate change, as well as safety and health &#; two pressing world challenges. For example, structural adhesives have enabled 10 kg weight savings per vehicle, which translates to an estimated 1.8MM gallons of fuel saved and 16.3 MM kg CO2 avoidance for a typical 100,000 vehicle build program over the five year life of program.

Enzyme&#;Free Biomass Depolymerization Using GVL: DRAFT: The need for renewable alternatives to petroleum&#;based resources has never been greater. Reliance on fossil fuel extraction currently poses environmental, economic, and political threats worldwide. Biomass&#;derived fuels and chemicals provide a renewable alternative to products traditionally generated from fossil fuels and yet previous efforts to transform cellulose&#;containing biomass into fuels and other products have often relied on expensive, energy&#;intensive, and sometimes toxic chemical protocols. Developing environmentally sustainable and economically viable biofuels and bio&#;based products thus depends on developing greener and more streamlined ways of breaking down cellulose into sugar.

Researchers at the University of Wisconsin&#;Madison have shown that γ&#;valerolactone &#; a small molecule solvent that can be renewably sourced from biomass &#; promotes efficient and selective thermal breakdown of cellulose in the presence of dilute aqueous acid. The researchers have successfully performed laboratory&#;scale production of soluble carbohydrates from corn stover, hardwood, and softwood at high yields (70 to 90 percent) in a solvent mixture of biomass&#;derived γ&#;valerolactone (GVL), water, and dilute acid (0.05 weight percent H2SO4). A key advantage to this process is that it replaces enzymes and significant quantities of acid with a green solvent easily producible from biomass itself. GVL can also be easily separated by adding small amounts of liquid carbon dioxide.

An initial economic assessment indicates that this technology could produce ethanol, and perhaps other biofuels, at a cost savings of roughly 10 percent when compared with current state&#;of&#;the&#;art technologies. Through Wisconsin Alumni Research Foundation&#;s Accelerator Program, University of Wisconsin researchers are now constructing a high&#;efficiency biomass reactor that will use GVL to produce concentrated streams of sugars and intact lignin solids for use by scientific collaborators optimizing the conversion into valuable chemicals and fuels. With the use of this technology, it turns out that the secret to success in creating plant&#;based fuels was within the plants themselves.

G&#;Clean® Line of Green Cleaning Products Designed to Clean Hydrocarbons Safely and Effectively: DRAFT: In all industries that deal with cleaning hydrocarbons, maintaining profitability while ensuring safety of people and the environment are top priorities. Increasing regulations, media attention, public perspective, fears of climate change, and water and energy conservation are only adding to the importance of staying ahead of the curve on how companies approach production and maintenance.

G&#;Clean® combines domestically sourced renewable feedstocks with proprietary technologies molded around the multiple green ideologies including biodegradable, recyclable, renewable, and environmentally safe as well as being commercially viable. G&#;Clean® offers companies effective and environmentally safe cleaning products that substantially lower their carbon footprint but ultimately offers companies a lower cost of cleanups or an increase in revenues (sometimes both).

Each of the products in the G&#;Clean® product line is based on proprietary colloidal chemistry processes at the nanoscale. Food grade ingredients, such as soy, corn, grain, potatoes, and trees are processed to form a particle called a micelle. Micelles work to breakdown long chain hydrocarbon bonds in fats, oils, and grease and hold them in suspension when mixed with water. Ultimately, the wash off is completely biodegraded by bacteria resident in the crude oil.

G&#;Clean®, developed by Inventek, all have "zero" ratings according to National Fire Protection Association: zero reactivity, zero flammability, zero health hazard, and no special hazards. These 100 percent biodegradable and non&#;toxic products can be used instead of solvents and other hazardous materials like diesel that are commonplace when cleaning oil. G&#;Clean® cleaners in their organic form are safe for the skin, the air, water, animals, and ground.

According to studies done in the oilfields of E&B Natural Resources and other oil companies, G&#;Clean® has proven to reduce water needed to clean a typical storage tank by over 50 percent. Therefore, waste disposal is also reduced substantially. G&#;Clean® is listed on the EPA National Contingency Plan list and was highlighted as being successful in the BP Deepwater Horizon cleanup. Other industry validations have come from the Oil & Gas Awards, the Louisiana Gulf Coast Oil Exposition "spotlight on new technology award," as well as winning a "Pollution Prevention" award from Kern County (California) Green Awards.

Environmentally Responsible Spore Control Program Through Effective Cleaning and Sanitizing of Heat Exchange Dairy Process Equipment: DRAFT: Explosive population growth, massive growth of technology, and accelerating change is occurring globally. For example; between and , global population has increased two&#;fold, the economy seven&#;fold, food consumption three&#;fold, water use three&#;fold, and fossil fuel use four&#;fold. Food is one resource lost throughout the supply chain. The recent FAO (Food and Agricultural organization of the UN) study reports that roughly one third of food produced for human consumption is lost. This waste is compounded by lost resources (e.g., water and energy) associated with food production.

In this context, production methods such as Ecolab&#;s novel spore control program that minimize water and energy requirements while producing safe high quality food that is free of spoilage&#;inducing contaminants is an important step forward. To meet current and future demands, food must be able to be efficiently processed without waste while leveraging renewable energy and working with a minimum amount of water that can be reused or recycled.

The Ecolab spore control program combines technologies described in two separate patents to solve a very difficult food and beverage manufacturing problem. This novel cleaning and sanitizing process employs environmentally responsible biocides that decompose to organic acids and water after reaction and dilution. Given this positive environmental profile, it is even more surprising that this product effectively kills themophilic spores, which are among the most resistant living organisms. Commercialization of these patented technologies enhances food security by enabling products suitable for direct human consumption, increasing the value of the product, and bolstering the economic sustainability of producers in the United States.

Targeted Chemotherapy for Solid Tumor Cancer Treatment: DRAFT: Kadcyla® (INN: trastuzumab emtansine) is an antibody drug conjugate approved by the FDA for treatment for HER2&#;positive metastatic breast cancer patients who have received prior treatment with Herceptin® and a taxane chemotherapy. Antibody drug conjugates combine the targeting capabilities of antibodies with the potency of chemotherapy. Kadcyla®, specifically, links trastuzumab, a monoclonal antibody that binds to HER2&#;positive cancer cells, via a stable linker to DM1, an antimicrotubule agent that blocks cell growth by stopping cell division. In clinical studies, patients treated with Kadcyla® lived nearly six months longer and lived over 3 months longer without their cancer getting worse compared to the standard treatment. In addition, fewer patients who received this medication experienced severe (&#;grade 3) adverse events. Environmental studies have shown that Kadcyla® is readily degradable (84 percent in 28 days). In wastewater treatment facilities, the antibody portion of the conjugate is readily degraded leaving the linker&#;DM1 (MCC&#;DM1) portion of the molecule. Ready and inherent biodegradation tests have shown that MCC&#;DM1 is not toxic to activated sludge bacteria nor does it bioaccumulate, thus Kadcyla® does not pose a pharmaceutical in the environment risk.

Kadcyla® has been shown to be less toxic to patients than the standard treatment (as defined by the number of adverse events experienced) because it delivers the chemotherapeutic agent directly to the cancer cells. Additionally, Kadcyla® is biodegradable and does not bioaccumulate. Antibody&#;drug conjugate technology generally has the potential to reduce the amount of toxic agents used in the clinic as these therapeutics provide a targeted alternative to systemic chemotherapy dosing.

Naturama &#; Oil Surfactant, Green Degreaser and Cleaner: DRAFT: Naturama is a naturally&#;derived, plant&#;based feedstock that is a water soluble solution utilized in an array of industries to remove grease and clean surfaces, without leaving the harmful environmental impact evidenced in other comparable products. The benefits of Naturama are extensive. It is 100 percent biodegradable, non&#;enzyme&#;based, non&#;toxic, and non&#;ionic. It is hypo&#;allergenic, non&#;caustic, and non&#;flammable.

Other industries&#; products contain toluene, tetrachloroethylene, hexane, heptanes, and other toxic chemicals that pose extreme fire hazards as well as both short&#; and long&#;term health hazards. Additionally, the cost of these competitor products extend beyond the product to regulatory compliance, training, protective gear, environmental controls, waste management services, and employee cost. With Naturama, the oil molecules quickly degrade through a much expedited photosynthesis process ranging from minutes to a few weeks.

The primary industrial applications targeted for Naturama are automotive and food service. Specifically, degreasing and cleaning of automotive parts and cleaning facilities. Significant opportunities have been identified in manufacturing, drilling, marine, and even household applications.

When compared to other toxic products, Naturama saves a tremendous amount of energy because it does not require a heat source when used. Being non&#;toxic, employee safety is not compromised, and no special storage is required. The volume of material needed is reduced to very small quantities. The waste of particulate matter, after filtration, is the only hazardous material to be disposed of, reducing the waste stream. Naturama is not hazardous in its initial component, nor in its life cycle after filtration. Naturama can be used completely during its life as a cleaner/degreaser in various applications and industries.

Green Approaches of Nanocomposite Material Synthesis for Energy Storage, Environmental Surveillance and Sustainable Food Systems: DRAFT: Graphene sheets have high specific surface area, large electrical conductivity, and robust mechanical strength. It is readily produced in tons. Current economical and effective production of graphene in mass from graphene oxide (GO) requires reducing reagents such as hydrazine, alkaline, ethylenediamine, NaBH4, and urea, which are toxic, corrosive, or even explosive. The process with reducing reagents and stabilizers to improve reduced GO dispersion are time&#;consuming and usually undesirable due to their damage on electronic properties. Graphene nanocomposites with metal nanoparticles can have synergistic effects for use in different applications such as energy storage, biosensors, and optical electronics. However, the synthesis of these nanoparticles from their salt precursor solutions also needs hazardous reducing reagents. Therefore, a large&#;scale greener and more effective synthetic route of graphene and graphene nanocomposites is an unmet need. A facile, controllable, and cheap electrochemical approach was used to perform rapid and green synthesis of graphene and graphene&#;based nanocomposite materials for energy storage, environmental surveillance, and sustainable food systems. Compared to reduction by constant potential or current, a repetitive cathodic potential cycling reduction was designed, which can completely remove unfavorable electrochemically unstable oxygenated groups and generate a two&#;dimensional, defect&#;free homogeneous graphene film with excellent stability and electronic properties. The synthesis can be successfully conducted on different flat and rough substrates such as indium tin oxide glass, glassy carbon, and graphitic carbon. Applications of graphene and graphene nanocomposites from this green route without generating any hazardous wastes are exhibited as supercapacitor, oxygen reduction reaction, and biosensing in food and environmental samples. By using a patented replaceable technology for the developed solid&#;state electrodes, wastes such as alumina slurry and water from electrode washing can be avoided.

An Innovative Catalytic Intramolecular Asymmetric Reductive Amination of a Dialkyl Ketone Enables a Highly Efficient, Green Synthesis of Suvorexant (MK&#;): DRAFT: A highly efficient and environmentally responsible synthesis of suvorexant has been discovered and demonstrated. Suvorexant is a new treatment for insomnia which is currently under review in a number of countries. The first scalable route to the molecule was based on a classical resolution, and used to prepare material for early drug development. Although this approach could have been the basis of a viable manufacturing process, it did not meet Merck&#;s high green chemistry goals and hence Merck researchers decided to totally revise the synthesis. A highly selective and previously unprecedented catalytic intramolecular reductive amination reaction of a dialkyl ketone with an alkyl amine was discovered and used to introduce the challenging stereocenter. Detailed kinetic studies led to understanding of the reaction mechanism and hence optimization of catalyst loading, yield, and enantiomeric excess. The fundamental knowledge gained from this work greatly expands the utility of the reductive amination, a ubiquitous transformation in fine chemical production, and can be applied to the large scale synthesis of other chiral molecules. In addition, the entire synthesis of suvorexant was scrutinized with respect to amount and type of solvents and reagents used, number of operations and isolations, and process robustness. This allowed the complete removal of the undesirable solvent dichloromethane and led to a 56 percent reduction in the amount of waste produced by the process. The technology discovered, developed and implemented by Merck for the manufacture of suvorexant is an excellent example of scientific innovation resulting in significant benefits to the environment.

Bt Technology, Transforming Insect Control: DRAFT: Insect pest infestation of crop species have limited food production for centuries. Until the s, chemical insecticides were the most advanced tools for insect control. However, they created significant challenges, including undesirable environmental consequences, toxic effects against non&#;target organisms, and often required repeated applications. The vision of biotechnology as a solution for these challenges became a reality in the mid&#;s.

Biotechnology means pesticide manufacturing and chemical pesticide applications are needed less frequently. Unlike traditional pesticide manufacturing, some Bacillus thuringiensis (Bt &#; a ubiquitous soil microbe) bacteria contain genes expressing proteins that naturally control insect pest species. Monsanto used biotechnology to take advantage of the characteristics of these toxins &#; Cry (crystal) proteins &#; combining this knowledge with plant molecular genetics to create plants that express specific toxins to control crop plant pests by producing the crystal protein through naturally occurring biological mechanisms within the plants. In addition to reducing the use of pesticides, the specificity of Cry proteins ensures only target organisms are affected, and avoids pesticide exposure of humans, animals, and non&#;target beneficial insects.

Bt technology continues to be applied across many plant varieties, increasing yields and reducing the need for chemical pesticides. All Bt traits in commercial use have been created through the use of Monsanto&#;s patented synthetic Bt gene technology, and many of Monsanto&#;s traits developed using this technology have been licensed to and sold by numerous seed companies. In , three quarters of all corn and cotton grown in the United States included one or more Bt traits.

Farmers planting insect&#;resistant crops experience improved safety and health because of reduced pesticide use, and spending less time applying insecticides. This reduced number of applications mean fewer containers, less fuel and decreased aerial spraying, and reduced costs per acre farmed, all benefiting the environment while increasing yields and enhancing farmers&#; lives.

Ultrasound Induced, Copper Mediated Homo&#;Coupling Using Polymer Supported Aryltrifluoroborates: DRAFT: The homocoupling of aryl compounds is an important reaction used in the formation of fundamental building blocks for numerous industrial and pharmaceutical materials. Unfortunately, many of the widely used homocoupling reactions require expensive catalysts or use harsh reaction conditions with large quantities of metal while producing only modest product yields. In an attempt to improve the negative aspects of these reactions, researchers have employed a variety of tactics including the use of different metals, ultrasound or microwave energy sources, various solvent systems, and different ligands, all with varying degrees of success. There are a number of reports that indicate successful synthesis of biaryl compounds using polymer supports. Benefits of the modification include successful reactions run in water and under atmospheric conditions with good product yields. Regrettably, these reactions are not atom efficient, and require extensive preparation of the polyethylene glycol, with harsh chemicals and environmentally toxic solvents, before it can be used in the reaction. Since Dowex is commercially available, the Kabalka group attempted a homocoupling reaction similar to the reported polyethylene glycol methods. Palladium(II) acetate was chosen as the survey metal, following the reported methods. Initial survey reactions using heat and stirring indicated only minimal product yield (seven percent) after 72 hours. It was decided to carry out the reaction using an ultrasound energy source, which provided a significantly improved yield of 92 percent while decreasing reaction time to six hours. To develop a more environmentally friendly reaction, the copper acetate replaced the palladium salt, and the aqueous tetrahydrofuran solvent was changed to aqueous ethanol. Product yields remained excellent at 96 percent. The reaction is green, atom efficient, and, in later reactions, shown to be scalable as compared to currently used industry reactions.

Evotherm® Warm Mix Asphalt Technology: DRAFT: Traditional hot mix asphalt paving is a significant source of greenhouse gas emissions. MWV Specialty Chemicals, a division of MeadWestvaco Corporation, developed Evotherm warm mix asphalt technology. Evotherm is a unique, bio&#;based surfactant that enhances the ability of asphalt mix to be produced at temperatures 60°&#; 90°F lower than conventional hot mix asphalt. This reduction in temperature enables plant energy savings of 55 percent, resulting in lower carbon dioxide (CO2) and nitrogen oxide (NOx) emissions. Since Evotherm was introduced to the marketplace in , over 50 million tons have been used on United States roadways, creating a savings of 27 million gallons fuel and 605 million pounds of CO2. The lower temperature asphalt mix also creates a safer and more pleasant work environment by reducing the temperature of the mix at the paving site to limit vapor and thermal worker exposure.

Evotherm technology, derived from renewable tall oil fatty acids and distilled tall oil, was developed by MWV Specialty Chemicals in Charleston, South Carolina as a part of the Innovation Strategy to support the transportation industry. The technology also allows for increased utilization of recycled materials. As states seek to maximize transportation funding dollars, utilizing recycled materials provides economical, high&#;performance roadways. Evotherm improves the workability recycled materials, allowing for up to 75 percent more recycled content.

Amended Silicates® HgX: DRAFT: Amended Silicates® HgX (AS&#;HgX) is a non&#;carbon mercury capture reagent that removes mercury from coal&#;fired power plant flue gas, enabling utilities to comply with the EPA&#;s soon&#;to&#;be&#;implemented Mercury & Air Toxic Standards (MATS). This mineral&#;based product removes mercury via a chemical reaction, providing economic and environmental advantages unavailable with carbon&#;based products. AS&#;HgX is currently being used in 14 coal&#;fired power generation units.

AS&#;HgX consists of a bentonite substrate that is amended with a metal sulfide that acts as the reagent to capture mercury from coal&#;fire flue gas. A chemical reaction forms mercuric sulfide on the reaction sites of particle surfaces in flue gas. Mercuric sulfide is the most stable form of mercury, occurring naturally as the mineral metacinnabar. Mercuric sulfide is extremely insoluble and does not leach into the environment.

Prior to the availability of Amended Silicates, coal&#;fired power plants had little choice but to use carbon&#;based products (Powdered Activated Carbon &#; PAC) to remove mercury. However, PAC contaminates fly ash (a byproduct of burning coal), necessitating landfill burial of millions of tons of fly ash annually. AS&#;HgX does not contaminate fly ash thus preserving its resale value to concrete manufacturers, eliminating landfill disposal, and avoiding an estimated one million tons annually of CO2 emissions related to Portland cement production.

AS&#;HgX removes mercury three times more efficiently than PAC products. Extensive testing demonstrated that compared to PAC products, AS&#;HgX provides a 25&#;50 percent cost savings, reduced operating expenses and consistent MATS compliance. AS&#;HgX is non&#;flammable, noncorrosive, and compatible with a power plant&#;s existing injection equipment with few or no modifications.

The carbon footprint for producing AS&#;HgX is about 90 percent less than that created by PAC production (a potential reduction in CO2 emissions of 175,000 metric tons per year if just 10 percent of the market used AS&#;HgX instead of PAC).

Polyethylene Terephthalate (PET) Derived Polymers for Coatings: DRAFT: PET is a polymer with a polyester backbone. This class of compounds relies upon a reversible reaction: the substitution at saturated carbonyl. This reaction is usually accomplished through elimination of a leaving group that is in most cases water or methanol for industrial production. This esterification in appropriate conditions can be reversed to go back to the starting raw material, with different methods existing to do so. For this green chemistry technology, glycolysis was chosen to reverse the esterification. Using an appropriate polyfunctional glycol, the polymer is broken down to lower molecular weight portions and, with appropriate stoichiometric conditions, is possible to leave a hydroxyl active functionality at the end. Those lower molecular weight fractions can further react with other acids or anhydrides to obtain a new polymer in which they represent part of the backbone mixing up physical&#;chemical properties with those of other raw material. In a process invented by PPG Industries, the final polymer is produced using the PET as starting raw material with a simple and compact process.

The polymer produced can have multiple characteristics depending on the raw materials and process chosen. A number of different polymers can be obtained from this process including: polyester resins, alkyd resins; polyester or alkyd acrylated resins; and urethane polymers. Many of these polymers are suitable for use in various coatings chemistries. Currently, the most significant use of this technology is in the production of a 2K polyurethane primer for use in automotive refinish coatings. The 2K polyurethane is produced by reaction of a hydroxyl functionalized polymer with a polyisocyanate to obtain a cross&#;linked film. While PPG is using the recycled&#;PET based polymer in a 2K polyurethane primer paint, there are many other potential uses of this technology within the coatings industry.

Utilization of Elemental Sulfur as a New Chemical Feedstock for Polymeric Materials: DRAFT: The nominated technology focuses on the development of new polymerization methods to convert elemental sulfur into useful polymeric materials. A new generation of sulfur&#;based plastics has resulted from these new synthetic advances, where these materials have been demonstrated to possess useful electrochemical and optical properties. The surfeit of elemental sulfur (S8) generated from petroleum refining has created an incredibly abundant and inexpensive supply of sulfur. However, there remain only limited uses for elemental sulfur toward the production of other chemicals (e.g., sulfuric acid), and there is a paucity of synthetic chemical methods to modify, or directly convert elemental sulfur into useful polymers and alternative materials. This challenge arises from the incompatibility and limited miscibility of sulfur with the majority of chemical reagents and solvents. To obviate these fundamental synthetic challenges, the team of Pyun and Glass has developed a new concept of using molten liquid sulfur as an unconventional solvent and reagent for chemical reactions used to prepare gold nanoparticle nanocomposites and high content sulfur polymers. To convert sulfur into a chemically stable and useful plastic, Pyun and Glass&#; team has developed a new polymerization method termed inverse vulcanization that for the first time uses molten liquid sulfur as the reaction medium and comonomer for the synthesis of sulfur&#;rich copolymers. They demonstrated that these sulfur&#;based plastics possess unique electrochemical and optical properties, which enabled their application in devices for enhanced lithium&#;sulfur batteries and infrared thermal imaging. These collective findings point to the creation of a new field of sustainable sulfur chemistry for advanced materials with significant environmental and technological benefit through the use of excess sulfur. This work has generated five publications and one patent application.

STEPOSOL® MET&#;10U: A Bio&#;derived, Nonionic Surfactant Solution for Solvent Replacement: Source Reduction and Inherently Lower Health Hazards in Hard Surface Cleaning and Adhesive / Paint Removal: DRAFT: Highly toxic solvents and corrosive formulations represent a health hazard and environmental concern. There have been, for example, 14 recorded deaths since the year attributed to paint strippers formulated with methylene chloride, a suspected human carcinogen. Additionally, N&#;methyl pyrrolidone raises concerns regarding reproductive hazards. Stepan Company has recently introduced STEPOSOL® MET&#;10U, an efficient, effective, and low toxicity solution to these problems. This surfactant, developed through a joint effort with Elevance Renewable Sciences (ERS), realizes commercialization of ERS&#; novel bio&#;derived, unsaturated short&#;chain methyl ester to achieve the same level of adhesive and paint removal performance in 5 percent aqueous formulations as 100 percent solvent&#;based materials. The unsaturated ester raw material is produced from renewable feedstocks via Nobel&#;prize winning metathesis technology that generates 50 percent less greenhouse gases.

The performance of this groundbreaking surfactant stands in stark contrast to previously available green solvent options. The cleaning power of a solvent is often measured through its Kauri Butanol value. In external labs, STEPOSOL® MET&#;10U scored >1,000 on this scale while d&#;limonene, a weaker green alternative solvent, rated a 67. STEPOSOL® MET&#;10U is 75 percent renewable, non&#;VOC (boiling point = 297°C), non&#;flammable, less toxic, readily biodegradable, effective in aqueous solution at more neutral pH than current formulations, and cost&#;effective in use. The performance of STEPOSOL® MET&#;10U is attributable to its metathesis&#;enabled double bond, its derivatization as an amide, and its wide ranging formulation compatibility. STEPOSOL® MET&#;10U is the first of a new generation of bio&#;derived, high&#;performance chemicals that Stepan Company and joint development partner ERS have brought to both commercial and consumer markets as an alternative to less sustainable and more hazardous chemicals. In this manner, Stepan is providing superior performance while also delivering source reduction and inherently lower hazards to workers, consumers, and the environment.

CIRKIL Biopesticide: DRAFT: Pesticides are critical to society, increasing agricultural output, managing disease, and enhancing human comfort. Despite these benefits, Conventional Chemical Pesticides (CCPs) are under increasing scrutiny. For years, CCP producers have created small&#;molecule pesticides, delivering efficacy primarily through toxicity. Regrettably, these pesticides can be toxic to target and non&#;target pests, humans, and other animals. Insects also develop resistance to CPPS and CPPs typically biodegrade slowly becoming persistent in the environment. Put simply, CPPs are important but indiscriminately toxic, are easily "outsmarted" by the target insect, and persist in the environment. The conventional approach to deal with these challenges has been to "double&#;down" and create more synthetic pesticides.

Terramera has a significantly different approach. Rather than creating novel molecules, the company has created a novel, patent pending formulation technology that stabilizes and potentiates the natural efficacy of plant bioactives. Terramera has shown that plant biochemicals are effectively delivered into the insect&#;s organism as a result of this technology, enabling development of plant&#;based biopesticides that perform as well or better than CCPs.

Terramera has successfully commercialized a bio&#;pesticide targeting bed bugs with this technology potentiating cold pressed neem oil to deliver superior efficacy to CCPs, in a minimally toxic formula. Terramera is extending this technology into agriculture developing novel products using botanical bioactives to treat insects, plant parasites, and fungi with field trials in progress. By substituting with Terramerra, a single large strawberry grower in California could annually displace 540,000 pounds of methyl bromide/chloropicrin, a CCP being phased out in the United States.

Green Detergents for Industrial Laundries: DRAFT: Since , Washing Systems made the commitment to develop washing chemistry for industrial laundries across the United States that would enable customers to improve their environmental profile and financial well&#;being. This endeavor began in , through the company&#;s voluntary phase out of nonylphenol ethoxylates (NPEs) in laundry detergents, a known endocrine disruptor and toxic chemical. Through diligently incorporating strict success criteria, consisting of formulating a more environmentally friendly detergent capable of reaching the same quality, chemical usage, and cost for the customer, Washing Systems efficaciously eliminated NPEs from the laundry formulations. In addition, the new formulations (industrial and two linen detergents) were developed without the addition of other harmful chemical of concern. From the projects inception, Washing Systems customers have reduced over 21.6 million pounds (an average of 3.6 million pounds/year) of NPEs discharged into the environment.

In order to fully align with Washing Systems new corporate commitment, the three new detergents were submitted for DfE recognition and approved in . As part of this new partnership with DfE, Washing System continued to evaluate alternate chemistry to create the best products and further reduce the environmental impact for all customers. This initiative and desire has led to the development of another DfE&#;recognized detergent in , Pinnacle Liquid Detergent, and two additional products in (Spectrum and Supreme).

UCR Co&#;Solv Technology Achieves Unprecedented Yields of Fuel Precursors from Lignocellulosic Biomass: DRAFT: Professor Wyman and his team has developed an integrated biomass pretreatment and conversion strategy, named "Co&#;Solv," to promote the production of fuel precursors furfural and 5&#;hydroxymethylfurfural (5&#;HMF) directly from lignocellulosic biomass as a future platform for sustainable biofuel production. These fuel precursors have been considered by the U.S. Department of Energy as top platform chemicals for the production of renewable chemicals and liquid transportation fuels if they can be obtained at high yields and at low cost from lignocellulosic biomass. As biomass feedstocks costing $60/dry ton are equivalent in energy cost to petroleum at about $20/barrel, they are distinctive in being the only sustainable resource sufficiently inexpensive and abundant to make a large impact on liquid fuel use. Green processes that can economically convert low&#;cost biomass into compatible transportation fuels that have enormous benefits for addressing global climate change, national energy security, economic growth and employment, trade deficits, and global competitiveness issues. Co&#;Solv is a highly tunable and scalable process to simultaneously solubilize lignocellulosic biomass and catalytically convert hydrolyzed sugars into fuel precursors. In one arrangement, Co&#;Solv technology employs a one&#;pot monophasic reaction combining a renewable solvent with non&#;corrosive solid acid catalysts to produce the highest overall yields furfural (>90 percent) and 5&#;HMF (>45 percent) directly from biomass. Co&#; Solv is greener and more effective than other competing strategies such as biphasic reactions, ionic liquid systems, and other co&#;solvent systems because it is low&#;boiling, relatively non&#;toxic, and can be renewably produced from furfural as a final product to supplement a continuous reaction strategy. Professor Wyman and his team has also successfully compared these results with current industrial methods to show an impressive product yield advantage, which could result in low&#;cost, largescale production. Lignin removal is also extensive, achieving ~90 percent delignification of hard woods to maximize the utility of all major fractions of lignocellulose reducing solid waste products.

Pathex®/PathShieldTM Antimicrobial Filter Media for the Control of Bacteria in Stormwater and Industrial Process Waters: DRAFT: Pathex® antimicrobial filter media (PathShield&#; is alternate brand name) reduces and controls coliform bacteria in industrial wastewater, recirculating cooling towers, heat transfer systems, industrial fresh water systems, stormwater, service water and auxiliary systems, and municipal wastewater treatment.

The unique surface bond of this organosilicon quaternary ammonium chloride compound to siliceous materials, without release of chemicals, offers a new approach to water treatment. Pathex®/PathShield&#; kills bacteria as it moves over the filter media granules. The media is effective, even at loading rates up to 20 gpm/ft2, without releasing, discharging, or leaching antimicrobial agents, chemicals, harmful disinfection byproducts, or heavy metals. When used within sidestream filters for industrial cooling towers, the filter media achieves 20% water savings. The filter media can also achieve up to 40% energy savings due to enhanced temperature exchange capacity from biofilm reduction and at least a 90% decrease in the use of traditional chemical biocides.

It is projected that Pathex®/PathShield&#; antimicrobial filter media annually can eliminate the use of 486 million pounds (243,000 tons) of chemical biocides, repurpose 280 billion gallons of makeup water for potable water, and eliminate the need for biocide chemical removal from the same 280 billion gallons of water at local waste treatment facilities. The filter media is stable, non-toxic, not consumed, non-corrosive, requires no power source to kill bacteria, and is not affected by temperature changes.

Using Bioethanol as A Raw Material, To Produce: 1. SAFEN: A Low Cost Nematicide And Fungicide, Based on Ethyl Formate, Which Is Generally Regarded as Safe by the FDA, and Which Biodegrades Into Two Naturally Occurring Substances, with No Lasting Detrimental Effects to Air, Soil and Water; and 2. Ethyl Formate in a Second Development as a Suitable Raw Material for Propionic Acid and Acrylate Production: DRAFT: SAFEN is a green chemical nematicide and fungicide that is environmentally friendly to air, soil, and water. The Montreal Protocol emphasized the need for pesticides that were environmentally friendly and eliminated the use of methyl bromide, an ozone depleting agent commonly used worldwide. SAFEN represents a green alternative to methyl bromide. SAFEN&#;s components are made from low cost raw materials and its primary component ethyl formate is made from ethanol, a renewable resource. SAFEN&#;s simple molecules biodegrade into naturally-occurring substances after use.

Photocatylic Oxidations of Ethers with Visible/Near UV Light and the Development of a Continuous Flow Photoreactor: DRAFT: Water soluble ethers such as methyl t-butyl ether (MTBE) and 1,4-dioxane (DIOX) are common solvents and gasoline additives and have found their way into public water systems. Other compounds such as ethyl t-butyl ether (ETBE), t-amyl methyl ether (TAME) and diisopropyl ether (DIPE) are also water soluble ethers and potential sources of water contamination. This work shows that MTBE, ETBE, and TAME along with 1,4-dioxane and DIPE are actually undergoing a degradation process involving near UV light of 320-375 nm. Using the a batch slurry process incorporating a borosilicate filter that eliminated short wavelength UV light, rate constant for degradation for MTBE, 4.2 x 10-4 s-1, ETBE, 4.63 x 10-4 s-1 and TAME, 7.72 x 10-4s-1 were observed, comparable with those seen previously, while 1,4-dioxane and DIPE showed rates of 1.1 x 10-3 s-1, and 6.3 x 10-4 s-1, respectively. In all cases, over 80% of the initial substrate was destroyed in less than 150 minutes.

Using these results, a series of continuous flow photoreactors were designed using conventional fluorescent light source. An in-series design, using TiO2-coated glass tubing, produced 10-15% substrate conversion. A larger in-parallel design using a purgeless oxygenation system and TiO2-coated glass beads, also yielded a 10-15% conversion rate even at higher flow rates. These reactors clearly demonstrated that water soluble ethers can be degraded using simple fluorescent lighting. While results are preliminary, substrate degradation of up to 15% or 2.0-3.0 mg/L was observed in less than 1 meter of reaction flow distance.

Eastman OmniaTM Solvent &#; Changing the Chemistry of Clean. New, Safe, Highly Effective Solvent for Cleaning Applications: DRAFT: To enable development of cleaners that are safer for humans and the environment, formulators need safer ingredients. It is rare, however, for a solvent used in cleaning products to be safe for people, the environment, and surfaces being cleaned &#; and still enable efficient cleaning and compliance with air quality requirements. With this unmet need in mind, Eastman developed a solvent offering exceptional safety, performance, and value throughout the industry &#; from formulators to cleaning staff to customers.

With thousands of molecules to consider, Eastman narrowed the solvent universe using computer modeling based on human health and environmental safety criteria and specific physical/chemical properties to predict good performance. Minimum safety criteria for candidates were based on Design for the Environment (DfE)&#;s Solvent Screen.

The final candidate, Eastman Omnia&#; solvent, has an excellent safety profile, as evidenced by meeting DfE&#;s Solvent Screen criteria, listing in GreenBlue&#;s CleanGredients® database with no restrictions, and listing in DfE&#;s Safer Chemical Ingredients List with highest rating. Performance testing demonstrates Omnia&#;&#;s excellent cleaning ability: neutral&#;pH formulations with Omnia&#; were highly effective and outperformed alternatives.

Eastman satisfied requirements for Toxic Substances Control Act (TSCA) Inventory listing and began manufacture of Omnia&#; in October . Since then, Omnia&#; has been commercialized by multiple customers in a wide range of applications, with over 75 additional customers currently evaluating it in a variety of applications. Based on Eastman&#;s volume projections and the fact that a typical janitorial cleaning formulation contains around 2% solvent, the use of Omnia&#; could represent a safe, effective alternative in over 60 million gallons of cleaning products per year in the United States.

The combination of powerful cleaning and excellent safety profile makes Omnia&#; an excellent choice for formulators challenged to comply with increasingly stringent safety, regulatory, and market demands. Eastman Omnia&#; solvent is changing the chemistry of clean.

OxyCideTM Daily Disinfectant Cleaner: DRAFT: OxyCide&#; Daily Disinfectant Cleaner (OxyCide) is a broad spectrum, EPA-registered hospital grade disinfectant developed by Ecolab. OxyCide was the first non-bleach concentrate sporicidal disinfectant sold to the acute care market. It is a multi-faceted solution for improving hospital performance in the areas of infection prevention, efficiency, source reduction, and impact to the environment.

Healthcare-associated infections (HAIs) are a persistent issue in hospitals, affecting one in every 25 hospital patients. In there were an estimated 722,000 HAIs in United States acute care hospitals, and about 10% of these patients died during their hospitalizations. One of the most prevalent HAI causing organisms is Clostridium difficile (C. difficile), which causes 17.1% of all HAIs and is linked to 14,000 deaths annually. OxyCide provides hospitals with a powerful tool in the fight to prevent HAIs. In only five minutes, OxyCide kills 33 microorganisms commonly found in healthcare settings, including C. difficile spores.

OxyCide&#;s active ingredients hydrogen peroxide and peracetic acid replace environmentally persistent ingredients found in other concentrated hospital disinfectants with similar efficacy profiles. The concentrated format of OxyCide reduces the number of containers by 40 times for an equivalent amount of ready-to-use disinfectants. Its innovative closed loop packaging and dispensing system work together to properly dilute the product, ensuring disinfectant efficacy while reducing product waste from over-dilution. Additionally, the diluted product, when applied according to label instructions, requires no personal protective equipment.

Environmentally Preferable Biocide For Water Treatment in Hydraulic Fracturing: DRAFT: In the past years, unconventional oil and natural gas production has steadily increased in the United States. Driven by the development of new technologies such as horizontal drilling and hydraulic fracturing, shale gas has led to major increases in reserves of oil and natural gas. During hydraulic fracturing, water and chemicals are injected, at high pressure, into the geologic formation to increase the fractures in the rock layers and allow hydrocarbons to flow. Because large quantities of water are used during this process, the need for water treatment and reuse has become critical. Water treatment prevents the introduction of microorganisms in the formation, which can result in problems such as reservoir souring, biofouling, and microbiologically-induced corrosion. Additionally, facilitating the reuse of produced water through cleaning reduces the constant demand for fresh water. Based upon these concerns, Ecolab developed an improved formulation of the oxidizing biocide peracetic acid (PAA). This chemistry shows superior results when compared to other conventional biocides (e.g., glutaraldehyde, chlorine dioxide), including faster and longer duration microbial efficacy, water cleanup properties, solids dropout, and less corrosion. Importantly, PAA had no adverse effects on other chemistries present in the hydraulic fracturing fluids, such as friction reducers and scale inhibitors. Ecolab&#;s PAA biocide is an environmentally preferable chemistry as it breaks down into innocuous components &#; water and acetic acid (e.g., vinegar). A concern associated with hydraulic fracturing is impacts on surface water quality. Ecolab&#;s ECA PAA biocide enables the reuse of produced water brine, reducing fresh water draw. Use of this biocide facilitates safe, cost-effective onsite water disposal by minimizing emissions, and reduces plugging by controlling biological growth and thus maintaining hydraulic conductivity. These benefits contribute significantly to better quality and management of surface waters.

The Reinvention of Biomass Based n-Butanol for the Renewable Chemicals Industry: DRAFT: Through application of modern biology, combined with the engineering of advanced solvent recovery systems, GBI has developed an integrated, patent-pending process ready to be installed for commercial deployment in Little Falls, Minnesota. As a result of scale-up success, GBI is leading the industry race in bringing renewable acetone and n-butanol to the chemical ingredient marketplace.

Chemical grade n-butanol is currently produced through petrochemical processes, but can also be produced through fermentation of sugars derived from biomass. Until the mid-s, n-butanol was produced largely through fermentation of molasses using Clostridia bacteria. The petro-industry captured the market by offering cheaper sources. With scientific advances in microbiology and synthetic biology, as well as dramatic improvements in process technology, GBI&#;s process has achieved economics that can again compete with the much larger carbon-intensive petrochemical processes. Process outputs offer higher purity n-butanol with a carbon footprint approximately 40% better than petroleum-based butanol.

n-Butanol is used in derivatives that are key raw materials in paints, coatings, adhesives, and inks, as well as cosmetics, cleaners, food ingredients, and specialty products. In addition to a drastic source reduction of carbon, renewable n-butanol offers consumer goods manufacturers the opportunity to &#;green&#; their products without facing cost disadvantage.

The primary source reduction is derived through replacing petro-derived chemicals with chemicals produced through renewable biomass feedstocks. GBI&#;s Clostridia micro-organisms have high C-5 (cellulosic sourced sugars) productivity and business development plans seek low-value biomass or waste resources. With the commercial launch project in Minnesota, source reductions are similar to ethanol production and equate to approximately 31,000 metric tons per year. Forward projects will incorporate C-5 sugars and be much less carbon intensive. Once GBI business model volumes have been reached, it is expected that total source reductions will exceed 314,000 metric tons per year.

Low Global Warming, Non-VOC, Zero-ODP Molecule for Energy Efficient Polyurethane Foam Insulation Blowing Agent, Solvents, and Heat Transfer: DRAFT: Honeywell has risen to and is delivering on the EPA plans to tackle the super-potent heat-trapping pollutants called hydrofluorocarbons (HFCs), an important step forward in carrying out President Obama&#;s Climate Action Plan with the development and commercialization of a greener chemical 1-chloro-3,3,3-trifluoropropene, or HFO-zd(E).

The 100-year global warming potential (GWP) for HFO-zd(E) is equivalent to that of CO2 (GWP=1), which is 1,000 times lower than the hydrofluorocarbons (HFCs) it is designed to replace. It is non-flammable, non-toxic, non-ozone depleting, and classified by the EPA as VOC exempt. In May , VOC exempt status was also granted by per the highly stringent California Southcoast Air Quality Management District (SCAQMD). Honeywell&#;s extensive testing proves that HFO-zd(E) offers lower GWP, is safer, more energy efficient, and more cost-effective to implement compared to existing blowing agents such as cyclopentane and HFCs.

HFO-zd(E) is being adopted globally in a wide variety of industries such as appliances, transport, construction, refrigerants, and precision cleaning for metals and electronics. Widespread use of HFO-zd(E) to replace HFCs in these industries in the United States alone will result in a reduction of more than 25M tonnes per year of CO2-equivalent; globally this number would exceed 90M tonnes based on Honeywell&#;s internal analysis. This new product will not only help reduce global warming, but it will spur economic growth and job creation in the United States.

A Solar Chemical Process to End Anthropogenic Global Warming: STEP Generation of Energetic Molecules: DRAFT: Anthropogenic levels of atmospheric carbon dioxide (CO2) have reached record levels. The global warming consequences of increasing atmospheric CO2 concentrations encompass species extinction, population displacement, glacier and ice cap loss, sea level rise, droughts, hurricanes and flooding, and economic loss. One path towards CO2 reduction is to utilize renewable energy to produce electricity. Another, less explored, path is instead to utilize renewable energy to directly produce societal staples such as metals, fuels, bleach, fertilizer, and cement. STEP is a green chemical process that reduces carbon pollution at its source.

STEP &#; Professor Stuart Licht&#;s Solar Thermal Electrochemical Process &#; uses the full sunlight spectrum to produce essentials in excess of 50% solar efficiency in unusual green chemical processes without carbon pollution. The processes for making iron, cement, and ammonia for fertilizer have emitted massive amounts of CO2 to the atmosphere for centuries. Instead, new molten salt chemistry allows solar thermal energy to drive production without any CO2 emission. STEP distinguishes radiation that is sufficient to drive photovoltaic charge transfer from solar thermal energy that decreases the chemical splitting energy. The STEP process provides a new pathway to use renewable energy by tuning the chemical reaction energy, rather than the semiconductor bandgap energy, to match and efficiently capture sunlight. As a result, electrosynthesis occurs at solar energy efficiency greater than any photovoltaic conversion efficiency, and the converted solar energy is stored in the products. STEP has been experimentally demonstrated with the efficient, CO2-free formation of (a) ammonia, (b) fuels, (c) organics, (d) iron, (e) direct atmospheric carbon capture, (f) cement, (g) water treatment, (h) chlorine, and (i) desalinization.

High Performance Solvent-Free Coating Technology: DRAFT: Corrosion is a tremendous problem and cost to society, with a staggering annual cost of $400 billion in the United States. Many primers and paints used to coat metal surfaces for corrosion resistance and decoration pose environmental hazards from cradle to grave. Conventional epoxy-based coatings commonly contain corrosive components, hazardous air pollutants (HAPs), volatile organic compounds (VOCs), and other solvents, and often contain chromium compounds. Urethane-based paints contain isocyanates and often contain other HAPs, VOCs, and other solvents. Because isocyanates are strong irritants to mucous membranes, they can sensitize exposed individuals, in some cases causing severe asthma attacks. The hexavalent form of chromium is carcinogenic, particularly for lung cancer.

Light Curable Coatings has developed pollution-free coating technology for high performance protection of industrial and aerospace surfaces, including corrosion resistance, solvent resistance, and weathering resistance. Light Curable Coatings technology also provides the advantages of efficiency and economy, with fast cure under an ultraviolet (UV) light and with improved properties with much less material usage than conventional materials. The green chemistry of Light Curable Coatings does away with chromium compounds, isocyanates and other HAPs, solvents, and VOCs completely, producing high-performance, corrosion-resistant solvent-free technology without using any toxic chemicals. Field application and fast UV cure of Light Curable Coatings technology has been demonstrated with good performance on large structures at temperatures as low as 34°F. Customer studies show savings of over 90% in the time required for painting operations for maintenance activities and factory processes.

Light Curable Coatings technology is a green alternative to current systems that contain toxic components, and provides a significant positive societal impact in terms of a better quality of life for industrial workers and for citizens through safer workplaces and a cleaner environment.

Development of Vapormate as a Replacement for Methyl Bromide Fumigants: DRAFT: For decades, global trade in fresh fruits and vegetables has been dependent on the use of methyl bromide as a fumigant to kill indigenous insect pests. However, methyl bromide has been found to deplete the stratospheric ozone layer, and is being rapidly phased out under the Montreal Protocol. Without a viable replacement, global trade in fresh foods would be severely curtailed due to concerns about the spread of indigenous pests.

Linde North America has developed Vapormate &#; a combination of ethyl formate and carbon dioxide &#; as an effective and environmentally friendly replacement for methyl bromide. Vapormate&#;s active ingredient, ethyl formate, has no known ozone depletion or global warming potential. It eradicates pests efficiently, and quickly breaks down into metabolites that occur naturally in the environment. In addition to its important role as a replacement for a known contributor to ozone depletion, Vapormate has other environmental benefits. First, it is less toxic than methyl bromide and most commodity fumigants in current use and therefore safer for human exposure. Second, Vapormate fumigates and dissipates more rapidly than methyl bromide, allowing fresh foods to be shipped more expeditiously. This reduces spoilage and allows for more sustainable farming practices.

Vapormate is currently approved for use in select countries, including South Korea, Indonesia, the Philippines, New Zealand, and Australia. It was submitted to the EPA for registration in February , and is currently undergoing the established review process. As Vapormate wins approval in additional markets and achieves broader use, it will have two important benefits. It will reduce depletion of the ozone layer by eliminating current usage of methyl bromide. It will also enable more efficient global commerce in fresh foods by reducing spoilage.

Greener Synthesis of Surfactants: DRAFT: Surfactants are used broadly as foaming agents, emulsifiers, and dispersants. Today, surfactants are manufactured from petroleum, or from seed oils. For example, 250,000 metric tons of acyl amino acids are manufactured annually by combining palm-oil-derived fatty acids with amino acids using the Schotten-Baumann reaction. This reaction requires use of chlorinated fatty acids, which are produced industrially using either phosgene or thionyl chloride. Phosgene is highly toxic, while thionyl chloride is on the Hazardous Substances List, and reacts explosively with water, releasing toxic gas. About 100,000 metric tons of phosgene or thionyl chloride are used annually to manufacture acyl amino acid surfactants. The need for a greener method of production can be met with the use of engineered Bacillus subtilis strains for the production of acyl amino acid surfactants. The surfactants have been validated by key customers, with commercial launch anticipated in . No synthetic chemistry steps are used to produce these surfactants, as they are generated enzymatically by a microorganism and secreted into the fermentation broth. The surfactants are purified to a high level using green methods involving only low energy and water. An additional positive feature is that no oil is used to manufacture these surfactants. The bacterium converts cellulosic carbohydrate, which cannot be used as food, into a microbial oil (a fatty acid) and an amino acid, and links them together to create the surfactant. It has been estimated that a complete switch to microbial production of surfactants will eliminate annual emissions of atmospheric carbon dioxide equivalent to the combustion of 3.6 billion gallons of gasoline, while also reducing the rainforest destruction associated with palm plantation expansion.

grubGONE!®, beetleGONE!® and boreGONE!®, Biological Insecticides with Low Impact on Humans and the Environment Yet Effective Against Destructive Beetle Pests: DRAFT: Phyllom BioProducts Corp. (Phyllom) biological insecticides grubGONE!® beetleGONE!® and boreGONE!® are derived from microbes naturally found in soils and on plants, Bacillus thuringiensis (BT). While other forms of BT insecticides have been used by organic gardeners, farmers and foresters for decades, Phyllom licensed a novel strain called BT serovar galleriae SDS-502 strain with a patented natural Cry8Da protein. This protein is uniquely effective against certain beetles, weevils, and borers including the difficult to control adult stage. Phyllom&#;s bio-insecticides are produced via a bio fermentation process utilizing plant carbohydrates and proteins. The process uses no solvents and generates no hazardous wastes. Food grade inerts are used in the formulas and most formulas are compliant with the USDA National Organic Program.

Phyllom&#;s bio-insecticides demonstrate advantages such as improved plant/poultry health and control of invasive and/or insect pests resistant to traditional chemistries. Phyllom&#;s bio-insecticides demonstrated virtually no adverse effect on non-targets tested, including honey bees, wasps, lady bird beetles, mammals, birds, plants, fish, and aquatic invertebrates.

Wood boring invasives such as the Emerald Ash Borer are anticipated to cause nearly $1.7 billion in annual government expenditures and $830 million in lost residential property values. An Integrated Pest Management program including Phyllom&#;s bioinsecticides could economically slow the spread of invasives by providing the option to suppress adult beetle reproduction.

EPA Office of Pesticide Programs reports 93 million pounds of insecticides were applied within the United States in . Phyllom&#;s bio-insecticides will replace a portion of this volume with effective yet more human health and environmentally benign alternatives.

PROSOCO R-Guard: High-Performance Phthalate-Free Air and Water Resistive Barrier Sealant and Sealant Coating System: DRAFT: In , BEI and PROSOCO were working with Miller Hull architects to provide a high-performance vapor barrier sealant and coating system for the Bullitt Center, a Living Building Challenge (LBC) project in Seattle, Washington developed in partnership with Point32. Spearheaded by Denis Hayes of the Bullitt Foundation, the project demonstrates the ability to create a minimal impact commercial building using available technologies.

To meet air tightness requirements driven by net zero energy (NZE) goals and overall biomimicry in design principles, it was necessary to use a high&#;performance membrane that allowed wall assembly materials to flex and breathe, expelling water vapor, while keeping out external moisture. Miller Hull selected the PROSOCO/BEI &#;Cat 5&#; coating and related sealants based on previous successful use of the system designed for wet weather application typical in Pacific Northwest construction.

After further research, Point32 informed PROSOCO the system could not be used due to presence of dibutyl phthalate (CAS 84&#;74&#;2), a chemical restricted by LBC materials criteria. Phthalates are widely used as plasticizers and are a nearly ubiquitous environmental contaminant. Phthalates have been shown to have effects on the reproductive systems of lab animals and on human health.

In response, PROSOCO and BEI co&#;developed alternative formulations that substituted polypropylene glycol for dibutyl phthalate while preserving application characteristics and meeting International Code Council Evaluation Service (ICC&#;ES) air leakage and durability performance standards.

Initially, the formulations were specific to the Bullitt Center project. However, PROSOCO and BEI evaluated cost and performance and opted to switch the entire product line to the polypropylene glycol chemistry. This milestone was reached by the end of with subsequent commercial, residential, LBC, LEED, EnergyStar, and Passive House high-performance and NZE applications across North America. This project demonstrated that phthalate&#;free and commercially viable sealant systems can be manufactured using current technologies.

PLATech, Green Chemistry Universal Adhesive-Sealing Technology: DRAFT: With estimated sales and production in the adhesive and sealants market of over $42.4B/year and 28.3B pounds/year, respectively, the applications of these products are broad-based and include areas such as automotive, general wood products, and consumer products. Virtually all adhesives/sealants used worldwide are volatile organic compound (VOC)&#;based and not environmentally preferable. Addressing this market challenge, PLATech comprises a class of VOC&#;free adhesives/sealants in tandem with tailored application methods for enabling adhesion to most substrates. PLATech adhesives/sealants are based on polylactic acid (PLA) &#; a renewable corn/soy-based derivative &#; and offer high performance capabilities while remaining bio-renewable and selectively biodegradable. PLATech also provides enhanced functionality including versatility to adhere to a vast class of materials, including challenging materials such as aluminum to steel, and even Teflon. PLATech provides a sustainable alternative combined with the ability for tailored strength, flexibility, ease of application and removal, and set times. Indeed, the burgeoning use of adhesives in the auto industry is stymied by the inability of most adhesives to join aluminum to steel &#; something PLATech achieves readily, while remaining biodegrable and sustainable. PLATech can be tailored to meet or exceed the performance of commercially available polyurethane, cyanoacrylate, EVA, and formaldehyde-based adhesives by over 100%, reaching bond strengths of over 45 MPa (6,200 psi) with low cost applicators. No pressurization or substrate surface preparation is required for use on a wide range of substrates, eliminating the need for chemical and physical treatment. Furthermore, the ability to selectively tailor PLATech adhesives via radiation-based crosslinking has been demonstrated, allowing for enhanced formulation of application-specified bond strength and functionality even in elevated temperature environments over 200°C. PLATech adhesives/sealants provide sustainable alternatives for the marketplace while meeting the cost and performance requirements of the industry including strength, flexibility, and adhesion to even the most difficult substrates.

Cleaner Transportation Fuels and Commodity Chemicals from Methane: DRAFT: The abundance of methane supplies from shale gas and renewable sources has created a profound and global opportunity. However, difficulty in transportation and technical constraints of using methane has relegated it to a low-value commodity fuel, or worse, a wasted and unused resource. Today, methane is mostly burned to produce heat and/or power. As much as half of the world&#;s methane supply is logistically challenged or stranded in hard to reach geographies or is being flared with no economic value and negative environmental impact to the tune of 5,000 billion cubic feet per year. Globally abundant supplies of methane, the continuing need for transportation fuels and chemical and sustainability concerns are a combination for which the world needs a solution through new innovation.

Siluria Technologies has developed a novel catalytic process that transforms methane into transportation fuels and petrochemical building blocks in an efficient, cost-effective, scalable manner. Siluria&#;s breakthrough Oxidative Coupling of Methane (OCM) process technology is believed to be the first commercially viable and economically competitive process to directly convert methane to ethylene. Siluria&#;s second process technology can convert ethylene to liquid fuels such as gasoline, diesel, or jet fuel, enabling methane to potentially supplement petroleum as the worldwide basis for transportation fuels and commodity chemicals.

Siluria operates three pilot facilities and recently completed construction and startup of the world&#;s first OCM demonstration plant. Siluria is actively commercializing the technology in partnership with leading engineering and operating companies for a broad range of applications in the upstream, midstream gas processing, downstream chemicals production, and refining operations.

1, 1-Disubstituted Alkenes: DRAFT: Sirrus advances manufacturing technology through chemistry relating to the synthesis, stabilization, activation, and formulation of a unique and reactive class of 1,1-dicarbonyl substituted alkenes. These monomers, their derivatives, and resulting polymers provide the foundation for enabling Sirrus&#; partners and customers to meet their customer&#;s desire to reduce manufacturing costs, improve quality, and improve their environmental footprint. These monomers, their derivatives, and resulting polymers provide fast cure speeds at ambient temperatures to significantly reduce cycle times, increase throughput, reduce energy requirements, and enable new material selection in a broad range of customer and consumer applications, including automotive, electronics, packaging, and hygiene.

VF Corporation: CHEM-IQSM: DRAFT: Chemical management in the apparel and footwear industries is complex. VF Corporation produces close to 500 million units of product at more than 2,000 facilities annually, operating one of the largest and most sophisticated supply chains in the world. VF recognized the need for simplified solutions in chemical management and saw an opportunity to use its size and scale to improve workplace safety, environmental protection, and product quality by creating an innovative chemical program.

VF challenged itself to take an entirely different approach to existing chemical management programs which evaluate products for chemical composition after they are produced. Instead, VF focused on testing and eliminating potentially harmful chemicals before they enter manufacturing processes. CHEM-IQSM is a first-of-its kind, cost-effective, simple process for factory suppliers to submit chemicals to be screened of over 400 potentially harmful substances. Each test costs approximately $50 compared to $1,000 for other methods &#; a 95% cost reduction.

Chemical identification prior to manufacturing provides suppliers with clear instructions on which chemicals are preferred and non-preferred. CHEM-IQSM, developed in collaboration with an advisory council from Natural Resources Defense Council, University of Massachusetts-Lowell, Modern Testing Services, and the University of Leeds, scans chemical samples and delivers an easy-to-understand, color-coded rating to the supplier indicating whether or not the formulation is permitted for use.

CHEM-IQSM is currently used at VF-owned facilities and supplier factories in the United States, China, Turkey, Taiwan, and Mexico. To date, CHEM-IQSM has removed more than 250 tons of non-preferred textile auxiliaries from VF&#;s supply chain before they entered the factory. Thus, CHEM-IQSM has already had a positive impact on VF&#;s ability to prevent potential worker and customer exposure, as well as the discharge of non-preferred chemicals to air, water, or land.

Bacteriophage-Based Bacterial Identification and Antibiotic Resistance Test: DRAFT: Antibiotic-resistant bacterial infections are a serious and growing global health problem. Conventional antibiotic resistance determination techniques typically require laborious and time-intensive culture-based assays, which take up to 72 hours and expend an inordinate amount of disposable plastics and bacterial growth media. In contrast, the Colorado School of Mines (CSM) bacteriophage amplification platform allows for a greener alternative by (a) enabling rapid simultaneous identification and antibiotic resistance determination without the need for extensive culturing, (b) minimizing the use of disposable plastics, and (c) reducing overall environmental impact. More importantly, with respect to its impact on human diagnostics, these attributes result in more user-friendly tests with significantly reduced testing times of less than five hours. First described, developed, and patented by the Advanced Biodetection Technologies Laboratory at CSM, it has advanced the technology through several key breakthroughs that have applied the technology as a greener alternative for sensitive and rapid identification and detection of Burkholderia, Listeria, and Enterococcus while maintaining the technology&#;s minimal environmental footprint.

An Application of Hybrid Multispectral Analysis; Real-Time Wastewater Process Control: DRAFT: Hybrid Multispectral Analysis (HMA) is a unique combination of advanced optical, photonic, and statistical technologies applied to the challenge of providing synchronized high frequency data for complex water components. Such information is required to control treatment processes in real time. HMA allows plants to continuously adjust treatment recipes based on current and on-line historical data to eliminate over and under treatment, provide real time water security, and enable closer compliance with and more effective enforcement of environmental laws.

HMA utilizes a single optical probe to conduct over 3.3 million in situ measurements per day, collecting direct molecular data on absorption, reflectance, and fluorescence. Molecular data is used to rapidly quantify critical water quality parameters such as biochemical oxygen demand (BOD), chemical oxygen demand (COD), total free chlorine (HOCl+OCl-), total suspended solids (TSS), and ultraviolet A (UVA) over the concentration range spanning from wastewater influent to effluent. Parameter values and/or control signals are broadcast about every two minutes for real time process control which can be used to determine the chemical load or energy consumption of a plant and quality of water it discharges. This technology can help guide chlorine injection or UV lamp settings, as well as aeration blower speeds, nutrient injectors, or to stop pumps when water security parameters are violated.

HMA incorporates several green chemistry principles including elimination of reagents and standards for sampling, elimination of sample preparation and storage, elimination of treatment guard bands used to compensate for delays in conventional data, and the need for only 72 watts to operate. HMA is sold under the trade name LiquID&#;. To date, over 85 LiquID&#; Stations shipped have proven useful in the fields of municipal water, wastewater treatment, water reuse, and industrial process control. The HMA methodology was developed through support in part by the EPA, Office of Naval Research, Oregon State University, and Oregon Nanoscience and Microtechnologies Institute.

Ultra-High Energy Density Metal-Free Sugar Biobattery: DRAFT: Building high-energy density, green, and safe batteries is highly desirable for meeting rapidly-increasing needs of portable electronics. Enzymatic fuel cells (EFCs)/biobatteries are appealing metal-free bioinspired batteries, where low-cost enzymes are used to convert chemical energy stored in a few chemicals to electricity. Sugars, the most abundant renewable bioresource, are natural high-energy storage compounds. A sugar biobattery is a type of enzymatic fuel cell that converts sugars to electricity in a closed system. Incomplete oxidation of complex sugars mediated by few enzymes in EFCs suffers from low energy densities and slow reaction rate. Cell Free Bioinnovations Inc. designed a synthetic ATP-free and CoA-free catabolic pathway comprised of 13 enzymes for producing 24 electrons per glucose unit of maltodextrin through in an air-breathing EFC without mobile parts. Also, the biobattery exhibited the maximum power output of 1.2 mW cm-2 and current density of 8.6 mA/cm2, far higher than microbial fuel cells. A sugar-powered biobattery with a characteristic of complete oxidation of 15% maltodextrin had an energy storage density of 596 Ah kg-1, one order of magnitude higher than those of lithium batteries. These metal-free biobatteries featuring 100% biodegradability, absolute safety, and fast refillability would be next-generation green power sources, especially for portable electronics.

Green Biohydrogen Production from Renewable Carbohydrates and Water via in vitro Synthetic Enzymatic Pathways: PENDING

Alternative to Sulfur Hexafluoride Enables up to 99% Greenhouse Gas Emission Reduction: PENDING

Green Nanotechnology Product and Processes for Cleaning Up Contaminated Soil and Groundwater: PENDING

Novel Active Agents Inhibit Bacterial Biofilm Formation and Fouling: PENDING

Plating on Plastics: PENDING

Estolides: A Low-Cost, High-Performance Renewable Fluid Certified for Motor Oil: PENDING

Discovery, Development and Implementation of New Chemical Technology toward a Novel Commercial Synthesis for the HIV-Attachment Inhibitor, BMS-: PENDING

FLUEPAC® activated carbon products for superior mercury control from flue gas and green re-use of coal combustion residuals: PENDING

Disruptive Methantropic Technology for Sustainable Food, Fuel and Products: Green Chemistry Innovation Enabling US Global Competitiveness in Low-Carbon, New Economy: PENDING

Molecular Catalysts for Sustainable Wastewater Electrolysis: PENDING

PeroxyMAXTM a safer and less toxic alternative to chlorine oxidants: PENDING

Delta STM: An Environmentally Benign and Worker Safe Asphalt Rejuvenator: PENDING

Membrane Dehydration for Solvent Recovery and Reuse: PENDING

Dream Production &#; CO2 as a new building block for high-tech plastics: PENDING

Dow Polymeric Flame Retardant: PENDING

SOLDERONTM BP Lead-free Solder Plating Chemistry: PENDING

KathonTM 7 Tl Antimicrobial for Water Treatment Applications: PENDING

Creation, Integration, and Engineering of the World&#;s Largest Cellulosic Ethanol BioRefinery Production Platform: PENDING

Mg rich primer for Chrome free protection of Aluminum and its alloys: PENDING

Floral Soil: A Green Chemistry Alternative to Phenol Formaldehyde Foams for Floral & Horticulture Industries: PENDING

Catalytic Cross-Couplings Using a Sustainable Metal and Green Solvents: PENDING

Cooling Tower Water Conservation and Chemical Treatment Elimination: PENDING

Surface Engineered High-performance Catalysts for Fuel Cell Applications: PENDING

Evolution Polymerization To Produce Sustainable Polycarbonate Dendrimers: PENDING

A Greener Process for the Fragrance Veridian and Development/Implementation of IFF&#;s Green Chemistry Tool: PENDING

SPLAT® VERB: An Insecticide-Free, Green Repellent for Bark Beetle Pests of North American Forestry: PENDING

Carbon Engineering Platform: PENDING

Integrated Production of Sustainable Biobased Malonic Acid for Significant Source Pollution Reduction, Cost, and Performance Advantages: PENDING

GRANDEVO® advanced bioinsecticides: PENDING

ZEQUANOX®: PENDING

Degradable Polymers for Fracking Applications: PENDING

The Recovery of Organic Halides from Waste Streams by the Chemical Reaction of Hydrogen and Carbon Dioxide: PENDING

Replacing Packaging Plastics with Sustainable Bioplastics from Megacrop Waste: PENDING

Highly efficient and practical monohydrolysis of symmetric diesters: PENDING

Renewable Oils for High Performance Lubricants: PENDING

Bio-Derived Oligomer Technology to Replace Bis Phenol-A (BPA)-Based Thermoset Coatings: A Practical Solution for BPA-Free Metal Can Coatings for Beer, Beverage, and Food Containers: PENDING

SunCryl HP 114, an Environmentally Friendly Release Coat: PENDING

A Green, Energy Efficient, Chemoenzymatic Process to Manufacture Pregabalin: PENDING

Cold-Water Enzyme: Reducing the Environmental Footprint of Residential Laundry through Low Temperature Cleaning: PENDING

Breakthrough Catalyst Technology Enables Cost Competitive Drop-in Bio-Based Nylons and Polyurethanes: PENDING

Building Multi-Functional Polyols Using Recycled Raw Material Streams: PENDING

Rivertop Renewables - Sugar Oxidation Process: PENDING

Environmentally Friendly Colored Pyrotechnic Illuminants: PENDING

Input and Waste Associated with the Isomerization of Linear Alpha Olefins: PENDING

Environmental protection reagents from MSW: one-step quantitative resourcing municipal solid waste: PENDING

A Feedstock Flexible Process to produce Diesel and/or Jet Fuel from Renewable Resources: PENDING

SPEARTM Insecticide: First Member of a New Class of Biopesticides which shows Efficacy comparable to Synthetic Insecticides: PENDING

Accel 5 RTU, an Accelerated Hydrogen Peroxide® (AHP®) based cleaner-disinfectant that provides a sustainable and safer choice for infection prevention and control: PENDING

Atom-Efficient Process for Producing Taurine: PENDING

AquaRefining: PENDING

Green and Sustainable Processing for the Fractionation of Botanicals for Cosmetic Use: Zeta FractionTM Technology: PENDING

A Condensation Chemistry-Inspired Biorefinery to Produce Superior Low Carbon Fuels and Lubricants: PENDING

Infrared Spectroscopic Determination of Oil in Anhydrous Ammonia with Solid State Extraction: PENDING

The More Sustainable Choice: 100% Renewable Ethoxylates: PENDING

BLUEDGETM Polymeric Flame Retardant (FR) Technology for Extruded and Expanded Polystyrene Foams: PENDING

CANVERATM Polyolefin Dispersions: PENDING

Efficient Industrial Scale Production of 2,5-Furancarboxylic Acid (FDCA): Bio-Based Alternative to Purified Terephthalic Acid (PTA): PENDING

EASTMAN 168TM: The Societal Impact of Plastics Improvement: PENDING

FARADAYIC® HF-FREE ElectroPolishing Process for Niobium Superconductin Radio Frequency (SRF) Cavities: PENDING

Software Models Lead and Copper Solubility and Corrosion in Municipal Water Distribution Systems To Minimize Lead and Copper Contaminants, Predict the Impact of Changes: PENDING

Saving Water In Oil And Gas Production: PENDING

A green chemistry platform for synthesis of double-stranded RNA: First market application in insect control: PENDING

Eco Sheep® AquaSheepTM Washable Bicycle Chain Lubricant: PENDING

Transition Metal-Free Heteroatom-Transfer Reactions Utilizing Bio-renewable and Multifunctional Reagent Scaffolds: PENDING

Roof Maxx Shingle Sealer: PENDING

FloPRO®: A Multifunctional Proppant Coating Technology Delivers Exceptional Solutions for Numerous Hydraulic Fracturing Challenges: PENDING

Green Renewable Nanoparticles: PENDING

The Development of SynBurst OB-ECO: PENDING

PhosZeroTM Scale & Corrosion Inhibitor: PENDING

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