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 2023.1 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 20171. 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 13000kg of silicone in 2019. 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 2019 and $500,000 system sales. The polymer technology is patented. A commercial roll-out is planned in 2020. 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 16128), 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 2018. 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 2018. It is in advanced stages of qualification at major battery producers with implementation targets in June 2020.

"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 2020, 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 2020. 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 1Q2019. 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 2020. 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 D8181-19), which was approved in 2018 and adopted in 2019, 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 2020 and expand to full operations by the end of 2020."

"At least as early as 2011, 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 2015. 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 2017, 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 2020, and to declare a long-term goal of fully replacing petroleum-derived oils by 2040."

"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 1970s 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 2017 to $25 billion by 2022. 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 2016 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 2040*, 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 1978, 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 1992 by researchers to find a way to deconstruct potential cancer-causing PCBs from used transformer oil. In 2001 Hydrodec was founded to commercialise the technology. The first plant was built in Australia in 2006, followed by Canton, Ohio ten years ago. In 2017, Hydrodec US avoided 6.7 million gallons of used oil to become waste. The total of PCB contaminated oil received between 2012 and 2016 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 2017 --- This technology, “Refining of used oil” (US Patent number: 9828558) 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 2009 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 2008 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 2020.

Since the 1940s, 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 2018 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 2019.

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 2018, 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 2004. 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 1987, the Montreal protocol was signed, which called for a freeze on the production and use of chlorofluorocarbons at 1986 levels with subsequent reductions and complete elimination by January 1, 1996. 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 2006, 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 2005 and 2006 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, Accupril^TM. 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 Nanostructured^TM 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 2005 and 2006, 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-0524): 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-0524A) and with both niacin and simvastatin (MK-0524B) 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 2006 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 2004, 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 1011), 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 1995, the United States produced 9 million tons of biosolids and is expected to produce 11 million tons/year by the year 2000. 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.