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Green Chemistry Program Nomination Table

This table contains information on each unique technology nominated for the Green Chemistry Challenge from 1996 through 2019. Although EPA has received 1,766 nominations during this period, only 912 unique technologies are represented here because sponsors may nominate a technology more than once.

The columns:
  • Year: The year of the most recent nomination for this technology.
  • Winner: The status of each nomination as an award-winning technology or a nominee.
  • Nomination Sponsor: The sponsor or sponsors of the nomination; generally, the name of the company, academic researcher (and institution), or other organization that developed the technology.
  • Nominated Technology Title: The title for the nominated technology as given by the sponsor. Each title is followed by a link to the associated summary page (for award-winning technologies) or abstract (for all other technologies).
  • City: The city given in the nomination; this is usually the city of the headquarters for a company or primary location of an academic institution, but may be the city of a plant or research facility. In a few cases, the city is that of a consultant who prepared the nomination.
  • State (St.): The state given in the nomination; as for the city of nomination, this may not represent the headquarters for a company or the primary location of an academic institution.

You can also download similar information about all nominated technologies as either:

  1. Green Chemistry Challenge Nominations.xls(1 pg, 3 MB)
  2. Green Chemistry Challenge Nominations.csv(1 pg, 2 MB)
Nomination Table

Sort alphabetically or by year, use the search function, or both together.

Year Winner Nomination Sponsor Nominated Technology Title (abstract/summary) City St.
1996 No Advanced Micro Devices (AMD) The Emission Quantification Model (abstract) Austin TX
1996 No Bayer Corporation Aldimine-Isocyanate Chemistry: a Foundation for Environmentally-Friendly High Solids Coatings (abstract) Pittsburgh PA
1996 Yes Donlar Corporation Production and Use of Thermal Polyaspartic Acid (summary) Bedford Park IL
1996 Yes Dow Chemical Company, The 100 Percent Carbon Dioxide as a Blowing Agent for the Polystyrene Foam Sheet Packaging Market (summary) Midland MI
1996 No Eastman Chemical Company Water-Dispersible Sulfopolyester for Reduced VOC Consumer Products (abstract) Kingsport TN
1996 No GE Plastics (General Electric Corporation) New Catalyst for Producing ULTEM® Thermoplastic Resin (abstract) Mt. Vernon IN
1996 Yes Holtzapple, Mark; Texas A&M University Conversion of Waste Biomass to Animal Feed, Chemicals, and Fuels (summary) College Station TX
1996 No Hudlicky, Tomas; University of Florida Enzyme-Assisted Conversion of Aromatic Substances to Value-Added End Products. Exploration of Potential Routes to Biodegradable Materials and New Pharmaceuticals (abstract) Gainesville FL
1996 No Merck & Co., Inc. Waste Minimization in the Manufacture of an Antibiotic Produced by Chemical Synthesis (abstract) Whitehouse Station NJ
1996 Yes Monsanto Company Catalytic Dehydrogenation of Diethanolamine (summary) St. Louis MO
1996 No Recombinant BioCatalysis, Inc. (RBI) Development of a Biodiversity Search and Enzyme Optimization Technology (abstract) Sharon Hill PA
1996 Yes Rohm and Haas Company Designing an Environmentally Safe Marine Antifoulant (summary) Spring House PA
1996 No Stanson Corporation National Conversion to Low Sudsing Hand Dish Detergents for Industrial, Institutional, and Especially Consumer Application (abstract) S. Kearny NJ
1996 No Taylor, Larry T.; Virginia Tech and Virginia Tech Intellectual Properties A Nontoxic Liquid Metal Composition for Use as a Mercury Substitute (abstract) Blacksburg VA
1996 No Tremco, a BF Goodrich Company Automotive Windshield Adhesives (abstract) Akron OH
1996 No U.S. Department of Energy, Los Alamos National Laboratory A Microwave Oven Dissolution Procedure for a Ten Gram Sample of Soil Requiring Radiochemical Analysis (abstract) Los Alamos NM
1996 No U.S. Department of Energy, Los Alamos National Laboratory; Phillips, Jonathan; Pennsylvania State University Two-Stage Catalyst for NOx Reduction, CO Oxidation, and Hydrocarbon Combustion in Oxygen Containing Exhaust Mixtures (abstract) Washington DC
1996 No U.S. Department of Energy, Office of Industrial Technologies Programs The Alternative Feedstocks and Biological and Chemical Technologies Research Programs (abstract) Washington DC
1997 Yes Albright & Wilson Americas THPS Biocides: A New Class of Antimicrobial Chemistry (summary) Ashland VA
1997 No Alliance for Environmental Technology (AET) The Use of Chlorine Oxide, the Foundation of Elemental Chlorine-Free Bleaching for Pulp and Paper, as a Pollution Prevention Process (abstract) Washington DC
1997 No Altus Biologics Inc. Cross-Linked Enzyme Crystals (CLECs) as Robust and Broadly Applicable Industrial Catalysts (abstract) Cambridge MA
1997 No American Chemical Corporation Utilization of High Performance, Environmentally Compliant Chemicals: GREEN LINE Adhesive, Sealant, and Coating Technologies (abstract) Washington DC
1997 No Anderson, Marc A.; University of Wisconsin-Madison Green Technology for the 21st Century: Microporous Ceramics (abstract) Madison WI
1997 No Benchmark Products, Inc. Development of a Nickel Brightener Solution (abstract) Indianapolis IN
1997 Yes BHC Company (Hoechst Celanese) BHC Company Ibuprofen Process (summary) Dallas TX
1997 No Circuit Research Corporation A Nontoxic, Nonflammable, Aqueous-Based Cleaner/Degreaser and Associated Parts Washing Systems Commonly Employed in the Automotive Repair Industry (abstract) Delano MN
1997 Yes DeSimone, Joseph M.; University of North Carolina at Chapel Hill (UNC) and North Carolina State University (NCSU) Design and Application of Surfactants for Carbon Dioxide (summary) Chapel Hill NC
1997 No Dow Chemical Company, The INVERTTM Solvents in Aircraft Paint Stripping (abstract) Midland MI
1997 No Dumesic, James A.; University of Wisconsin-Madison Rational Design of Catalytic Reactions for Pollution Prevention (abstract) Madison WI
1997 No DuPont Company The DUCARE 'Zero Effluent' Recycle Chemistry System (abstract) Wilmington DE
1997 No Eastman Chemical Company Biodegradable Copolyester (abstract) Kingsport TN
1997 No Eastman Chemical Company Biofiltration Technology (abstract) Kingsport TN
1997 No Eastman Chemical Company Water-Dispersible Hot-Melt Adhesive Raw Material (abstract) Kingsport TN
1997 No Gross, Richard A.; University of Massachusetts Lowell Biotechnological Routes to 'Tailored' Polymeric Products of Environmental and Industrial Importance (abstract) Lowell MA
1997 No Hatton, T. Alan; Massachusetts Institute of Technology Derivatized and Polymeric Solvents for Minimizing Pollution During the Synthesis of Pharmaceuticals (abstract) Cambridge MA
1997 No Henkel Corporation Alkyl Polyglycoside Surfactants (abstract) Ambler PA
1997 No Hughes Environmental Systems, Inc. DryWashTM Carbon Dioxide Dry Cleaning Technology (abstract) El Segundo CA
1997 No IBM-Austin Elimination of Ozone-Depleting Chemicals in the Printed Wire Board and Electronic Assembly and Test Processes (abstract) Austin TX
1997 No IBM-Austin Innovative Techniques for Chemical and Waste Reductions in the Printed Wire Board Circuitize Process (abstract) Austin TX
1997 Yes ImationTM Corporation DryViewTM Imaging Systems (summary) Oakdale MN
1997 No King, Charles M.; University of Georgia Biomimetic Transition Metal Complexes for Homogeneous Catalytic Reductive Dechlorination of the PCBs/One-Step Extraction-Detoxification in Subcritical and Supercritical Fluids (abstract) Athens GA
1997 No Klenzoid, Inc. Zero Discharge System For Cooling Towers (abstract) Conshohocken PA
1997 Yes Legacy Systems, Inc. ColdstripTM, A Revolutionary Organic Removal and Wet Cleaning Technology (summary) Fremont CA
1997 No Materials Technology Limited SuperCTM, The Use of Supercritical Carbon Dioxide (abstract) Reno NV
1997 No Molten Metal Technology, Inc. Catalytic Extraction Processing (CEP) (abstract) Waltham MA
1997 No Monsanto Company Roundup ReadyTM Technology (abstract) St. Louis MO
1997 No Sandoz Pharmaceutical Corporation A New Process for the Manufacture of Pharmaceuticals (abstract) East Hanover NJ
1997 No Shaw, Henry; New Jersey Institute of Technology (NJIT) The Replacement of Hazardous Organic Solvents with Water in the Manufacture of Chemicals and Pharmaceuticals (abstract) Newark NJ
1997 No Technic, Inc. Noncyanide Silver Electroplating (abstract) Providence RI
1997 No Texaco, Inc. CleanSystem3 Gasoline (abstract) White Plains NY
1997 No U.S. Department of Energy, Los Alamos National Laboratory Application of Green Chemistry Principles to Eliminate Air Pollution From the Mexican Brickmaking Microindustry (abstract) Los Alamos CA
1997 No U.S. Department of Energy, Los Alamos National Laboratory Solvent Replacement and Improved Selectivity in Asymmetric Catalysis Using Supercritical Carbon Dioxide (abstract) Los Alamos NM
1997 No U.S. Department of Energy, Pacific Northwest National Laboratory DOE Methods for Evaluating Environmental and Waste Management Samples (abstract) Richland WA
1998 No AlliedSignal Federal Manufacturing and Technologies Synergy CCSTM Precision Cleaning Solvent: A Government/Industry Solution to a Complex Environmental Problem (abstract) Kansas City MO
1998 No Beckman, Eric J.; University of Pittsburgh Design of CO2-Soluble Ligands for Affinity Extraction Using CO2 (abstract) Pittsburgh PA
1998 No CTS Corporation Resistor Networks No-Clean Soldering (abstract) Berne IN
1998 No Doherty, Michael F.; Malone, Michael F.; University of Massachusetts, Amherst Reactive Distillation Technology to Reduce Waste at the Source (abstract) Amherst MA
1998 Yes Draths, Karen M. and Frost, John W.; Michigan State University Use of Microbes as Environmentally Benign Synthetic Catalysts (summary) East Lansing MI
1998 No DuPont Company NAFION Membrane Technology (abstract) Wilmington DE
1998 No DuPont Company The INFINITY Process (abstract) Wilmington DE
1998 No DuPont Polyester DuPont Petretec(SM) Polyester Regeneration Technology - Making Polyester Evergreen (abstract) Wilmington DE
1998 No E. I. DuPont de Nemours & Co., Inc. Zero Effluent Photographic Processing in the Printing Industry (abstract) Wilmington DE
1998 No Eastman Kodak Company Polycarbonate/Polydimethylsiloxane Copolymers for Thermal Print Media (abstract) Rochester NY
1998 No Eastman Kodak Company Replacement of Methanol Solutions with Aqueous Dispersions in Photographic Coatings (abstract) Rochester NY
1998 No Eli Lilly and Company Waste Reduction During Development of a New Process for Manufacture of Pharmaceutical Products (abstract) Indianapolis IN
1998 Yes Flexsys America L.P. Elimination of Chlorine in the Synthesis of 4-Aminodiphenylamine: A New Process That Utilizes Nucleophilic Aromatic Substitution for Hydrogen (summary) Akron OH
1998 No Govind, Rakesh; University of Cincinnati Bioconversion of Carbon Dioxide into Organic Feedstocks (abstract) Cincinnati OH
1998 No Hendrickson, James B.; Brandeis University The SYNGEN Program for Generation of Alternative Syntheses (abstract) Waltham MA
1998 No Lockheed Martin Tactical Aircraft Systems Development and Implementation of Low Vapor Pressure Cleaning Solvent Blends (abstract) Fort Worth TX
1998 No Lockheed Martin Tactical Aircraft Systems (LMTAS) Implementation and Verification of Aqueous Alkaline Cleaners (abstract) Fort Worth TX
1998 No MEMC Electronic Materials, Inc. Elimination of Ozone-Depleting Chemicals Through the Use of a Water Soluble Adhesive "Green Wax" (abstract) St. Peters MO
1998 No Mobil Technology Company Production of Cumene with Zeolite Catalyst--The Mobil/Badger Cumene Process (abstract) Paulsboro NJ
1998 No NICCA U.S.A., Inc. Heavy Metals Free, Non-Formaldehyde Fixing Agent for Direct and Fiber Reactive Dyes (abstract) Fountain Inn SC
1998 No Nortel Technology Molyphos: A Chromate-Free Alternative for Corrosion Protection of Metal Parts (abstract) Raleigh NC
1998 No Pharmacia and Upjohn, Inc. Environmental Improvements from Redesigning the Commercial Manufacture of Progesterone (abstract) Kalamazoo MI
1998 No Phillips Petroleum Company Reduced Volatility Alkylation Process (abstract) Bartlesville OK
1998 No Praxair, Inc. Liquid Oxidation Reactor (LOR) (abstract) Danbury CT
1998 Yes Pyrocool Technologies, Inc. Technology for the Third Millennium: The Development and Commercial Introduction of an Environmentally Responsible Fire Extinguishment and Cooling Agent (summary) Lynchburg VA
1998 No Rochester Midland Corporation Core Line of Cleaning Products (abstract) Rochester NY
1998 Yes Rohm and Haas Company Invention and Commercialization of a New Chemical Family of Insecticides Exemplified by CONFIRMTM Selective Caterpillar Control Agent and the Related Selective Insect Control Agents MACH 2TM and INTREPIDTM (summary) Philadelphia PA
1998 No Rybarczyk, James P.; Ball State University Premature Degradation of Coolant Oil in the Machining of Magnesium in the Automobile Industry (abstract) Muncie IN
1998 No Stepan Company Stepanfoam Water-Blown Polyurethane Foam HCFC-Free, Environmentally Friendly, Rigid Polyurethane Foam (abstract) Northfield IL
1998 Yes Trost, Barry M.; Stanford University The Development of the Concept of Atom Economy (summary) Stanford CA
1998 No U.S. Department of Agriculture, Agricultural Research Service, Northwest Irrigation and Soils Research Laboratory Polyacrylamide Technology Reduces Soil Erosion (abstract) Kimberly ID
1998 No U.S. Department of Defense, Office of Munitions; U.S. Department of Energy, Weapons Supported Research; Lawrence Livermore National Laboratory Environmentally-Driven Preparation of Insensitive Energetic Materials (abstract) Livermore CA
1998 Yes U.S. Department of Energy, Argonne National Laboratory Novel Membrane-Based Process for Producing Lactate Esters – Nontoxic Replacements for Halogenated and Toxic Solvents (summary) Argonne IL
1998 No U.S. Department of the Navy, Office of Naval Research; U.S. Department of the Navy, Naval Surface Warfare Center; DeSimone, Joseph, University of North Carolina; Aerojet Propulsion Use of Carbon Dioxide as an Alternative Green Solvent for the Synthesis of Energetic Thermoplastic Elastomers (abstract) Arlingtion VA
1998 No U.S. Department of the Navy, Office of Naval Research; U.S. Department of the Navy, Naval Surface Warfare Center; U.S. Army Armament Research, Development and Engineering Center; U.S. Department of Energy, Los Alamos National Laboratory; Aerojet Waste Reduction in the Production of an Energetic Material by Development of an Alternative Synthesis (abstract) Arlington VA
1998 No Union Camp Corporation C-FREETM Pulp Ozone Bleaching Project (abstract) Franklin VA
1999 No ABB Power T&D Company Inc. Fully Biodegradable Vegetable Oil-Based Electrical Insulating Fluid (BIOTEMPTM) (abstract) Raleigh NC
1999 No Akzo Nobel Business Unit Base Chemicals A Durable Hydrodechlorination Catalyst for Selective Conversion of CCl4 to CHCl3 (abstract) Dobbs Ferry NY
1999 No Akzo Nobel Sub Business Unit Phosphorus Chemicals Next Generation Fire-Resistant Fluids (abstract) Dobbs Ferry NY
1999 No American Society for Testing & Materials (ASTM) Analysis of Liquid Hazardous Waste for Heavy Metals by Energy-Dispersive X-ray Fluorescence (EDXRF) Spectrometry (abstract) West Conshohocken PA
1999 No Antia, Jimmy E.; Govind, Rakesh; University of Cincinnati Novel In-Situ Zeolite Coatings in Monoliths (abstract) Cincinnati OH
1999 No Beckman, Eric J.; University of Pittsburgh Metal Extraction and Recovery Using Carbon Dioxide (abstract) Pittsburgh PA
1999 Yes Biofine, Incorporated Conversion of Low-Cost Biomass Wastes to Levulinic Acid and Derivatives (summary) Waltham MA
1999 Yes Collins, Terry; Carnegie Mellon University TAMTM Oxidant Activators: General Activation of Hydrogen Peroxide for Green Oxidation Technologies (summary) Pittsburgh PA
1999 No Cussler, E.L.; University of Minnesota Pollution Preventing Lithographic Inks (abstract) Minneapolis MN
1999 Yes Dow AgroSciences LLC Spinosad: A New Natural Product for Insect Control (summary) Indianapolis IN
1999 No Dow Corning Corporation New Technology Converts Waste to Valuable Intermediates (abstract) Carrollton KY
1999 No Dow Corning Corporation Volatile Methyl Siloxanes: Environmentally Sound Solvent Systems (abstract) Midland MI
1999 No DuPont Company Reduction of Carbon Tetrachloride Emissions at the Source by the Development of a New Catalyst (abstract) Wilmington DE
1999 No Geon Company, The Increased Utilization of Raw Materials in the Production of Vinyl Chloride Monomer (abstract) Avon Lake OH
1999 No Harrell, J.W.; Lane, Allan M.; Jefcoat, I.A.; Nikles, David E.; The University of Alabama Waterborne Coating Formulations for Video Tape Manufacture (abstract) Tuscaloosa AL
1999 No Hauser, Inc. Paclitaxel Process Improvements (abstract) Boulder CO
1999 No IBM Corporation, T.J. Watson Research Center Green Card: A Biopolymer-Based and Environmentally Conscious Printed Wiring Board Technology (abstract) Yorktown Heights NY
1999 No Imation Corporation Imation No Process Plates (abstract) Oakdale MN
1999 No IMC-Agrico Company AGROTAIN® N-(n-butyl)Thiophosphoric Triamide (abstract) Bannockburn IL
1999 No International Metalizing Corporation Non Toxic Antifouling (abstract) Pennsauken NJ
1999 No Khalili, Nasrin R.; Arastoopour, Hamid; Walhof, Laura; Illinois Institute of Technology A Novel Waste Minimization Approach: Production of Carbon-Based Catalyst or Sorbent from Biosolids (abstract) Chicago IL
1999 No Ladisch, Michael R.; Purdue University Biobased Adsorbents for Desiccant Coolers (abstract) West Lafayette IN
1999 Yes Lilly Research Laboratories Practical Application of a Biocatalyst in Pharmaceutical Manufacturing (summary) Indianapolis IN
1999 No Lin, Chhiu-Tsu; Northern Illinois University Chrome-Free Single-Step In-Situ Phosphatizing Coatings (abstract) DeKalb IL
1999 No M.A. Hanna Color - Technical Center Reducing VOC Emissions by Eliminating Painting and Labeling Operations with a New Color Laser Marking System for Plastic Parts (abstract) Suwanee GA
1999 No Mallinckrodt Inc. The Removal of Oxides of Nitrogen by In Situ Addition of Hydrogen Peroxide to a Metal Dissolving Process (abstract) Chesterfield MI
1999 No Mathews, Alexander P.; Kansas State University Waste Biomass Utilization in the Production of a Biodegradable Road Deicer (abstract) Manhattan KS
1999 No Monsanto Company Metabolic Engineering of Crops for Commercial Production of Biodegradable Plastics (abstract) St. Louis MO
1999 No Nalco Chemical Company Nalco Fuel Tech NOxOUT® Process (abstract) Naperville IL
1999 No Nalco Chemical Company Nalco LAZON Technology (abstract) Naperville IL
1999 No Nalco Chemical Company Nalco NALMET® Heavy Metal Removal Technology (abstract) Naperville IL
1999 Yes Nalco Chemical Company The Development and Commercialization of ULTIMER®: The First of a New Family of Water-Soluble Polymer Dispersions (summary) Naperville IL
1999 No Nassaralla, Claudia Lage; Michigan Technological University Waste Reduction and Recycling of Magnesite-Chrome Refractory into the Steelmaking Process (abstract) Houghton MI
1999 No Novon International Natural Recycling of Plastics through Chemical and Biological Degradation (abstract) Tonawanda NY
1999 No Paquette, Leo A.; The Ohio State University Environmental Advantages Offered by Indium-Promoted Carbon-Carbon Bond-Forming Reactions in Water (abstract) Columbus OH
1999 No Peretti, Steven W.; North Carolina State University Biosynthetic Production of p-Hydroxybenzoate Improves Regiospecificity and Minimizes Byproduct Generation (abstract) Raleigh NC
1999 No Polaroid Corporation; Warner, John C.; University of Massachusetts Boston Environmentally Benign Supramolecular Assemblies of Hydroquinones in Polaroid Instant Photography (abstract) Waltham MA
1999 No Radiance Services Company The Radiance Process: A Quantum Leap in Green Chemistry (abstract) Bethesda MD
1999 No Raghavan, Dharmaraj; Howard University Design of Rubberized Concrete from Recycled Rubber Tires (abstract) Washington DC
1999 No Raghavan, Dharmaraj; Howard University Novel Applications of Polymer Composite from Renewable Materials (abstract) Washington DC
1999 No Richard H. Fish, Lawrence Berkeley National Laboratory, University of California Fluorous Biphasic Catalysis: A New Paradigm for the Separation of Homogeneous Catalysts from Their Reaction Substrates and Products, as Demonstrated in Alkane and Alkene Oxidation Chemistry (abstract) Berkeley CA
1999 No Rogers, Robin D.; University of Alabama Green Separation Science and Technology: Using Environmentally Benign Polymers to Replace VOCs in Industrial Scale Liquid/Liquid or Chromatographic Separations (abstract) Tuscaloosa AL
1999 No Rowe, H. Alan; Norfolk State University New Reducing Sugar Assay (abstract) Norfolk VA
1999 No SaLUT Inc. Chemically Modified Crumb Rubber Asphalt (abstract) McLean VA
1999 No Sequa Chemicals, Inc. Starch Graft Polymers as Phenolic Resin Extenders (abstract) Chester SC
1999 No Singh, Mono M.; Szafran, Zvi; Pike, Ronald M.; Merrimack College National Microscale Chemistry Center: The Leader in Worldwide Implementation of Microscale Technology (abstract) North Andover MA
1999 No Solutia Inc. Greenhouse Gases: From Waste to Product (abstract) St. Louis MO
1999 No Solvent Kleene Inc. Non-Hazardous Degreaser that Degreases as Efficiently as Trichloroethane and Outperforms Aqueous Products (abstract) Peabody MA
1999 No Stepan Company Stepan Company PA Lites Polyester Polyol (abstract) Northfield IL
1999 No Stewart, Jon D.; University of Florida Engineered Baker's Yeast as a Means to Incorporate Biocatalysis Early in Process Design: Application to the Asymmetric Baeyer-Villiger Oxidation (abstract) Gainesville FL
1999 No Subramaniam, Bala; University of Kansas A Novel Solid-Acid Catalyzed 1-Butene/Isobutane Alkylation Process (abstract) Lawrence KS
1999 No Supratech Systems Inc. Water Washable Flexo Photopolymer Plate "Flexceed" and Washout System (abstract) Charlotte NC
1999 No Synovec, Robert E.; University of Washington Novel Chemical Analysis Technologies by Water Liquid Chromatography, Raman Spectroscopy, and High Speed Gas Chromatography (abstract) Seattle WA
1999 No Synthon Corporation Development and Commercialization of High-Value Chemical Intermediates From Starch and Lactose. (abstract) Lansing MI
1999 No Tektronix, Inc. Designing Safer Chemicals: Spitfire Ink (abstract) Wilsonville OR
1999 No Thompson, Stephen; Colorado State University Small Scale Chemistry: Pollution Prevention in Inorganic Chemistry Instruction Program (abstract) Fort Collins CO
1999 No U.S. Army, U.S. Army Armament Research, Development, & Engineering Center Use of Solid Catalysts in Pollution Prevention in the Nitration of Aromatic Compounds (abstract) Picatinny Arsenal NJ
1999 No U.S. Department of Energy, Albany Research Center Chloride Free Processing of Aluminum Scrap (abstract) Albany OR
1999 No U.S. Department of Energy, Pacific Northwest National Laboratory Biocatalytic and Biomimetic Process for the Synthesis of Nitroaromatic Intermediates and Destruction of Nitrocompounds, Including Explosives (abstract) Richland WA
1999 No U.S. Department of the Treasury, Bureau of Engraving and Printing ISOMET: Development of an Alternative Solvent (abstract) Washington DC
1999 No Union Carbide Corporation Splittable Surfactants (abstract) Danbury CT
1999 No United States Postal Service Environmentally Benign Pressure Sensitive Adhesive Program (abstract) Washington DC
1999 No Varma, Rajender S.; Sam Houston State University Solvent-Free Chemical Synthesis (abstract) Huntsville TX
1999 No Viasystems Technology Corporation Solder Waste Reduction Environmental Project (abstract) Richmond VA
1999 No Washington State Department of Ecology Washington State Pollution Prevention, Health, and Safety Initiative in Academic Chemistry Laboratories (abstract) Spokane WA
1999 No Weimer, Alan W.; University of Colorado Vibrating Fluidized Bed Combustion Nitridation Processing Using Concentrated Solar Energy (abstract) Boulder CO
1999 No Zyvax Incorporated The Zyvax "Watershield" Mold Release (abstract) Boca Raton FL
2000 No 3M Center Hydrofluoroethers (HFEs)—The Right Balance of Properties (abstract) St. Paul MN
2000 No Albright & Wilson Americas, Inc. A New Environmentally Friendly Corrosion Inhibitor (abstract) Glen Allen VA
2000 No AMSOIL Incorporated Waste Oil Source Reduction Through Extended Oil Service Life (abstract) Superior WI
2000 No Arkenol Holdings, L.L.C. Sugars from Lignocellulosic Materials for the Production of Bio-Based Fuels and Chemicals (abstract) Mission Viejo CA
2000 No BAT Technologies Inc. Primer for Anti-Fouling Paint (abstract) New Rochelle NY
2000 Yes Bayer Corporation; Bayer AG (Germany) Two-Component Waterborne Polyurethane Coatings (summary) Pittsburgh PA
2000 No Beckman, Eric J.; University of Pittsburgh Catalysts for the Copolymerization of Carbon Dioxide and Cyclic Ethers (abstract) Pittsburgh PA
2000 No Bergbreiter, David E.; Texas A&M University The Use of Soluble Polymers to Recover Catalysts and to Control Catalytic Reactions (abstract) College Station TX
2000 No BetzDearborn, Inc. Designing an Environmentally Friendly Copper Corrosion Inhibitor for Cooling Systems (abstract) Trevose PA
2000 No BIOCORP, Inc. Biodegradable Thermoplastic Material (Mater-BiTM) (abstract) Redondo Beach CA
2000 No Brennecke, Joan F.; University of Notre Dame; Beckman, Eric J.; University of Pittsburgh Ionic Liquid/CO2 Biphasic Systems: New Media for Green Processing (abstract) Notre Dame IN
2000 No Center for Forest Products Research, Inc. Polymers and Plastics from Lignin Biomass (abstract) Albuquerque NM
2000 No CerOx Corporation The CerOx Process: A Non-Thermal Alternative for Hazardous Waste Destruction (abstract) Sunnyvale CA
2000 No Chemecol, LLC PVC Alternative Technology (abstract) Cornelius NC
2000 No Ciba Specialty Chemicals Corporation Ashless Friction Modifier/Antioxidant for Lubricants (abstract) Tarrytown NY
2000 No Ciba Specialty Chemicals Corporation New Organic Corrosion Inhibitors Help Replace Toxic Heavy Metals and Reduce Solvent Emissions (abstract) Tarrytown NY
2000 Yes Dow AgroSciences LLC SentriconTM Termite Colony Elimination System, A New Paradigm for Termite Control (summary) Indianapolis IN
2000 No Eastman Kodak Company Minimizing Environmental Emissions by Using Different Solvents in Manufacturing Processes (abstract) Rochester NY
2000 No Eka Chemicals, Inc. SVP-PureTM ClO2 Process Technology (abstract) Marietta GA
2000 No Environmental Technology and Education Center, Inc. (ETEC) High Energy Efficiency, Environmentally Friendly Refrigerants (abstract) Albuquerque NM
2000 No Freeman, Harold S.; North Carolina State University Synthetic Dyes Based on Toxicological Considerations (abstract) Raleigh NC
2000 No H and H Associates, Inc. DUAL-ICE®: A Non-Toxic, Non-Caustic Instant Cold Compress (abstract) Bena VA
2000 No Ho, Nancy W. Y.; Purdue University Genetic Engineering of Saccharomyces Yeasts for Effective Production of Ethanol and Other Green Chemicals from Renewable Cellulosic Biomass (abstract) West Lafayette IN
2000 No IBM Research Division, Almaden Research Center The Chemical Kinetics Simulator Program (abstract) San Jose CA
2000 No IonEdge Corporation Zero-Waste Dry Plating of Cadmium (abstract) Fort Collins CO
2000 No KM Limited Inc. The PIX Module Software: Combining Life Cycle Assessment with Activity-Based Costing to Reduce Global Environmental Impact and Sustain Industrial Profitability (abstract) Virginia Beach VA
2000 No Knipple, Douglas C.; Cornell University In Vivo Synthesis of Lepidopteran Pheromone Precursors in Saccharomyces Cereviseae: An Economical Process for the Production of Effective, Nontoxic, Environmentally Safe Insect Control Products (abstract) Geneva NY
2000 No Lubrizol Corporation, The Durable AMPS® Antimist Polymers for Aqueous Metalworking Fluids (abstract) Wickliffe OH
2000 No Lynd, Lee R.; Dartmouth College Overcoming the Recalcitrance of Cellulosic Biomass and Envisioning the Role of Biomass in a Sustainable World (abstract) Hanover NH
2000 No Mallinckrodt Baker Inc. Hydrogen Sulfide Elimination (abstract) Phillipsburg NJ
2000 No Micell Technologies The MICARE Liquid CO2 Dry Cleaning Process (abstract) Raleigh NC
2000 No Mobil Oil Corporation Membrane Separation in Solvent Lube Dewaxing (abstract) Fairfax VA
2000 No Morton International, Inc. ADVAFLEXTM Organic Stabilizer (abstract) Cincinnati OH
2000 Yes RevTech, Inc. EnvirogluvTM: A Technology for Decorating Glass and Ceramicware with Radiation-Curable, Environmentally Compliant Inks (summary) Edison NJ
2000 No Robbat, Jr., Albert; Tufts University Cheminformatics: Faster, Better, Cheaper Chemical Analysis Software (abstract) Medford MA
2000 No Robbat, Jr., Albert; Tufts University On-line Detection of Subsurface Pollutants by Thermal Extraction Cone Penetrometry-Thermal Desorption Gas Chromatography/Mass Spectrometry (abstract) Medford MA
2000 Yes Roche Colorado Corporation An Efficient Process for the Production of Cytovene, a Potent Antiviral Agent (summary) Boulder CO
2000 No Solvox Manufacturing Company Solvox Special 5501, an Anti-agglomerate and Stickies Neutralizer for the Paper Industry (abstract) Milwaukee WI
2000 No Tanko, James M.; Virginia Polytechnic Institute and State University Green Chemistry Through the Use of Supercritical Fluids and Free Radicals (abstract) Blacksburg VA
2000 No TechMatch, Incorporated N-Methylmorpholine-N-Oxide (NMMO): A Novel, Non-toxic, Reusable Solvent for Cellulose as Source Reduction in the Production of Textile Fibers (abstract) Saint Paul MN
2000 No U.S. Army, U.S. Army Edgewood Research, Development, and Engineering Center Filter Leak Test Using Ozone-Benign Substances (abstract) Aberdeen Proving Ground MD
2000 No U.S. Department of Energy, Argonne National Laboratory Clean Diesel Breakthrough: Simultaneous Decrease in Emissions of Both Particulates and Oxides of Nitrogen During Combustion (abstract) Argonne IL
2000 No U.S. Environmental Protection Agency, National Risk Management Research Laboratory Oxygenation of Hydrocarbons by Photocatalysis: A Green Alternative (abstract) Cincinnati OH
2000 Yes Wong, Chi-Huey; The Scripps Research Institute Enzymes in Large-Scale Organic Synthesis (summary) La Jolla CA
2001 No Anderson Chemical Company Total Impact Program - An Environmentally Preferable Program for Laundry (abstract) Litchfield MN
2001 No Aspen Systems, Inc. Genetic Enhancement of an Anti-Freeze Protein (abstract) Marlboro MA
2001 Yes Bayer Corporation; Bayer AG (Germany) BaypureTM CX (Sodium Iminodisuccinate): An Environmentally Friendly and Readily Biodegradable Chelating Agent (summary) Pittsburgh PA
2001 No Burlington Chemical Company, Inc. Development of a Practical Model and Process to Systematically Reduce the Environmental Impact of Chemicals Utilized by the Textile and Related Industries (abstract) Burlington NC
2001 No CDTech A New Process for Producing Dimethyl Carbonate (abstract) Pasadena TX
2001 No ChemNova Technologies, Inc. Chrome-free Single-step In-situ Phosphatizing Coatings: Anti-fingerprint Coatings on Galvanized Steel (abstract) DeKalb IL
2001 No Clearmate, Inc. ClearMate (abstract) Minneapolis MN
2001 No DeCopier Technologies, Inc. Advanced, Ecologically Safe De-inking Technology to Recover High Quality Pulp from Secondary Fibers/or Recyclable Waste (abstract) Lawrence MA
2001 No DuPont Crop Protection Biocatalytic Production of 5-Cyanovaleramide (abstract) Wilmington DE
2001 No Dynacs Engineering Co., Inc. Oxidizer Scrubber Project (abstract) Kennedy Space Center FL
2001 No E. I. DuPont de Nemours & Co., Inc. New Generation Adiponitrile Technology (abstract) Wilmington DE
2001 Yes EDEN Bioscience Corporation Messenger®: A Green Chemistry Revolution in Plant Production and Food Safety (summary) Bothell WA
2001 No Evergreen Nylon Recycling LLC Innovative Green Chemistry for Sustainable Manufacture of Caprolactam (abstract) Augusta GA
2001 No Huntsman Polyurethanes Equipment Flushing Agent for the Polyurethane Industry (abstract) West Deptford NJ
2001 No IBM Burlington (IBM Microelectronics Division) Solvent Waste Reduction Via An Acetic Acid Bowl Cleaning Process (abstract) Essex Junction VT
2001 Yes Li, Chao-Jun; Tulane University Quasi-Nature Catalysis: Developing Transition Metal Catalysis in Air and Water (summary) New Orleans LA
2001 No Mitzel, Thomas; Trinity College Formation of Ene-Diyne Molecules Under Indium Mediated Aqueous Barbier-Conditons (abstract) Hartford CT
2001 No Motorola Corporation; ULVAC Technologies, Inc. Eliminating Solvents from Silicon Wafer Manufacturing (abstract) Austin TX
2001 No Nextec Applications, Inc. Solventless Process for Improving Fabric Performance Properties (abstract) Vista CA
2001 No Northrup-Grumman Non-Destructive Testing of Corrosion Under Coatings (abstract) Bethpage NY
2001 Yes Novozymes North America, Inc. BioPreparationTM of Cotton Textiles: A Cost-Effective, Environmentally Compatible Preparation Process (summary) Franklinton NC
2001 Yes PPG Industries Yttrium as a Lead Substitute in Cationic Electrodeposition Coatings (summary) Pittsburgh PA
2001 No PPG Industries, Inc. Replacement of Asbestos in the Diaphragm Cell Process for Manufacture of Chlorine and Caustic Soda (abstract) Monroeville PA
2001 No QuesTek Innovations, LLC Computational Design of Corrosion Resistant Steels for Structural Applications In Aircraft (abstract) Evanston IL
2001 No Rochester Midland Corporation Development of an Effective, Coordinated Family of Safe, Green Cleaning and Maintenance Products (abstract) Rochester NY
2001 No U.S. Air Force, Air Force Research Laboratory Sol-Gel Technology for Low-VOC, Non-Chromated Adhesive & Sealant Applications (abstract) Wright Patterson AFB OH
2001 No U.S. Air Force, Air Force Research Laboratory Replacement Non-Toxic Sealants for Standard Chromated Sealants and Repair (abstract) Wright Patterson AFB OH
2001 No U.S. Army, TACOM-ARDEC - Picatinny Arsenal, NJ Primerless RTV Silicone Sealants/Adhesives (abstract) Picatinny Arsenal NJ
2001 No U.S. Army, U.S. Army Armament Research, Development, and Engineering Center Low VOC Chemical Agent Resistance Coatings (abstract) Picatinny Arsenal NJ
2001 No U.S. Army, U.S. Army Research Laboratory Non-Polluting Composites Remanufacturing and Repair for Military Applications (abstract) Aberdeen Proving Ground MD
2001 No U.S. Army, U.S. Army Research Laboratory - Aberdeen Proving Ground, MD Recycling Propellants in Non-Polluting Supercritical Fluids: Novel Computational Chemistry Models for Predicting Effective Solvents (abstract) Aberdeen Proving Ground MD
2001 No U.S. Department of Agriculture, National Center for Agricultural Utilization Research Environmentally Benign Synthesis of Monoglyceride Mixtures Coupled With Enrichment by Supercritical Fluid Fractionation (abstract) Peoria IL
2001 No U.S. Department of Agriculture, National Center for Agricultural Utilization Research Vegetable Oil Based Printing Inks and Their Environmental Advantages (abstract) Peoria IN
2001 No U.S. Environmental Protection Agency, National Risk Management Research Laboratory Paris II Solvent Design Software (abstract) Cincinnati OH
2002 No AEGEANS, Inc. Tasphox Water Treatment System (abstract) Harrisburg PA
2002 No Air Products and Chemicals, Inc. DEOXO-FLUORTM Reagent (abstract) Allentown PA
2002 No Applied CarboChemicals, Inc. Bioderived Succinic Acid as a Platform for a Carbohydrate Chemistry (abstract) Alto MI
2002 Yes Beckman, Eric J.; University of Pittsburgh Design of Non-Fluorous, Highly CO2-Soluble Materials (summary) Pittsburgh PA
2002 No Bristol-Myers Squibb Company The Process Greenness Scorecard: Design for Environmental Health and Safety Through Green Chemistry (abstract) New York NY
2002 Yes Cargill Dow LLC NatureWorksTM PLA Process (summary) Minnetonka MN
2002 Yes Chemical Specialties, Inc. (CSI) ACQ Preserve®: The Environmentally Advanced Wood Preservative (summary) Charlotte NC
2002 No ChitinWorks America; Payne, Gregory F.; University of Maryland Biotechnology Institute Industry-University-Government Partnership for Converting Regional Wastes into Chemical Products (abstract) College Park MD
2002 No Crisp, John N.; University of New Orleans Lakefront Campus An Innovative Replacement for Chromium for Aluminum Coatings (abstract) New Orleans LA
2002 No Donohue, Marc; Johns Hopkins University Supercritical Fluid Spray Application Process for Adhesives and Primers (abstract) Baltimore MD
2002 No Dordick, Jonathan S.; Rensselaer Polytrechnic Institute Development of Extraordinarily Active Biocatalysts for Highly Selective and Efficient Synthesis of Chemicals and Pharmaceuticals (abstract) Troy NY
2002 No DynynStyl Inc. EcoFuel - A Safe and Effective Canned Heat Alternative (abstract) Lake Worth FL
2002 No EarthShell Corporation EarthShell Packaging: Designed with the Environment in Mind (abstract) Lutherville MD
2002 No EPI Environmental Plastics Inc. Totally Degradable Plastic Additives (TDPATM) (abstract) Conroe TX
2002 No Evans Cooling Systems, Inc. The EVANS DE-TOXTM Process for the Detoxification of Ethylene Glycol (abstract) Sharon CT
2002 No ExxonMobil Chemical Development of Two Unique Processes for Manufacturing High-Purity Cyclopentane from Dicyclopentadiene (abstract) Baytown TX
2002 No Farris, Richard J.; University of Massachusetts Amherst Recycling of Cross-Linked Materials Via "High-Pressure High-Temperature Sintering": Redefining Thermosets (abstract) Amherst MA
2002 No GE Plastics Recovery and Beneficial Use of Sodium Nitrite from a Wastewater Stream (abstract) Mount Vernon IN
2002 No Henkel Surface Technologies Water-Based Synthesis and Purification of Mannich Base Modified Polyphenols (abstract) Madison Heights MI
2002 No Hill, Craig L.; Emory University; Weinstock, Ira A.; U.S. Department of Agriculture Forest Service, Forest Products Laboratory Effluent-Free and Selective Delignification Using Only Oxygen and Water (abstract) Atlanta GA
2002 No Hudlicky, Tomas; University of Florida Tandem Enzymatic-Electrochemical Methods for Green Manufacturing: Efficient Synthesis of Pharmaceuticals from Halogenated Aromatic Waste (abstract) Gainesville FL
2002 No Hybrid Plastics A Green Revolution with NanostructuredTM Chemicals (abstract) Fountain Valley CA
2002 No Itronics Metallurgical, Inc. Fertilizer From Photowaste (abstract) Reno NV
2002 No Madison Chemical Company Cadmium Replacement in Mechanical Coating (abstract) Madison IN
2002 No Mohan, Ram S.; Illinois Wesleyan University Environmentally Friendly Organic Synthesis Using Bismuth Compounds (abstract) Bloomington IL
2002 No OMNOVA Solutions Inc. Short Perfluoroalkyl Chain, Polymeric Fluorosurfactants as Wetting, Flow and Leveling Agents for Aqueous Coatings (abstract) Fairlawn OH
2002 No ONDEO Nalco Company Nalco ACT – Advanced Condensate Treatment for Boiler Systems (abstract) Napervile IL
2002 Yes Pfizer, Inc. Green Chemistry in the Redesign of the Sertraline Process (summary) New London CT
2002 No RADTECH International, North America Eliminating Air Pollution (VOC and HAP) at the Source through the Use of Ultraviolet and Electron Beam Polymerization (abstract) Bethesda MD
2002 Yes SC Fluids, Inc. SCORR – Supercritical CO2 Resist Remover (summary) Nashua NH
2002 No SePRO Corporation Integrated Methods for the Control of Aquatic Plants (IMCAPTM): Innovative Chemical and Precision Technologies (abstract) Carmel IN
2002 No Sunshine Makers, Inc. Crystal Simple Green® (abstract) Huntington Harbour CA
2002 No Tempyrox Company, Inc. World-wide Elimination or Reduction of Solvent and Chemical Cleaning of Laboratory Glassware Using Thermal Pyrolysis-oxidation Chemistry (abstract) Dallas TX
2002 No U.S. Army, U.S. Army Soldier and Biological Chemical Command Electronic and Photonic Polymers from Biocatalysis (abstract) Natick MA
2002 No U.S. Department of Agriculture, National Center for Agricultural Utilization Research Environmentally Benign Two-Step Synthesis of Fatty Alcohol Mixtures Using Supercritical Carbon Dioxide (SC-CO2) and SC-CO2/Hydrogen Mixtures (abstract) Peoria IL
2002 No U.S. Department of Agriculture, Southern Regional Research Center Environmentally Benign Antibacterial Agents (abstract) New Orleans LA
2002 No U.S. Department of Energy, Argonne National Laboratory Autothermal Reforming Catalyst for Fuel Cells (abstract) Argonne IL
2002 No U.S. Department of Energy, Argonne National Laboratory Electrometallurgical Treatment of Nuclear Waste (abstract) Argonne IL
2002 No U.S. Department of Energy, Argonne National Laboratory Electrorefining of Spent Nuclear Fuel (abstract) Argonne IL
2002 No U.S. Department of Energy, Los Alamos National Laboratory Environmentally Benign Enzyme Reactor for Polymer Synthesis (abstract) Los Alamos NM
2002 No U.S. Department of Energy, Pacific Northwest National Laboratory CSSX Process Demonstration (abstract) Richland WA
2002 No U.S. Navy, U.S. Naval Research Laboratory Patterned Channel-Constrained Process for Additive Electroless Metal Deposition (abstract) Washington DC
2002 No U.S. Polychemical Corporation DispersitTM: A Waterbased Oil Dispersant for Oil Spills in Salt and Fresh Water (abstract) Chestnut Ridge NY
2002 No Young, Ming-Wan; Xanthos, Marino; New Jersey Institute of Technology Melt Processing for Solvent-Less Manufacture of High Performance Dry Powder Coatings (abstract) Newark NJ
2003 No AC Products Enviromask - A Zero VOC Method to Aircraft Metal Forming (abstract) Placentia CA
2003 Yes AgraQuest, Inc. Serenade®: An Effective, Environmentally Friendly Biofungicide (summary) Davis CA
2003 No Allen, Christopher W.; University of Vermont; Peterson, Eric S.; Idaho National Engineering and Environmental Laboratory Environmentally Benign Preparation and Polymerization of Phosphazene Polymers (abstract) Burlington VT
2003 No Allen, Dianne; University of Massachusetts Amherst A Novel Additive System for Time-Controlled Degradation of Polypropylene (abstract) Jamaica Plain MA
2003 No Allen, Robert D.; IBM Almaden Research Center; Carbonell, Ruben; North Carolina State University; DeSimone, Joseph M.; University of North Carolina at Chapel Hill; Gleason, Karen K.; Massachusetts Institute of Technology; Ober, Christopher K.; Cornell University Environmentally Benign Lithography for Semiconductor Manufacturing (abstract) Chapel Hill NC
2003 No Buckman Laboratories International, Inc. Enzymes as an Alternative to Toxic Materials for Treatment of Slime Deposits in the Paper Industry (abstract) Memphis TN
2003 No Crivello, James V.; Rensselaer Polytechnic Institute Synthesis and Photopolymerization of Monomers Derived from Biorenewable Sources (abstract) Troy NY
2003 No Crompton Corporation ACRAMITETM - A New Selective and Safe Miticide (abstract) Greenwich CT
2003 No Deft, Inc. Zero VOC Protective Coatings for Aerospace Applications (abstract) Irvine CA
2003 Yes DuPont Microbial Production of 1,3-Propanediol (summary) Wilmington DE
2003 No Epmar Corporation Kemiko and Sta-Crete Low VOC Architectural Coating (abstract) Santa Fe Springs CA
2003 No Flexabar Corporation Aquagard Waterbase Antifouling Bottom Boat Paint (abstract) Lakewood NJ
2003 Yes Gross, Richard A.; Polytechnic University New Options for Mild and Selective Polymerizations Using Lipases (summary) Brooklyn NY
2003 No H2OK Engineering The Use of Vitamin C To Neutralize Oxidants Such as Chlorine in Drinking Water Which Is Often Discharged to the Environment (abstract) Mount Vernon WA
2003 No Hudlicky, Tomas; University of Florida Direct Biocatalytic Synthesis of Functionalized Catechols: A Short Route to Combretastatin A-1 (abstract) Gainesville FL
2003 No Kaplan, David L.; Tufts University Antioxidant-Functionalized Polymers (abstract) Medford MA
2003 No Kraus, George A.; Iowa State University Photoacylation and Photoalkylation of Quinones (abstract) Ames IA
2003 No Micro Interconnect Technology An Economically Advantaged, Green Process, for the Fabrication of Printed Circuit Boards (abstract) Bedford NH
2003 No Nicolaou, K.C.; University of California, San Diego Tandem Reactions, Cascade Sequences and Biomimetic Strategies in Chemical Synthesis (abstract) La Jolla CA
2003 No ONDEO Nalco Company STABREX® Microorganism Control Chemical: An Environmentally Sensible Chlorine Alternative for Industrial Water Treatment (abstract) Naperville IL
2003 No Periana, Roy Anthony; University of Southern California Low Temperature, Hydrocarbon Hydroxylation: The Key to Greener, Lower Cost Chemistry for Chemicals, Fuel and Power for the 21st Century (abstract) Los Angeles CA
2003 No Plug Power Inc. High CO Tolerant Polymer Electrolyte Membrane Fuel Cell Technology (abstract) Latham NY
2003 No RajanBabu, T. V.; Ohio State University Asymmetric Catalysis in Water: Hydroxyphosphine and Hydroxyphosphinite Ligands for Amino Acid Synthesis (abstract) Columbus OH
2003 Yes Shaw Industries, Inc. EcoWorxTM Carpet Tile: A Cradle-to-Cradle Product (summary) Dalton GA
2003 No Shi, Yian; Colorado State University An Environmentally Benign Asymmetric Epoxidation Me (abstract) Fort Collins CO
2003 No Smart Sonic Corporation 440-R SMT Detergent Hazardous Solvent Alternative for Printed Circuit Board Stencil Cleaning (abstract) Van Nuys CA
2003 Yes Süd-Chemie Inc. A Wastewater-Free Process for Synthesis of Solid Oxide Catalysts (summary) Louisville KY
2003 No Syngenta Crop Protection, Inc. Conversion of the Herbicide, Metolachlor, to S-Metolachlor in the U.S. Marketplace (abstract) Greensboro NC
2003 No Treyco Supply, Inc. Development of a Safer and More Effective Biodegradable Antimicrobial Cleaning Product (abstract) Wilson NC
2003 No U.S. Air Force, Air Force Research Laboratory, Wright Patterson Air Force Base New, Environmentally Protective Aircraft De-Icing Technology (abstract) Dayton OH
2003 No Wachs, Israel E.; Lehigh University Converting Pollution to Profits: Valuable Chemicals & Energy (abstract) Bethlehem PA
2003 No Xerox Corporation Xerographic Dry Ink Resin Manufacturing Hazard & Emission Reduction (abstract) Webster NY
2004 No Advanced Marine Technologies (AMT) BioProducts Corporation Reducing Nitrates in Buzzards Bay with the Production of Organic Gem® Fertilizer from New Bedford's Fish Processing Wastes (An SGNB Project) (abstract) South Dartmouth MA
2004 No BASF Corporation All-Acrylic Binders for Low VOC Architectural Coatings (abstract) Charlotte NC
2004 No Beckman, Eric J.; University of Pittsburgh In-Situ Generation of H2O2 in CO2 for Green Oxidations (abstract) Pittsburgh PA
2004 No Bergman, Robert G.; University of California at Berkeley Developing Highly Efficient C-H Activation of Hydrocarbons (abstract) Berkeley CA
2004 No Bose, Ajay K.; Stevens Institute of Technology Cost Effective Green Chemistry Approaches to Pharmaceuticals: Microwave Techniques & "Grindstone Chemistry" for Solventless Reactions and Less Pollution (abstract) Hoboken NJ
2004 Yes Bristol-Myers Squibb Company Development of a Green Synthesis for Taxol® Manufacture via Plant Cell Fermentation and Extraction (summary) New York NY
2004 Yes Buckman Laboratories International, Inc. Optimyze®: A New Enzyme Technology to Improve Paper Recycling (summary) Memphis TN
2004 No C.H. Thompson Co. Inc. Non Chromate Chemical Conversion Alternative Coating (abstract) Binghamton NY
2004 No Cargill, Inc. BioTrans® 1000 Soybean-Based Transformer Fluid (abstract) Wayzata MN
2004 No Dionysiou, Dionysios D.; University of Cincinnati Water Immiscible Room Temperature Ionic Liquids as Green Solvents for Extraction and In-Situ Photolytic Destruction of Environmental Organic Contaminants (abstract) Cincinnati OH
2004 No Dow Chemical Company, The n-Alkyl Propionate Ester Solvents (abstract) Midland MI
2004 Yes Eckert, Charles A.; Liotta, Charles L.; Georgia Institute of Technology Benign Tunable Solvents Coupling Reaction and Separation Processes (summary) Atlanta GA
2004 No Emisphere Technologies, Inc. Environmental Advantages Offered by Boric Acid Mediated Amidation Between a Carboxylic Acid and an Amine to Form a Carboxamide, a Basic Unit of Peptides and Proteins (abstract) Tarrytown NY
2004 Yes Engelhard Corporation Engelhard RightfitTM Organic Pigments: Environmental Impact, Performance, and Value (summary) Iselin NJ
2004 No Environmentally Sensitive Solutions, Inc. Utilization of Neutral Cleaners for Reducing Environmental and Health Impacts (abstract) Mequon WI
2004 No Ethyl Petroleum Additives Inc. Metal, Phenol and Ash-Free Antiwear Hydraulic Additive Providing Performance Previously Only Achieved by Use of Zinc Containing Additives (abstract) Richmond VA
2004 No Folia, Inc. Reactin SeriesTM AS Copolymers: Specialty Reactive Aspartic Acid Copolymers (abstract) Birmingham AL
2004 No Goodyear Tire & Rubber Company, The RPS Technology: Breakthrough Technology for Water-Based Paints, Coatings, Adhesives and Sealants (abstract) Akron OH
2004 No Janda, Kim D.; Lerner, Richard A.; The Scripps Research Institute Antibody Catalysis (abstract) La Jolla CA
2004 No Janssen Pharmaceutica Inc. ECONEA® 028: Designing and Developing a Metal-Free, Environmentally Safe, and Effective Antifoulant for Use Against Hard Fouling Marine Organisms (abstract) Titusville NJ
2004 Yes Jeneil Biosurfactant Company Rhamnolipid Biosurfactant: A Natural, Low-Toxicity Alternative to Synthetic Surfactants (summary) Saukville WI
2004 No Knockout Group, The "Knockout": A Dynamic Cleaning Experience, In a Colloidal Format, With Pollution Prevention Qualities (abstract) Chicago IL
2004 No LCP Tech Holdings LLC Development of Novel Liquid Crystal Polymers (abstract) Cincinnati OH
2004 No Li, Chao-Jun; Tulane University Developing Direct Catalytic Addition of Alkynes to Aldehydes and Imines in Water and under Solventless Conditions (abstract) New Orleans LA
2004 No PanTerra Technologies, Incorporated Reducing Domestic Petroleum Consumption by Twenty-five Percent (abstract) Goshen CT
2004 No Plug Power Inc. Demonstration of a Home Energy Station for Production of Electricity, Heat, and Hydrogen (abstract) Latham NY
2004 No Plug Power Inc. Zero-to-Landfill Fuel Cell Systems (abstract) Latham NY
2004 No PPG Architectural Finishes, Inc. Pure Performance "Zero" VOC Latex Coating (abstract) Pittsburgh PA
2004 No ProChemTech International, Inc. ElectroBrom Biocide System (abstract) Brockway PA
2004 No Ragauskas, A.J.; Georgia Institute of Technology Mill Designed Biobleaching Technologies (abstract) Atlanta GA
2004 No RD Chemical Company ChemBondTM EC An Alternate Printed Circuit Board Oxide Process (abstract) Mountain View CA
2004 No Sahinidis, Nikolaos V.; University of Illinois at Urbana A Systematic Methodology for the Design and Identification of Environmentally Benign Chemicals (abstract) Urbana IL
2004 No Sheth, Atul C.; University of Tennessee Space Institute From Waste-to-Energy: Catalytic Steam Gasification of Poultry Litter (abstract) Tullahoma TN
2004 No U.S. Department of Energy, Los Alamos National Laboratory Formamide Replacement in Genetic Sequencing (abstract) Los Alamos NM
2004 No Ulano Corporation Waste Minimization and Pollution Prevention Programs for the Production of Films & Chemicals in the Graphic Arts Industry (abstract) Brooklyn NY
2004 No Uniseal Inc. Elimination of Trichloroethylene, a Hazardous Air Pollutant (HAP), From A Production Process (abstract) Evansville IN
2004 No Zeller International Aqua FormTM, a water based, odorless, non-emissive, non-styrenated bonding/laminating resin for structural/advanced composites (abstract) Downsville NY
2005 No Afton Chemical Corporation Metal-, Phenol-, and Ash-Free Antiwear Hydraulic Additive: Providing Performance Previously Only Achieved by Use of Zinc-Containing Additives (abstract) Richmond VA
2005 No Air Products Polymers, L.P. Airflex® EF811 Vinyl Acetate Ethylene (VAE) Emulsion Polymer: A Binder for Environmentally Friendly, High-Performance, Cost-Effective Architectural Coatings (abstract) Allentown PA
2005 Yes Archer Daniels Midland Company Archer RCTM: A Nonvolatile, Reactive Coalescent for the Reduction of VOCs in Latex Paints (summary) Decatur IL
2005 Yes Archer Daniels Midland Company; Novozymes NovaLipidTM: Low Trans Fats and Oils Produced by Enzymatic Interesterification of Vegetable Oils Using Lipozyme® (summary) Decatur IL
2005 No Atmospheric Glow Technologies, Inc. Sterilization of Medical Devices with Atmospheric Plasma (abstract) KNOxville TN
2005 Yes BASF Corporation A UV-Curable, One-Component, Low-VOC Refinish Primer: Driving Eco-Efficiency Improvements (summary) Whitehouse OH
2005 No Beckman, Eric J.; University of Pittsburgh N-Vinyl Formamide: The "Greening" of a Green Replacement for Acrylamide (abstract) Pittsburgh PA
2005 No Bose, Ajay K.; Stevens Institute of Technology Unconventional High-Efficiency Green Synthesis (abstract) Hoboken NJ
2005 No Chemical Compliance Systems, Inc. Green Product and Munitions Compliance Analytical Systems (abstract) Lake Hopatcong NJ
2005 No Cholli, Ashok L.; University of Massachusetts Lowell Biocatalytically Synthesized High-Performance Novel Antioxidants for Materials (abstract) Lowell MA
2005 No Cleary Chemical Corporation ROACH TERMINALTM Insect Control: A Non-toxic Alternative that Prevents the Development of Pest Cockroach Populations (abstract) Dayton NJ
2005 No Crane & Company, Inc. Substitution with Carbon Dioxide Eliminates Major Use of Sulfuric Acid (abstract) Dalton MA
2005 No DeSimone, Joseph M.; University of North Carolina at Chapel Hill Surfactant-Free Supercritical Carbon Dioxide Fluoroolefin Polymerization Technology (abstract) Chapel Hill NC
2005 No Dow BioProducts Ltd. WOODSTALKTM Strawboard (abstract) Midland MI
2005 No Dow Chemical Company, The VORANOL* VORACTIV* Polyols for Flexible Polyurethane Foams (abstract) Midland MI
2005 No Ecolab Formula 1TM Laundry System (abstract) Inver Grove Heights MN
2005 No Eli Lilly and Company An Improved Approach to the Preparation of Duloxetine and Atomoxetine (abstract) Lafayette IN
2005 No GlaxoSmithKline Discovery and Development of a Green Process for Radafaxine (abstract) Philadelphia PA
2005 No Harris Labs Evapo-RustTM: Nonhazardous Rust Removal by Selective Chelation (abstract) Springdale AR
2005 No Highland Supply Corporation Using Chemistry and Engineering Technology to Reduce Volatile Organic Compound (VOC) Emissions and Eliminate Hazardous Process Waste in the Printing Industry (abstract) Highland IL
2005 No International Chemical Products, Inc. (ICP) PICKLEX®: An Environmentally Safe Metal Surface Preparation and Pretreatment Chemical (abstract) Huntsville AL
2005 No Lonza, Inc. EquinoxTM: A Greener Approach to Microbiological Control (abstract) Fair Lawn NJ
2005 No MacRitchie, Finlay; Kansas State University The Application of Ultrasound to Catalyze Reactions in Some Industrial Processes (abstract) Manhattan KS
2005 Yes Merck & Co. A Redesigned, Efficient Synthesis of Aprepitant, the Active Ingredient in Emend®: A New Therapy for Chemotherapy-Induced Emesis (summary) Rahway NJ
2005 Yes Metabolix, Inc. Producing Nature's Plastics Using Biotechnology (summary) Cambridge MA
2005 No METSS Corporation Environmentally Friendly Aircraft Deicing Fluid (abstract) Westerville OH
2005 No Microcide, Inc. Technology of Safe, Biodegradable, and Non-Polluting Products as Alternatives to Toxic Microbicidal Chemicals (abstract) Troy MI
2005 No Novartis Pharmaceuticals Corporation Development of Green and Practical Processes Utilizing Dialkyl Carbonates as Alkylating Reagents (abstract) East Hanover NJ
2005 No Pfizer Global Research and Development A Green Process for the Synthesis of Quinapril Hydrochloride (abstract) New London CT
2005 No Pfizer Global Research and Development Separation of Racemic Tetralone (abstract) New London CT
2005 No Pfizer Global Research and Development The Discovery and Development of an Environmentally Benign Commercial Route to Sildenafil Citrate (abstract) New London CT
2005 Yes Rogers, Robin D.; University of Alabama A Platform Strategy Using Ionic Liquids to Dissolve and Process Cellulose for Advanced New Materials (summary) Tuscaloosa AL
2005 No Rynex Holdings, Ltd. RYNEX® Dry Cleaning Solution (abstract) Woodbury NY
2005 No Severtson, Steven J.; University of Minnesota Research, Development, and Commercialization of Environmentally Benign Thermoplastic Pressure-Sensitive Adhesive Label Products (abstract) St. Paul MN
2005 No Stoller Enterprises, Inc. Stoller STIMULATE: A Natural Product for Improving Crop Plant Performance and Enhancing Pest Resistance (abstract) Houston TX
2005 No U.S. Army, U.S. Army Engineer Research and Development Center Environmentally Friendly Water Treatments for Control of Corrosion, Scale, and Bioactivity in Heating and Cooling Systems (abstract) Champaign IL
2005 No U.S. Army, U.S. Army Engineer Research and Development Center Mold Prevention through the Novel Use of In Situ Electrochemistry to Eliminate Water Seepage in Concrete Structures (abstract) Champaign IL
2005 No Westech Aerosol Corporation WT-HSC13: A High-Strength, Low-VOC Aerosol Adhesive (abstract) Port Orchard WA
2006 No ArchAngel Enterprises, LLC Stalosan F Microbial and Environmental Control for Use in Housing of All Animals (abstract) Cedar Rapids IA
2006 Yes Arkon Consultants and NuPro Technologies, Inc. Environmentally Safe Solvents and Reclamation in the Flexographic Printing Industry (summary) Winston Salem NC
2006 No Broin and Associates BFRACTM and BPXTM: Launching the Biorefining Revolution (abstract) Sioux Falls SD
2006 No Bunge North America; Novozymes North America, Inc. Enzymatic Degumming of Vegetable Oils: Reducing Environmental Impact and Improving Oil Yield (abstract) Saint Louis MO
2006 No Coastwide Laboratories Sustainable Earth® Cleaning Products Designed for Health and the Environment (abstract) Wilsonville OR
2006 Yes Codexis, Inc. Directed Evolution of Three Biocatalysts to Produce the Key Chiral Building Block for Atorvastatin, the Active Ingredient in Lipitor® (summary) Redwood City CA
2006 No Diwekar, Urmila; University of Illinois at Chicago Greener by Design: An Efficient, Multiobjective Framework Under Uncertainty (abstract) Chicago IL
2006 No Dow AgroSciences LLC Aminopyralid: Increasing Protection of Endangered Species through Improved Management of Non-Native Plants While Maximizing Land Use and Significantly Reducing Herbicide Volume and Application (abstract) Indianapolis IN
2006 No Dow AgroSciences LLC; U.S. Department of Agriculture, Agricultural Research Service GF-120TM NF NaturalyteTM Fruit Fly Bait (abstract) Indianapolis IN
2006 No DuPont Company Bioderived Solvents, Surfactants, Fuel Additives, and Monomers (abstract) Wilmington DE
2006 No DuPont Company New Asymmetric Hydroxylation Technology for the Commercial Manufacture of Indoxacarb (abstract) Wilmington DE
2006 No Duraflame, Inc. Duraflame® All-Natural Manufactured Firelog (abstract) Stockton CA
2006 No FluidPhase Technologies Inc. A Preproduction System for Re-Refining Used Oil Using Closed-Loop, Patented, Atomization Technology (abstract) Pittsburgh PA
2006 No Foster-Miller, Inc. Environmentally Advantaged Formulations for Aircraft Ice Control (abstract) Waltham MA
2006 No Garcia-Garibay, Miguel A.; University of California, Los Angeles Solvent-Free, Crystal-to-Crystal Photochemical Reactions: The Synthesis of Adjacent Stereogenic Quaternary Centers (abstract) Los Angeles CA
2006 No GE Plastics Flexible NORYL* Resins for Wire Coating (abstract) Selkirk NY
2006 No Go-Tec, Inc. Acetylene: A Viable Fuel Alternative for the Internal Combustion Engine (abstract) Columbia MO
2006 No GreenEarth® Cleaning, LLC GreenEarth® Cleaning, Dry Cleaning with Silicone Solvent (abstract) Kansas City MO
2006 No Halliburton Energy Services ACCOLADETM Synthetic-Based Drilling Fluid System (abstract) Houston TX
2006 No HALOX New Water-Based Organic Corrosion Inhibitor (abstract) Hammond IN
2006 No Innovative Formulation Company Ecological Paint Antimicrobial Clear Coat (abstract) Tucson AZ
2006 No Interface Fabrics Closing the Loop with "Benign by Design" Biobased Fabrics and Backings (abstract) Grand Rapids MI
2006 No iSoy Technologies Corporation Biocatalytic Production of Biobased Personal Care Products (abstract) Trout Valley IL
2006 No Johnson Polymer, LLC JONCRYL® FLX 5000: A High-Performance, Water-Based Polymer to Facilitate the Conversion from Solvent- to Water-Based Inks in Surface Film Flexible Packaging Printing (abstract) Sturtevant WI
2006 No JohnsonDiversey, Inc. A Novel Cleaning System Using Less Toxic, Safer Chemicals (abstract) Sturtevant WI
2006 No LANXESS Corporation Picaridin: A Safe, Effective, and Environmentally Friendly Insect Repellent that People Will Use (abstract) Pittsburgh PA
2006 Yes Merck & Co., Inc. Novel Green Synthesis for β-Amino Acids Produces the Active Ingredient in JanuviaTM (summary) Rahway NJ
2006 No MLI Associates Environmentally Benign Deicing/Anti-Icing Agents (abstract) Shoreham NY
2006 No Montana Polysaccharides Corporation Multipurpose Exopolymer as a Raw Material (abstract) Rock Hill SC
2006 No Netravali, Anil N.; Cornell University Green Composites: Environment-Friendly and Fully Sustainable (abstract) Ithaca NY
2006 No Nike, Inc. Development of Nike Brand Footwear Outsole Rubber as Environmentally Preferred Material (abstract) Beaverton OR
2006 No Pfizer Global Research and Development Green Chemistry in the Redesign of the Celecoxib Process (abstract) New London CT
2006 No PostSaver USA PostSaver® (abstract) Memphis TN
2006 No Praxair, Inc. Oxygen-Enhanced Combustion for NOx Control (abstract) Tonawanda NY
2006 No Recovery Systems Inc. Innovative Process for Treatment of Hog Waste and Production of Saleable Products from This Waste (abstract) Wilmington NC
2006 No Rhodia Inc. Guar-Based Chemistry Advances Targeted Performance of Crop Sprays by Reducing Drift and Improving Retention (abstract) Cranbury NJ
2006 No Rohm and Haas Company; Johns Manville Invention and Commercialization of Environmentally Smart Thermosetting Binders (abstract) Philadelphia PA
2006 No Rust-Oleum Corporation Zero-VOC, Zero-HAP, No-Odor Industrial Coatings (abstract) Vernon Hills IL
2006 Yes S.C. Johnson & Son, Inc. GreenlistTM Process to Reformulate Consumer Products (summary) Racine WI
2006 No Separation Technologies LLC Beneficiation and Use of Coal Combustion Fly Ash: A Major Success in Reducing Solid Waste and Increasing Supplies of Construction Materials While Reducing Greenhouse Gas Emissions (abstract) Needham MA
2006 Yes Suppes, Galen J.; University of Missouri-Columbia Biobased Propylene Glycol and Monomers from Natural Glycerin (summary) Columbia MO
2006 No Syngenta Mesotrione and Callisto® Plant Technology (abstract) Washington DC
2006 No Tester, Jefferson W.; Massachusetts Institute of Technology Replacing Organic Solvents and Homogeneous Catalysts with Water and Carbon Dioxide (abstract) Cambridge MA
2006 No U.S. Department of Energy, Pacific Northwest National Laboratory Self-Assembled Monolayers on Mesoporous Silica Technology: A Green Alternative Synthesis of a Novel Adsorbent for Mercury Source Reduction (abstract) Richland WA
2006 No Ventana Research Corporation Development of High Performance, Environmentally Benign Hard Disk Drive Polishing Fluids and Corrosion Inhibitors (abstract) South Tucson AZ
2006 No W.F. Taylor Co., Inc. Meta-TecTM Low-VOC, One-Component, Cross-Linking Adhesive: Innovative Science–Applied Technology (abstract) Dalton GA
2006 No Warner, John C.; University of Massachusetts Lowell Bioinspired Thymine-Based Photopolymers: A Green Chemistry Platform for Innovation, Research, Education, and Outreach (abstract) Lowell MA
2006 No Xerox Corporation Xerox’s Emulsion Aggregation Toner Technology (abstract) Webster NY
2006 No ZIVATECH Corporation High-Efficiency Olefin to Polyolefin Process with Toxic Solvent Elimination (abstract) North Hills CA
2006 No ZIVATECH Corporation New Biomass Catalytic Reforming Process for Solid Oxide Fuel Cell Power Generation (abstract) North Hills CA
2007 No 3M Office Supplies Division Laboratory Development of Water-Based Materials for Post-it® Super Sticky Notes (abstract) St. Paul MN
2007 No Advanced BioCatalytics Corporation Uncoupling Biochemical Processes for Enhanced Biological Efficiency (abstract) Irvine CA
2007 No Amerikal Products Corporation Genesis® BRIGL Wash (abstract) Waukegan IL
2007 No Arch Treatment Technologies, Inc. Wolman® AG Metal-Free Wood Preservative (abstract) Smyrna GA
2007 No Arkema Inc. Green Chemistry in the Manufacture of Thioglycolic Acid (abstract) Philadelphia PA
2007 No Aspen Technology, Inc. Correlating and Predicting Drug Molecule Solubility with a Nonrandom, Two-Liquid Segment Activity Coefficient Model (abstract) Cambridge MA
2007 No Barricade International, Inc. Environmentally and Toxicologically Safe Firefighting Gel (abstract) Hobe Sound FL
2007 No BASF Corporation A Non-HAP (Hazardous Air Pollutant) Coating for Extruded Aluminum (abstract) Southfield MI
2007 No Beaulieu Group, LLC NexterraTM Carpet: Modified PET Carpet Backing (abstract) Adairsville GA
2007 No Benchmark Performance Group, Inc. GreensKeeper® Polymer Slurries for Oil and Gas Well Stimulation (abstract) Houston TX
2007 No Bristol-Myers Squibb Company Irbesartan (Avapro®) Greenness Project (abstract) New York NY
2007 No Buckman Laboratories International, Inc. Enzymes to Reduce Energy Use and Increase Recycling of Paper (abstract) Memphis TN
2007 Yes Cargill, Incorporated BiOHTM Polyols (summary) Wayzata MN
2007 No Century Industrial Coatings Inc. NuloTM Technology: HAP-Free, Low-VOC, Water-Based, Air-Dry Coatings (abstract) Jacksonville TX
2007 No Changing World Technologies, Inc. Waste to Renewable Diesel (abstract) West Hempstead NY
2007 No Cholli, Ashok L.; University of Massachusetts Lowell High Performance Macromolecular Antioxidants for Materials: A Green Chemistry Approach (abstract) Lowell MA
2007 No Crosslink Corrosion-Resistance without Chromium: On-Demand Release of Environmentally Safe, Non-Chromium Corrosion Inhibitors from Electroactive Polymer Coatings (abstract) Fenton MO
2007 No Dasgupta, Purnendu K.; The University of Texas at Arlington A Green Analyzer for Arsenic in Drinking Water (abstract) Arlington TX
2007 No Eastman Chemical Company Optifilm Enhancer 400 – A Nonvolatile Coalescent for Formulating High-Performance, Reduced-VOC Architectural Coatings (abstract) Kingsport TN
2007 No Ecology Coatings Green Chemistry for Industrial Coatings (abstract) Akron OH
2007 No ECOSIL Technologies LLC New One-Step, Chromate-Free Anticorrosion Coatings for Aluminum Alloys and HDG Steel (abstract) Fairfield OH
2007 No Emerson & Cuming Tin- and Copper-Compatible Conductive Adhesive for Lead-Free Electronic Circuit Assembly (abstract) Billerica MA
2007 No Environmentally Sensitive Solutions, Inc. Liquid Seal and Nonhazardous Cleaner Eliminate Odor, Health, and Maintenance Problems Stifling the Acceptance and Implementation of Waterless Urinals (abstract) Mequon WI
2007 No Exelus, Inc. ExSact – A "Green" Gasoline Technology (abstract) Livingston NJ
2007 No Exelus, Inc. ExSyM – The Next Generation of Styrene Monomer Technology (abstract) Livingston NJ
2007 No Fungi Perfecti, LLC Mycopesticides and Mycoattractants (abstract) Olympia WA
2007 No Georgia-Pacific Chemicals, LLC; Tao, Daniel, University of Kentucky Georgia-Pacific Mining Reagents That Improve Recovery, Reduce Wastes, and Conserve Water and Other Natural Resources (abstract) Decatur GA
2007 No Georgia-Pacific Corporation Nitamin Steady Delivery Fertilizers for Improved Nitrogen Efficiency in Crops (abstract) Decatur GA
2007 No Green Blue (Green Blue Institute) CleanGredientsTM: Systems-Based Information Technology for Green Chemistry (abstract) Charlottesville VA
2007 Yes Headwaters Technology Innovation Direct Synthesis of Hydrogen Peroxide by Selective Nanocatalyst Technology (summary) Lawrenceville NJ
2007 No Hutchison, James E.; University of Oregon Greener Production of Functionalized Nanoparticles (abstract) Eugene OR
2007 No IPAX Cleanogel, Inc. The Use of Green Unikleen in Oil Spill Clean-Up, Both on Land and in Water (abstract) Detroit MI
2007 Yes Krische, Michael J.; University of Texas at Austin Hydrogen-Mediated Carbon–Carbon Bond Formation (summary) Austin TX
2007 No LATA Group, The New Green Technology for Eliminating Hydrogen Sulfide in Aqueous Systems, Especially Petroleum Industry Systems (abstract) Ochelata OK
2007 Yes Li, Kaichang; Oregon State University; Columbia Forest Products; Hercules Incorporated Development and Commercial Application of Environmentally Friendly Adhesives for Wood Composites (summary) Corvallis OR
2007 No Maffia, Gennaro J.; Widener University Application of Collagen Nanofibrils in Green Processing and Synthesis (abstract) Chester PA
2007 No McCullough, Richard D.; Carnegie Mellon University Regioregular Polythiophenes as a Platform for Organic Photovoltaic Technology (abstract) Pittsburgh PA
2007 No Merck & Co., Inc. A New, Highly Efficient, Environmentally Responsible Synthesis of Laropiprant (MK-0524) (abstract) Rahway NJ
2007 No Merck & Co., Inc. Kilogram-Scale Purification of Pharmaceutical Candidates and Intermediates Using Preparative Supercritical Fluid Chromatography (abstract) Rahway NJ
2007 No Momentive Performance Materials Inc. Commercialization of NXT Z®: An Ethanol-Free, Low-VOC, High-Performance Silane for Silica Tires (abstract) Tarrytown NY
2007 No Momentive Performance Materials Inc. Novel Superspreading Siliconized Surfactants (abstract) Tarrytown NY
2007 No MYCELX Technologies Corp. Novel Device for Removing Mercury from Produced Water and Vapor Streams (abstract) Gainesville GA
2007 No Nalco Company A New Corrosion Inhibitor Reduces the Environmental Impact of Industrially Treated Water (abstract) Naperville IL
2007 No Nitrate Elimination Co., Inc., The Greener Chemistry for Nitrate Analysis: Enzymatic Reduction Method (abstract) Lake Linden MI
2007 Yes NovaSterilis, Inc. Environmentally Benign Medical Sterilization Using Supercritical Carbon Dioxide (summary) Lansing NY
2007 No Osmose, Inc. MicroProTM Technology in Wood Preservation (abstract) Griffin GA
2007 No Pantheon Chemical PreKote® Surface Pretreatment: Replacing Hexavalent Chromium with an Environmentally Safe Solution (abstract) Phoenix AZ
2007 No Pirrung, Michael C.; University of California, Riverside Environmentally Friendly Isonitrile-Based Syntheses (abstract) Riverside CA
2007 No Procter & Gamble Company, The Tide Coldwater®: Energy Conservation through Residential Laundering Innovation and Commercialization (abstract) Cincinnati OH
2007 No Schultz, Tor P.; Nicholas, Darrel D.; Mississippi State University Enhancing the Efficacy of Totally Organic Wood Preservatives with Low-Cost, Benign Additives (abstract) Mississippi State MS
2007 No Severn Trent Services Iron Oxide for Arsenic Removal from Drinking Water (abstract) Fort Washington PA
2007 No Soloshonok, Vadim A.; Ueki, Hisanori; The University of Oklahoma Biomimetic Reductive Processes (abstract) Norman OK
2007 No Stoller Enterprises, Inc. Alternative to Methyl Bromide to Overcome Nematode Damage to Crops and Concomitantly Enhance Yield, Crop Quality, and Abiotic and Biotic Tolerance (abstract) Houston TX
2007 No Super Trap Inc. GEL-COR®: A New, Environmentally Compatible, Bullet-Trapping Medium for Small-Arms Firing Ranges (abstract) Corona CA
2007 No U.S. Army, U.S. Army Edgewood Chemical Biological Center Enzyme-Based Technology for Decontaminating Toxic Organophosphorus Compounds (abstract) Aberdeen Proving Ground MD
2007 No U.S. Department of Energy, Argonne National Laboratory Solventless Process for Making Tackifiers and Adhesives (abstract) Washington DC
2007 No U.S. Department of Energy, Los Alamos National Laboratory Green Primaries: Environmentally Friendly, Sensitive Explosives (abstract) Los Alamos NM
2007 No U.S. Department of Energy, Los Alamos National Laboratory Ultrapure Carbon and Carbon–Nitride Nanomaterials Derived from Simple Pyrolyses of Nearly Chock-Full Nitrogen Compounds (abstract) Los Alamos NM
2007 No van Ooij, Wim J.; University of Cincinnati Novel, One-Step, Chromate-Free Coatings Containing Anticorrosion Pigments to Replace Chromate Pretreatment and Pigments (abstract) Cincinnati OH
2007 No Velocys Inc. Olefins by High-Intensity Oxidation (abstract) Plain City OH
2007 No Zhang, Xumu; The Pennsylvania State University Practical Asymmetric Catalytic Hydrogenation (abstract) University Park PA
2007 No Zhao, Huimin; van der Donk, Wilfred A.; Metcalf, William W.; University of Illinois A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology for Industrial Biocatalysis (abstract) Urbana IL
2008 No Adventus Group, The EHCTM for a Greener Groundwater Treatment Technology (abstract) Freeport IL
2008 No Arkema Inc. Replacement of Perfluorinated Alkyl Surfactants with Nonfluorinated Surfactants in Polymer Manufacturing (abstract) King of Prussia PA
2008 No Ashland Inc. GEOSET NEO®: Low Emission Technology for the Metal Casting Industry (abstract) Dublin OH
2008 No Ashland Inc. Reducing the Environmental, Health and Safety Impact of Cooling Water Treatment Programs (abstract) Boonton NJ
2008 No Ashland Inc. Solventless, Low-Toxicity, Thermosetting Oligomers that Require Only Low Energy to Cure (abstract) Dublin OH
2008 No ATK Lake City Ammunition Division P4rimerTM: A Non-Toxic, Heavy-Metal-Free Primer Fueled by Red Phosphorus for Small Arms Cartridges (abstract) Independence MO
2008 No Augustine, Robert L.; Seton Hall University; NutraSweet Corporation, The Bromine Free, TEMPO Based Catalyst System for the Oxidation of Alcohols (abstract) South Orange NJ
2008 Yes Battelle Development and Commercialization of Biobased Toners (summary) Columbus OH
2008 No ChK group, Inc. Nanophase Mn(VII) Oxide: Synthesis using Green Technology and Applications (abstract) Plano TX
2008 No Codexis, Inc. Greening Montelukast Manufacture: Replacing a Stoichiometric Chiral Boron Reagent with a Green-by-Design, Economical Biocatalytic Reduction Enabled by Directed Evolution (abstract) Redwood City CA
2008 No Cutting Edge Formulations, Inc. Nature's Avenger® Organic Herbicide: A Fast-Acting, Highly Effective, Organic Alternative to Synthetic and Natural Herbicides (abstract) Buford GA
2008 No Cytec Industries Inc. Cytec Innovation Management System: Sustainable Development of New Products (abstract) West Paterson NJ
2008 No Cytec Industries Inc. Revolutionizing Energy-Curing Resins for Food Packaging Applications (abstract) West Paterson NJ
2008 Yes Dow AgroSciences Spinetoram: Enhancing a Natural Product for Insect Control (summary) Indianapolis IN
2008 No Dow Chemical Company Novel Process for Producing Polyols Based on Natural Oils (abstract) Midland MI
2008 No Dow Corning Corporation Water and Energy Conservation in Denim Finishing (abstract) Midland MI
2008 No DuraBan International, Inc. Environmentally Friendly Antimicrobial Surface Treatment (abstract) Buffalo MN
2008 No Eastman Chemical Company IntegRex Technology (abstract) Kingsport TN
2008 No Eli Lilly and Company A Practical and Green Chemical Strategy for the Manufacture of Neurokinin 1 Antagonist, LY686017 (abstract) Indianapolis IN
2008 No EverNu Technology, LLC Enabling Technology for Methacrylic Acid Production using Isobutane as the Feedstock (abstract) Maple Glen PA
2008 No EverTech LLC Everdex-Enhanced Alowood (abstract) Ferndale WA
2008 No G3 Technology Innovations, LLC Surface Functionalized Nanomaterials: Significantly Reducing Fluorochemicals in Consumer Items (abstract) Pittsford NY
2008 No GlaxoSmithKline GlaxoSmithKline's Eco-Design ToolkitTM (abstract) Philadelphia PA
2008 No Hach Company Arsenic-Free SPADNS Chemistry for Fluoride Analysis in Water (abstract) Loveland CO
2008 No Huntsman Corporation G2 Catalyst for New and Improved SURFONIC® Non-Ionic Surfactants (abstract) The Woodlands TX
2008 No Inland Environmental Resources, Inc. Environmentally Friendly Antacid Formulations for Wastewater Treatment (abstract) Pasco WA
2008 No International Polyol Chemicals, Inc. (IPCI) Production of Diverse Industrial Glycols from Renewable Six and Five-Carbon Sugars and Glycerin, the Byproduct of Biodiesel Manufacture (abstract) Ephrata WA
2008 No Jiang, Shaoyi; University of Washington Development of Environmentally Benign Nonfouling Materials and Coatings for Marine Applications (abstract) Seattle WA
2008 No Johnson & Johnson Application of Green Chemistry Principles in the Scale-Up of the Darunavir Process (abstract) New Brunswick NJ
2008 No Leadbeater, Nicholas E.; University of Connecticut Microwave Heating as an Enabling Tool for Greener Synthesis (abstract) Storrs CT
2008 No Lubrizol Corporation, The Novel Green Chemistries Extend the Useful Life of Automobile Catalytic Converters and Reduce Exhaust Gaseous Emissions (abstract) Wickliffe OH
2008 Yes Maleczka, Robert E., Jr.; Milton R. Smith, III; Michigan State University Green Chemistry for Preparing Boronic Esters (summary) East Lansing MI
2008 No MIOX Corporation On-Site Generation of Mixed Oxidants as a Safe, Green Alternative to Chlorine Gas and Concentrated Bulk Bleach (abstract) Albuquerque NM
2008 Yes Nalco Company 3D TRASAR® Technology (summary) Naperville IL
2008 No NCH Corporation System for Bioremediation of Effluents (abstract) Irving TX
2008 No Organic Recovery, LLC. Biochemical Hydrolyzation of Organics in Food Wastes into a Liquid Fertilizer and Soil Amendment (abstract) Pompano Beach FL
2008 No Peng, Xiaogang; University of Arkansas; Nanomaterials and Nanofabrication Laboratories, LLC (NN-Labs) Doped Semiconductor Nanocrystals as Heavy-Metal-Free Quantum Dots (abstract) Fayetteville AR
2008 No Pfizer, Inc. Convergent Green Synthesis of Linezolid (ZyvoxTM), an Oxazolidinone Antibacterial Agent (abstract) Kalamazoo MI
2008 No Pyrotechnique by Grucci, Inc. Perchlorate-Free Pyrotechnic Composition for Military Training Munitions (abstract) Brookhaven NY
2008 No Ragauskas, Arthur J.; Georgia Institute of Technology Developing Lignocellulosic Biorefineries (abstract) Atlanta GA
2008 No Rhein Chemie Corporation Additives for Optimizing Renewable Resources in the Production of Polyurethane Systems and Plastics (abstract) Chardon OH
2008 No Roche Carolina Inc. Scalable Non-Aqueous Process to Prepare Water-Soluble Aminodiol (abstract) Florence SC
2008 No Sepracor, Inc. Adventures in Green Chemistry (abstract) Marlborough MA
2008 Yes SiGNa Chemistry, Inc. New Stabilized Alkali Metals for Safer, Sustainable Syntheses (summary) New York NY
2008 No Specialty Fertilizer Products Biodegradable, Water-Soluble Anionic Polymers, Prepared in an Environmentally Benign Process, Enhance the Efficiency of Phosphorus Use by Plants (abstract) Belton MO
2008 No Tennant Company ech2oTM - Electrically Charged Water (abstract) Minneapolis MN
2008 No Thames, S. F.; Rawlins, J. W.; The University of Southern Mississippi Vegetable Oil Based Macromonomers in Emulsion Polymers for High-Performance, Zero-VOC Architectural Coatings (abstract) Hattiesburg MS
2008 No Thermo Fisher Scientific Green pH Electrodes (abstract) Beverly MA
2008 No Torch Technologies LLC Manufactured Firelogs Based on Whole Timber (abstract) Ferndale WA
2008 No TyraTech, Inc. Greening Insecticides and Parasiticides (abstract) San Francisco CA
2008 No Wildeman, Thomas; Colorado School of Mines Passive Treatment of Metal-Contaminated Water (abstract) Golden CO
2009 No 3MTM Reformulation of 3MTM Neutral Cleaner and 3MTM General Purpose Cleaner for the 3MTM Twist 'n FillTM Chemical Management System Reduces Air Pollution and Employee Health Hazards (abstract) St. Paul MN
2009 No American Ordnance LLC Inert Filler TB-1 (abstract) Middletown IA
2009 No Ashland Hercules Water Technologies Pulp Mill Defoamers Based on Vegetable Oil (abstract) Wilmington DE
2009 No Ashland Inc. Water-Based Refractory Coatings with Wet/Dry Color Change Indication (abstract) Dublin OH
2009 No Bayer MaterialScience LLC AURA® Infusion Technology: A Green Method to Incorporate Color and Performance Additives (abstract) Pittsburgh PA
2009 Yes CEM Corporation Innovative Analyzer Tags Proteins for Fast, Accurate Results without Hazardous Chemicals or High Temperatures (summary and podcast) Matthews NC
2009 No Clorox Company, The GreenWorksTM Natural Cleaners from the Makers of Clorox: Home Cleaning Products (abstract) Pleasanton CA
2009 No Codexis, Inc. Greening Atorvastatin Manufacture: Replacing a Wasteful, Cryogenic Borohydride Reduction with a Green-by-Design, More Economical Biocatalytic Reduction for a Higher Quality Product (abstract) Redwood City CA
2009 No Davis, James Hillard Jr.; University of South Alabama Liquid but Nonvolatile Sulfonic Acids and Amines: Greener Chemicals for Greening Processes (abstract) Mobile AL
2009 No Doty Energy Recycling Carbon Dioxide into Carbon-Neutral Liquid Fuels (abstract) Columbia SC
2009 No Dow Chemical Company, The Glycerin to Epichlorohydrin Process: How Green is my Epichlorohydrin? (abstract) Freeport TX
2009 Yes Eastman Chemical Company A Solvent-Free Biocatalytic Process for Cosmetic and Personal Care Ingredients (summary and podcast) Kingsport TN
2009 No Ecolab Inc. Wash 'n WalkTM Floor Care System (abstract) Inver Grove Heights MN
2009 No Eli Lilly and Company New Manufacturing Route for Arzoxifene Hydrochloride (abstract) Indianapolis IN
2009 No FlyAshDirect Ltd.; Cognis Corporation Carbon BlockerTM Fly Ash Conditioning Treatment (abstract) Cincinnati OH
2009 No French Creek Software, Inc Chemical Treatment Modeling and Optimization Software: The French Creek Software Calculation Engine (abstract) Kimberton PA
2009 No Gill, Raminderjit (Sonam); Alvarez, Jessica; University of California, Santa Barbara The University of California, Santa Barbara Green Chemistry Initiative (abstract) Santa Barbara CA
2009 No GVD Corporation Novel Solvent-Free Fluoropolymer Coating Process (abstract) Cambridge MA
2009 No Gyberg, Arlin E., Augsburg College; SarTec Corporation The Mcgyan Process: A Green Synthetic Route for Biodiesel Production (abstract) Anoka MN
2009 No Henkel Corporation Aquence® Autodeposition Coating: The Smart Coating Solution (abstract) Madison Heights MI
2009 No Henkel Corporation Bonderite® TecTalis: Next-Generation Coating (abstract) Madison Heights MI
2009 No Huntsman Advanced Materials Corporation Manufacturing More Efficient Fuel Cells to Reduce Carbon Dioxide Emissions (abstract) The Woodlands TX
2009 No Ingenuity IEQ, Inc. Green Chemistry for Energy Conservation and Indoor Environmental Quality (abstract) Midland MI
2009 Yes Matyjaszewski, Krzysztof; Carnegie Mellon University Atom Transfer Radical Polymerization: Low-impact Polymerization Using a Copper Catalyst and Environmentally Friendly Reducing Agents (summary and podcast) Pittsburgh PA
2009 No Merck & Co., Inc. Green Chemistry in Action: A Remarkably Efficient and Sustainable Synthesis of the HIV Integrase Inhibitor, RaltegravirTM (abstract) Rahway NJ
2009 No Method Products Method Smarty Dish for Fish: An Environmentally Responsible and Effective Cleaning Solution: No Phosphates, Acrylates, or Ethylenediaminetetraacetic Acid (abstract) San Francisco CA
2009 No Milliken & Company TractionBack®: Alternative Green Adhesives Solutions for Textile Composites Used in Commercial Buildings (abstract) Spartanburg SC
2009 No Narayan, Ramani; Michigan State University: KTM Industries, Inc. Biodegradable, Chemically Modified Starch Polymers for Protective Foam Packaging and Insulation Applications (abstract) East Lansing MI
2009 No Ozone International LLC Cleaning and Disinfecting with Ozone: Making Green Chemistry with WhiteWaterTM Ozone (abstract) Bainbridge Island WA
2009 No Plasmatreat North America Inc.; Ford Motor Company OpenairTM Plasma Surface Treatment: Reducing Emissions of Volatile Organic Compounds and Improving Environmentally Sensitive Paint Processes (abstract) Dearborn MI
2009 No PPG Industries, Inc. Green LogicTM: Chitosan-Enhanced Paint Detackifier (abstract) Troy MI
2009 No PPG Industries, Inc. ZircobondTM Pretreatment (abstract) Troy MI
2009 Yes Procter & Gamble Company, the; Cook Composites and Polymers Company Chempol® MPS Resins and Sefose® Sucrose Esters Enable High-Performance Low-VOC Alkyd Paints and Coatings (summary and podcast) Cincinnati OH
2009 No SABIC Innovative Plastics Chemical Conversion of Post-Consumer Recycled Polyethylene Terephthalate Waste into Sustainable Valox iQTM and Xenoy iQTM Engineering Thermoplastic Products (abstract) Mount Vernon IN
2009 No Schweitzer, Linda; Oakland University; Reed, Robert; University of Missouri; Earth Science Laboratories, Inc. EarthTec®: Green Water Treatment (abstract) Rochester MI
2009 No Sherwin-Williams Company, The High-Solids Hybrid Sucrose Ester Polymer Technology (abstract) Cleveland OH
2009 No STERIS Corporation; Virox Technologies An Alternative to Aldehyde-Based Liquid Chemical Sterilants and High-Level Disinfectants for Reprocessing Heat-Sensitive, Semi-Critical Medical Instruments (abstract) Mentor OH
2009 No TDA Research, Inc.; Cytec Industries Inc. Replacement for Solvent-Based, Chromate-Containing Primer (abstract) Golden CO
2009 No U.S. Department of Energy, Argonne National Laboratory Diesel DeNOx Catalyst (abstract) Argonne IL
2009 No U.S. Department of Energy, Argonne National Laboratory Resin Wafer Technology (abstract) Argonne IL
2009 No VeruTEK Technologies, Inc. Green Synthesis of Nanometal Catalysts and Plant Surfactant-Based, In Situ Chemical Oxidation for Sustainable Treatment and Remediation (abstract) Bloomfield CT
2009 Yes Virent Energy Systems, Inc. BioForming® Process: Catalytic Conversion of Plant Sugars into Liquid Hydrocarbon Fuels (summary and podcast) Madison WI
2009 No Water Conservation Technology International, Inc. Sustainable, Natural Green Chemistry for Cooling Water Treatment (abstract) Temecula CA
2009 No Wender, Paul A.; Stanford University Green Chemistry through Function-Oriented Synthesis, Step Economy, and Ideal Synthesis (abstract) Stanford CA
2009 No ZeaChem Inc. Cellulose-Based Fuels and Intermediate Chemicals (abstract) Lakewood CO
2009 No Zep Inc. Renewable-Resource Industrial Products (abstract) Atlanta GA
2010 No A.S. Trust & Holdings, Inc. HCR-188C1: A.S. Trust & Holdings, Inc.'s All-New, High-Efficiency Hydrocarbon Refrigerant With No Impact on Global Warming or the Ozone Layer (abstract) Kaneohe HI
2010 No Advanced Technology Materials, Inc. RegenSiTM: A Wafer Reclaim Solution with a Low Carbon Footprint that Extends the Life Cycle of Silicon Test Wafers (abstract) Danbury CT
2010 No AkzoNobel Functional Chemicals, LLC Bipolar Membrane Electrodialysis for Greener Processing of Chelates (abstract) Chicago IL
2010 No APTech Group, Inc. Safer, Sustainable, Biodegradable, Solid-State Chemistry for Treating Cooling Water Systems (abstract) Cincinnati OH
2010 No Baker Hughes Incorporated Highly Water-Dispersed Oilfield Corrosion Inhibitors Eliminate over One Million Pounds of Nonrenewable Solvents Annually (abstract) Sugar Land TX
2010 No Bayer MaterialScience, LLC IMPACT Technology: A Greener Polyether Polyol Process (abstract) South Charleston WV
2010 No BCR Environmental LLC; SABIC Innovative Plastics Recovering and Using a Formerly Incinerated Sodium Nitrite Waste Stream to Disinfect and Stabilize Municipal Biosolids (abstract) Jacksonville FL
2010 No Bend Research Inc. Spray-Dried Dispersions Based on Hydroxypropyl Methylcellulose Acetate Succinate for Delivery of Low-Solubility Drugs (abstract) Bend OR
2010 No Berry Plastics; Flame Chk Inc.; Chemische Fabrik Budenheim KG Nonhalogenated Flame Retardant for Use in High-Performance Adhesives and Coatings (abstract) Bristol RI
2010 No BioFuelBox, Inc. Supercritical–Solid Catalyst Reaction Process for Converting Waste Fats, Oils, and Greases into Premium Biodiesel (abstract) San Jose CA
2010 No Cargill, Incorporated The Development and Commercialization of a Low-pH, Lactic Acid Process for Renewable Plastics (abstract) Minnetonka MN
2010 No Chemguard Ltd. Elimination of Perfluorinated Alkyl Surfactants from Fire-Fighting Foams (abstract) Mansfield TX
2010 Yes Clarke NatularTM Larvicide: Adapting Spinosad for Next-Generation Mosquito Control (summary and podcast) Roselle IL
2010 No Codexis, Inc. Rapid Enablement of Green Processes for Chiral Alcohols by the CodexTM Panel of Robust, Divergent Evolvants of One Ancestral Ketoreductase (abstract) Redwood City CA
2010 No Cortec Corporation Corrosion Control with a Greener Pathway (abstract) St. Paul MN
2010 No Cytec Industries Inc. UV-Curable Pressure Sensitive Adhesive (abstract) Woodland Park NJ
2010 No Dionex Corporation Accelerated Solvent Extraction with Solvent Saver ModeTM: Reducing Organic Solvent Consumption and Waste in Laboratories (abstract) Sunnyvale CA
2010 No Dow Chemical Company, The An Innovative Approach to Texturizers without Hydrofluoric Acid or Nitric Acid for Multicrystalline Silicon Photovoltaics (abstract) Marlborough MA
2010 No Dow Chemical Company, The Energy Savings from a New Manufacturing Route for Vinyl Methyl Ether (abstract) Midland MI
2010 Yes Dow Chemical Company, The; BASF Innovative, Environmentally Benign Production of Propylene Oxide via Hydrogen Peroxide (summary and podcast) Midland MI
2010 No E. I. du Pont de Nemours and Company Cerenol® Polyol Technology Platform for a Sustainable Bio-Based Economy (abstract) Wilmington DE
2010 No Henkel Technologies A Safer, Environmentally Superior, High-Performance Acid Inhibitor Designed to Protect Metallic Infrastructure during Industrial Cleaning (abstract) Madison Heights MI
2010 Yes Liao, James C.; Easel Biotechnologies, LLC; University of California, Los Angeles Recycling Carbon Dioxide to Biosynthesize Higher Alcohols (summary and podcast) Los Angeles CA
2010 Yes LS9, Inc. Microbial Production of Renewable PetroleumTM Fuels and Chemicals (summary and podcast) South San Francisco CA
2010 No MacGillivray, Leonard R.; University of Iowa; University of Iowa Research Foundation Template-Controlled Reactivity in the Organic Solid State (abstract) Iowa City IA
2010 Yes Merck & Co., Inc.; Codexis, Inc. Greener Manufacturing of Sitagliptin Enabled by an Evolved Transaminase (summary and podcast) Rahway NJ
2010 No Pennakem LLC 2-Methyltetrahydrofuran: A Green Alternative to Oil Derived Ethers and Chlorinated Solvents (abstract) Memphis TN
2010 No Preventive Technology Inc. PRE-TEC 3000®: An Environmentally Friendly Wood Treatment (abstract) Greenville SC
2010 No STERIS Corporation An Environmentally Friendly Alternative for Cleaning Surgical Instruments in Healthcare Facilities (abstract) Mentor OH
2010 No Sun, Xiuzhi Susan; Kansas State University; SoyResin, LLC Green Process of Unfolding Soy Protein Polymers for Green Adhesives (abstract) Manhattan KS
2010 No Thermphos USA Corp. Dequest® PB: Carboxymethyl Inulin, A Versatile Scale Inhibitor from the Roots of Chicory (abstract) Mechanicsville VA
2010 No Troy Corporation Source Reduction and Sustainability through Use of Mergal® 753 Antimicrobial Preservative (abstract) Florham Park NJ
2011 No Aeroclay, Inc.; Schiraldi, David; Case Western Reserve University AeroClay®: A Green Aerogel for Industry (abstract) Solon OH
2011 No BASF Corporation Green SenseSM Concrete (abstract) Beachwood OH
2011 No Battelle Memorial Institute Bio-Derived Green Primary Polyvinyl Chloride Plasticizers with Improved Thermal Stability and Plasticization Efficiency (abstract) Columbus OH
2011 Yes BioAmber, Inc. Integrated Production and Downstream Applications of Biobased Succinic Acid (summary and podcast) Minneapolis MN
2011 No Champion Technologies, Inc. Lysine-Based Phosphonate Scale Inhibitor with Improved Biodegradation and Maintained Performance (abstract) Houston TX
2011 No Chemical Safety Software Source Reduction through Software Technology (abstract) Emeryville CA
2011 No Commercial Fluid Power LLC Elimination of Hexavalent Chromium from Hydraulic and Pneumatic Tubing and Bar (abstract) La Porte IN
2011 No Cytec Industries Inc. iSUSTAIN® Green Chemistry Index Tool for Sustainable Development (abstract) Woodland Park NJ
2011 No Cytec Industries Inc. Waterborne, Ambient-Cure, Stain-Blocking Primer (abstract) Woodland Park NJ
2011 No Desilube; United Soybean Board High Performance Soy-Based Metalworking Fluid (abstract) St. Louis MO
2011 No Diversey Inc. ReNew Air Scrubber Technology (abstract) Sturtevant WI
2011 No Dober Chemical Corporation A Safer, Less Toxic, Reliable, and Green Water Treatment by Smart Release® Technology (abstract) Woodridge IL
2011 No Earth Friendly Products Earth Conscious Chemistry: Eliminating 1,4 Dioxane in Cleaning Products (abstract) Garden Grove CA
2011 No Ecolab Inc. DryExx Conveyor Lubricant Program (abstract) Eagan MN
2011 No Ecolab Inc. Low-Temperature Cleaning In Place (abstract) Eagan MN
2011 No Eli Lilly and Company Continuous Processing Enables a Convergent Route to a New Drug Candidate: LY2624803*H3PO4 (abstract) Indianapolis IN
2011 No Finn, M. G.; The Scripps Research Institute Metal Adhesive Polymers from Cu(I)-Catalyzed Azide-Alkyne Cycloaddition: a New Approach to Solder Replacements (abstract) La Jolla CA
2011 No FMC Corporation VigorOx® Biocide: Advancing Environmentally Responsible Energy Production (abstract) Philadelphia PA
2011 No Foam Supplies, Inc. Ecomate® Environmentally Benign Blowing Agent for Polyurethane Foams (abstract) Earth City MO
2011 No Fuel Energy Service Corporation Surachi Fuel Technology (abstract) Mobile AL
2011 No Genencor Gentle Power BleachTM: A Revolutionary Enzymatic Textile Bleaching System (abstract) Palo Alto CA
2011 No General Motors Applying Green Chemistry Principles to Enable Zero-Waste Manufacturing (abstract) Grand Blanc MI
2011 Yes Genomatica Production of Basic Chemicals from Renewable Feedstocks at Lower Cost (summary and podcast) San Diego CA
2011 No Hach Company Simplified Total Kjeldahl Nitrogen Method for Wastewater: A Green Alternative to Traditional Kjeldahl Methodology (abstract) Loveland CO
2011 No JEEN International Polyelectrolytes: Reduce Your Carbon Footprint Using an Eco-Friendly Technology to Disperse Wax in Water without Heat (abstract) Fairfield NJ
2011 Yes Kraton Performance Polymers, Inc. NEXARTM Polymer Membrane Technology (summary and podcast) Houston TX
2011 Yes Lipshutz, Bruce H.; University of California, Santa Barbara Towards Ending Our Dependence on Organic Solvents (summary and podcast) Santa Barbara CA
2011 No L'Oreal USA Kiehl's "Aloe Vera" Biodegradable Liquid Body Cleanser (abstract) Clark NJ
2011 No Lubrizol Corporation, The Positive Environmental Impact of Novel Crankcase Lubricant Technology (abstract) Wickliffe OH
2011 No Natural State Research, Inc. Conversion of Waste Plastics into Fuel (abstract) Stamford CT
2011 No Novozymes North America, Inc. Enabling a Sustainable Biorefinery with Green Chemistry: Enzymatic Hydrolysis of Lignocellulosic Biomass for the Production of Advanced Biofuels and Renewable Chemicals (abstract) Franklinton NC
2011 No Orono Spectral Solutions Device and Method for Analyzing Oil and Grease in Wastewaters without Solvent (abstract) Old Town ME
2011 No Pacific Scientific Energetic Materials Co. New Lead Free Materials for Replacement of Existing Primary Explosives (abstract) Chandler AZ
2011 No Piedmont Biofuels Industrial, LLC Enzymatic Catalysis for Biodiesel Production (abstract) Pittsboro NC
2011 No Polar Industries, Inc. Zero-VOC, BioBased HiOmega® Linseed Oil Epoxies, Adhesives, and Alkyd Resins as Replacements for Epichlorohydrin–Epoxy Resins and Other VOC-containing Coatings, Paints, Adhesives, and Epoxies (abstract) Miami FL
2011 No PPG Industries, Inc. Waterborne Refi nish Coatings Manufacture (abstract) Strongsville OH
2011 No Rochester Midland Corporation Enhance O2 Soil Remover for Commercial Fryers (abstract) Rochester NY
2011 No Rochester Midland Corporation PRS Water Damage PreClean: Biological Cleaning for Restoration and Remediation (abstract) Rochester NY
2011 No Savage, Phillip E.; University of Michigan Terephthalic Acid Synthesis at High Concentrations in High-Temperature Liquid Water (abstract) Ann Arbor MI
2011 Yes Sherwin Williams Company, The Water-based Acrylic Alkyd Technology (summary and podcast) Cleveland OH
2011 No Sigma-Aldrich Green Chemistry Process for the Large-Scale Manufacture of Polyamino Acids (abstract) St. Louis MO
2011 No Solvair LLC Solvair Cleaning System (abstract) Naperville IL
2011 No Steward Advanced Materials Development and Commercial Application of SAMMS®: A Novel Compound that Adsorbs and Removes Mercury and Other Toxic Heavy Metals (abstract) Chattanooga TN
2011 No Terrabon, Inc. Conversion of Municipal Solid Wastes to Drop-In Fuels and Chemicals (abstract) Houston TX
2011 No Timber Treatment Technologies, LLC TimberSIL® (abstract) Springfield VA
2011 No Tower Oil & Technology Co. Saf-T-Vanish®: A Zero-VOC, Green Replacement for Petroleum Solvent Vanish Oils (abstract) Chicago IL
2011 No van Heiningen, Adriaan; Genco, Joseph; Pendse, Hemant; van Walsum, Peter; University of Maine Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel (abstract) Orono ME
2011 No WM Barr & Company, Inc. Klean‐Strip® GreenTM Safer Paint Thinner (abstract) Memphis TN
2012 No Albemarle Corporation Concrete-FriendlyTM Powdered Active Carbon (C-PACTM) to Remove Mercury from Flue Gas Safely (abstract) Baton Rouge LA
2012 No Armstrong World Industries, Inc. BioBased Tile®: A Non-PVC Flooring Made with Rapidly Renewable Resources (abstract) Lancaster PA
2012 No Ashland Performance Materials EnvirezTM Technology: Incorporating Renewable and Recycled Feedstocks into Unsaturated Polyester Resins (abstract) Dublin OH
2012 No BASF Corporation Compostable Multilayer Food Packaging (abstract) Wyandotte MI
2012 No Bayer MaterialScience and Bayer AG One-Component, UV-Curable, Waterborne Polyurethane Coatings (abstract) Pittsburgh PA
2012 No BCD Group-II, Inc. Producing Chemicals and Carbon from Waste Tires, Plastics, Carpet, and Biomass (abstract) Cincinnati OH
2012 No Bennett, Jacqueline; State University of New York Oneonta; SUNY Research Foundation Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of Diaryl Aldimines (abstract) Oneonta NY
2012 No Blue Marble Biomaterials LLC Greening the Design of Chemical Production with Microbes (abstract) Missoula MT
2012 Yes Buckman International, Inc. Enzymes Reduce the Energy and Wood Fiber Required to Manufacture High-Quality Paper and Paperboard (summary and podcast) Memphis TN
2012 No CCP Composites FIREBLOCKTM Intumescent Resin (abstract) Kansas City MO
2012 Yes Coates, Geoffrey W.; Cornell University Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon MoNOxide (summary and podcast) Ithaca NY
2012 Yes Codexis, Inc.; Yi Tang; University of California, Los Angeles An Efficient Biocatalytic Process to Manufacture Simvastatin (summary and podcast) Redwood City CA
2012 No Colonial Chemical, Inc. Suga®Nate: A Safer, Milder, Greener Surfactant (abstract) South Pittsburg TN
2012 No Cooper Power Systems Vegetable Oil Insulating Fluid for Improved High Voltage Transformer Capability (abstract) Waukesha WI
2012 No CPS Biofuels, Inc. Glycerol tert-Butyl Ether (GTBE): A Biofuel Additive for Today (abstract) Virginia Beach VA
2012 No Cytec Industries Inc. Saturated Polyester–Phenolic Resin Systems Eliminate Bisphenol A and Epoxy from Interior Can Coatings for Food Packaging (abstract) Woodland Park NJ
2012 Yes Cytec Industries Inc. MAX HT® Bayer Sodalite Scale Inhibitor (summary and podcast) Woodland Park NJ
2012 No DuPont Company Chlorantraniliprole: Increased Food Production, Reduced Risks, More Sustainable Agriculture (abstract) Wilmington DE
2012 No DuPont Company and ButamaxTM Advanced BioFuels LLC Production of Isobutanol from the Synergy between Metabolic and Process Engineering (abstract) Wilmington DE
2012 No e2e Materials, Inc. Formaldehyde-Free, High-Strength Biocomposites from Sustainable Resources (abstract) Ithaca NY
2012 No Ecology Coatings Generally Recognized as Safe (GRAS) Coatings (abstract) Warren MI
2012 No Electrovaya Inc. Zero-Emission Production of the Green Lithium Ion SuperPolymer® Battery (abstract) Malta NY
2012 Yes Elevance Renewable Sciences, Inc. Using Metathesis Catalysis to Produce High-Performing, Green Specialty Chemicals at Advantageous Costs (summary and podcast) Woodridge IL
2012 No Eli Lilly and Company Grignards Going Greener by Continuous Processing (abstract) Indianapolis IN
2012 No IBM Corporation Catalytic Treatment of Hydrogen Peroxide in IBM Semiconductor Wastewater (abstract) Hopewell Junction NY
2012 No IBM Corporation Elimination of PFOS and PFOA in IBM Semiconductor Manufacturing Processes and Development of Photoacid Generators Free of Perfluoroalkyl Sulfonates (abstract) Hopewell Junction NY
2012 No InfiChem Polymers, LLC InfiGreenTM Polyols (abstract) Sterling Heights MI
2012 No John, George; The City College of the City University of New York Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for Safe Oil-Thickening Agents (Amphiphiles) (abstract) New York NY
2012 No Johnson & Johnson Consumer Companies, Inc.; AkzoNobel Surface Chemistry LLC NATRASURFTM PS-111 Polymeric Surfactant: Achieving Next Generation Mildness in Personal Care Products with a Reduced Environmental Footprint (abstract) Skillman NJ
2012 No Kop-Coat, Inc. Tru-Core® Protection System for Wood (abstract) Pittsburg PA
2012 No LubriGreen Biosynthetics Development and Commercialization of Oleic Estolide Esters (abstract) Irvine CA
2012 No Mascal, Mark; University of California, Davis Chemical Conversion of Biomass into New Generations of Renewable Fuels, Polymers, and Value-Added Products (abstract) Davis CA
2012 No Masterchem Brands KILZ MAXTM PRIMER-SEALER-STAINBLOCKER: Oil-Based Performance in a Water-Based Formula with Less Environmental Impact (abstract) Chesterfield MO
2012 No NALCO NALCO's APEXTM Program: Sustainable Technology for Paint Detackification (abstract) Coraopolis PA
2012 No Novomer, Inc. High-Performance Polyols from CO2 at Low Cost (abstract) Waltham MA
2012 No NSR Technologies, Inc. Electrodialysis and Chromatographic Separation Technology for Chlorine-Free Production of Potassium Hydroxide and Hydrochloric Acid (abstract) Decatur IL
2012 No OPX Biotechnologies, Inc. Producing Industrial Chemicals by Fermenting Renewable Feedstocks at a Lower Cost (abstract) Boulder CO
2012 No Performance Chemicals, LLC BURN-OUTTM Durable, Green, Nontoxic Flame Retardant (abstract) Concord NH
2012 No Pfizer New Green Commercial Biocatalytic Route to Atorvastatin Calcium, the Lipitor API (abstract) Kalamazoo MI
2012 No Plata, Desirée L.; Duke University Improved Resource Use in Carbon Nanotube Synthesis via Mechanistic Understanding (abstract) Durham NC
2012 No RajanBabu, T. V. (Babu); The Ohio State University Ethylene: A Feedstock for Fine Chemical Synthesis (abstract) Columbus OH
2012 No RPS Environmental Solutions, LP Zero-VOC Cleaning and Remediation Technology (abstract) Dallas TX
2012 No SiGNa Chemistry, Inc. Sodium Silicide: A New Alkali Metal Derivative for Safe, Sustainable, and On-Demand Generation of Hydrogen (abstract) New York City NY
2012 No Tandus Flooring EthosTM Modular Commercial Floor Coverings (abstract) Dalton GA
2012 No U.S. Department of Energy, Pacific Northwest National Laboratory; Archer Daniels Midland Company Propylene Glycol from Renewable Resources (abstract) Richland WA
2012 No Verdezyne, Inc. Biobased Adipic Acid for Renewable Nylon and Polyurethane Resins (abstract) Carlsbad CA
2012 No Verenium Corporation Pyrolase® Cellulase Enzyme Breaker as a Biodegradable Replacement for Corrosive Acids and Oxidizers in Hydraulic Fracturing Operations (abstract) San Diego CA
2012 No VH Biotechnology, Inc. Bacteriocins: A Green, Antimicrobial Pesticide (abstract) League City TX
2012 Yes Waymouth, Robert M.; Stanford University; Hendrick, James L.; IBM Almaden Research Center Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry (summary and podcast) Stanford CA
2013 No Advanced Biocatalytics Corporation (ABC) Changing the Nature of Surfactants: Protein-Surfactant Synergists With Enhanced Cleaning Power and Bioremediation Abilities (abstract) Irvine CA
2013 No AkzoNobel Surface Chemistry, LLC Hybrid Polymers (abstract) Chicago IL
2013 No AnCatt Inc. Conductive Polymer Nanodispersion (CPND) and the Environmentally Friendly Heavy-Duty Anti-Corrosion Coating Platform Technology (abstract) Newark DE
2013 No Armstrong World Industries Breakthrough Coating for Ceiling Tiles (abstract) Lancaster PA
2013 No AstraZeneca and Forest Laboratories An Order of Magnitude Improvement in Sustainability through Core Application of Green Chemistry Principles: The Process Development of Avibactam (abstract)    
2013 Yes Cargill, Inc. Vegetable Oil Dielectric Insulating Fluid for High-Voltage Transformers (summary) Brookfield WI
2013 No Dow Chemical Company, The INFUSETM Olefin Block Copolymers (abstract) Midland MI
2013 Yes Dow Chemical Company, The EVOQUETM Pre-Composite Polymer Technology (summary) Midland MI
2013 No DSM Biobased Products and BP Biofuels Sugar to Diesel (Bio-Diesel from Microbial Oil) -- A Sustainable, Scalable and Affordable Option to Petroleum Diesel (abstract) Columbia MD
2013 No DuPont and Goodyear An Innovative Cell Factory and Bioprocess for Production of BiolsopreneTM Monomer (abstract) Palo Alto CA
2013 Yes Faraday Technology, Inc. Functional Chrome Coatings Electrodeposited from a Trivalent Chromium Plating Electrolyte (summary) Clayton OH
2013 No FRX POLYMERS® Inc. Polymeric, Non-Halogenated Flame Retardants with Broad Applicability in Multiple Industries (abstract) Chelmsford MA
2013 No GeoTree Technologies, Inc. GeoSprayTM Geopolymer Mortar System for Structural Rehabilitation of Sewer and Storm Water Infrastructure (abstract) Lafayette CO
2013 No Infinite Enzymes Infinite Enzymes: Low-Cost, Plant-Based Enzymes for Converting Cellulosic Biomass into Biofuels and Other Biobased Products (abstract) State University AR
2013 No International Products Corporation Temporary Assembly Lubricants for Rubber and Plastic Articles Using Renewable Oil-in-Water Emulsion Technology (abstract) Burlington NJ
2013 Yes Life Technologies Corporation Safe, Sustainable Chemistries for the Manufacturing of PCR Reagents (summary) Austin TX
2013 No Lonza, Inc. Dantogard 2000 Preservative: An Antimicrobial Technology with Reduced Environmental Impact for Hydraulic Fracturing of Shale Gas Plays (abstract) Allendale NJ
2013 No Monsanto and Biosynthetic Technologies Vistive® Gold Soybeans and Biosynthetic Technologies Enable Biodegradable, Non-Toxic, Renewable, and Economical Industrial Bio-Lubricants (abstract) St. Louis MO
2013 No Multi-Chem, A Halliburton Service The Use of Nitrate and Selected Live Strains of Nitrate Reducing Bacteria to Replace the Use of Biocide in Hydraulic Fracturing Operations (abstract) Houston TX
2013 No Myriant Corporation Expanding the Renewable Polymers "Tool Kit" with Bio-Succinic Acid (abstract) Woburn MA
2013 No Myriant Corporation Bio-based Chemicals from Low-cost Lignocellulosic Sugars (abstract) Woburn MA
2013 No Nalco Champion, An Ecolab Company eVerified ASP560: An Environmentally Friendly Corrosion Inhibitor (abstract) Sugar Land TX
2013 No New Sky Energy, LLC Sustainable Soda Ash for the Glass Industry (abstract) Boulder CO
2013 No Novozymes Enzymes for the Production of Economical Sugars: A Linchpin of the Carbohydrate Economy (abstract) Franklinton NC
2013 No Owens Corning Sustainability and Owens Corning's EcoTouchTM Insulation Conversion (abstract) Newark OH
2013 No Subramaniam, Bala; University of Kansas A Greener Hydroformylation Technology (abstract) Lawrence KS
2013 No Systea Scientific, LLC Easy (1-Reagent) Nitrate Method: A Green Alternative to Traditional USEPA Approved Nitrate Methods (abstract) Oak Brook IL
2013 No Thames, S. F.; Rawlins, J. W.; The University of Southern Mississippi Formaldehyde-Free Commercial-Grade Particleboards Based Solely on Soybean Protein Adhesive (abstract) Hattiesburg MS
2013 No U.S. Department of Energy, Argonne National Laboratory Upcycling Process That Converts Unsorted Plastic Waste into Functional Carbon Materials (abstract) Argonne IL
2013 No Virent, Inc. Converting Plant Sugars into Paraxylene for 100% Renewable, 100% Recyclable Packaging and Fibers (abstract) Madison WI
2013 No Washing Systems LLC Pure Solutions Chemical Line for Laundries (abstract) Loveland OH
2013 Yes Wool, Richard P.; U Delaware Sustainable Polymers and Composites: Optimal Design (summary) Newark DE
2014 No ACTA Technology Inc. A Greener, Safer and More Efficient Antifreeze (abstract) Boulder CO
2014 No Advanced Technology Materials, Inc. (ATMI), an Entegris company The eVOLVTM System, a Clean, Sustainable Solution to Electronic Waste (abstract) Danbury CT
2014 No AkzoNobel Functional Chemicals, LLC Improved Performance and HSE Profile of a Novel Stimulation Fluid for Oil and Natural Gas Wells (abstract) Chicago IL
2014 Yes Amyris Farnesane: a Breakthrough Renewable Hydrocarbon for Use as Diesel and Jet Fuel (summary and podcast) Emeryville CA
2014 No Archroma Earthcolors Technology (abstract) Charlotte NC
2014 No Arizona Chemical Company, LLC SYLVAROADTM RP 1000 Performance Additive: A Sustainable, Pine-Based Additive to Enable High Re-Use of Reclaimed Asphalt Pavement (abstract) Savannah GA
2014 No Atsumi, Shota; University of California, Davis Green Biological Production of Short and Medium Chain Esters (abstract) Davis CA
2014 No Bay State Tech, LLC Consumer Viable and Environmentally Friendly Solvent Replacements Developed From Food Grade Compounds (abstract) Baltimore MD
2014 No Blair, Richard; University of Central Florida, The The Scalable Production of Edge Functionalized Few Layer Graphene Oxide (abstract) Orlando FL
2014 No Boeing Company, The; Boeing Research & Technology Boegel Surface Activation Technology Suite (abstract) Seattle WA
2014 No Copperhead Chemical Company Inc. Novel, Effective, Safe Delivery System for Antimicrobial Agents Derived from Sustainable Vegetable Monoglycerides (abstract) Tampa FL
2014 No Cytec Industries Inc. Cylinderized Phosphine as Safer, More Environmentally Friendly Alternatives to Traditional Stored Product Fumigants (abstract) Stamford CT
2014 No Dow Chemical Company, The Sustainable Microbial Control Treatments for Hydraulic Fracturing (abstract) Buffalo Grove IL
2014 No Dow Chemical Company, The BETAMATETM and BETAFORCETM Structural Adhesives Improve Automotive Fuel Efficiency and Emissions (abstract) Midland MI
2014 No Dow Chemical Company, The FORMASHIELDTM Formaldehyde Abatement Technology (abstract) Collegeville PA
2014 No Dumesic, James A.; University of Wisconsin-Madison Enzyme-Free Biomass Depolymerization Using GVL (abstract) Madison WI
2014 No E&B Green Solutions G-Clean® Line of Green Cleaning Products Designed to Clean Hydrocarbons Safely and Effectively (abstract) Hermosa Beach CA
2014 No Ecolab Environmentally Responsible Spore Control Program Through Effective Cleaning and Sanitizing of Heat Exchange Dairy Process Equipment (abstract) Eagan MN
2014 No Genentech, Inc. Targeted Chemotherapy for Solid Tumor Cancer Treatment (abstract) South San Francisco CA
2014 No GreenLife Development Naturama - Oil Surfactant, Green Degreaser and Cleaner (abstract) Las Vegas NV
2014 No Gunasekaran, Sundaram; Yang, Jiang; University of Wisconsin-Madison; LignoCarbon Green Approaches of Nanocomposite Material Synthesis for Energy Storage, Environmental Surveillance and Sustainable Food Systems (abstract) Mountain View CA
2014 No Merck & Co., Inc. An Innovative Catalytic Intramolecular Asymmetric Reductive Amination of a Dialkyl Ketone Enables a Highly Efficient, Green Synthesis of Suvorexant (MK-4305) (abstract) Rahway NJ
2014 No Monsanto Company Bt Technology, Transforming Insect Control (abstract) St. Louis MO
2014 No Musolino, Bryan; University of Tennessee, Knoxville Ultrasound Induced, Copper Mediated Homo-Coupling Using Polymer Supported Aryltrifluoroborates (abstract) JBSA-FSH TX
2014 No MWV Specialty Chemicals, a division of MeadWestvaco Corporation Evotherm® Warm Mix Asphalt Technology (abstract) North Charleston SC
2014 No Novinda Corporation Amended Silicates® HgX (abstract) Denver CO
2014 No PPG Industries, Inc. Polyethylene Terephthalate (PET) Derived Polymers for Coatings (abstract) Pittsburgh PA
2014 No Pyun, Jeffrey; Glass, Richard; U of Arizona Utilization of Elemental Sulfur as a New Chemical Feedstock for Polymeric Materials (abstract) Tucson AZ
2014 Yes QD Vision, Inc. Greener Quantum Dot Synthesis for Energy Efficient Display and Lighting Products (summary and podcast) Lexington MA
2014 Yes Solazyme, Inc. Tailored Oils Produced from Microalgal Fermentation (summary and podcast) South San Francisco CA
2014 Yes Solberg Company, The RE-HEALINGTM Foam Concentrates–Effective Halogen-Free Firefighting (summary and podcast) Green Bay WI
2014 Yes Stahl, Shannon S.; University of Wisconsin-Madison Aerobic Oxidation Methods for Pharmaceutical Synthesis (summary and podcast) Madison WI
2014 No Stepan Company STEPOSOL® MET‐10U. A Bio‐derived, Nonionic Surfactant Solution for Solvent Replacement: Source Reduction and Inherently Lower Health Hazards in Hard Surface Cleaning and Adhesive / Paint Removal (abstract) Northfield IL
2014 No Terramera, Inc. CIRKIL Biopesticide (abstract) Buena Park CA
2014 No Washing Systems LLC Green Detergents for Industrial Laundries (abstract) Loveland OH
2014 No Wyman, Charles; University of California, Riverside UCR Co-Solv Technology Achieves Unprecedented Yields of Fuel Precursors from Lignocellulosic Biomass (abstract) Riverside CA
2015 No A S FiltrationTM, LLC Pathex®/PathShieldTM Antimicrobial Filter Media for the Control of Bacteria in Stormwater and Industrial Process Waters (abstract) Hixson TN
2015 No Acid-Amine Technologies, Inc. (AAT) Using Bioethanol as A Raw Material, To Produce: 1. SAFEN: A Low Cost Nematicide And Fungicide, Based on Ethyl Formate, Which Is Generally Regarded as Safe by the FDA, and Which Biodegrades Into Two Naturally Occurring Substances, with No Lasting Detrimental Effects to Air, Soil and Water; and 2. Ethyl Formate in a Second Development as a Suitable Raw Material for Propionic Acid and Acrylate Production (abstract) Woodcliff Lake NJ
2015 Yes Algenol The Algenol Biofuel Process: Sustainable Production of Ethanol and Green Crude (summary and picture) Fort Myers FL
2015 No Barreto, Reynaldo; Purdue University North Central Photocatylic Oxidations of Ethers with Visible/Near UV Light and the Development of a Continuous Flow Photoreactor (abstract) Westville IN
2015 Yes Chen, Eugene Y.-X.; Colorado State University Greener Condensation Reactions for Renewable Chemicals, Liquid Fuels, and Biodegradable Polymers (summary and picture) Fort Collins CO
2015 No Eastman Chemical Company Eastman OmniaTM Solvent – Changing the Chemistry of Clean. New, Safe, Highly Effective Solvent for Cleaning Applications (abstract) Kingsport TN
2015 No Ecolab OxyCideTM Daily Disinfectant Cleaner (abstract) Eagan MN
2015 No Ecolab Environmentally Preferable Biocide For Water Treatment in Hydraulic Fracturing (abstract) Eagan MN
2015 No Green Biologics, Inc. (GBI) The Reinvention of Biomass Based n-Butanol for the Renewable Chemicals Industry (abstract) Gahanna OH
2015 No Honeywell International Low Global Warming, Non-VOC, Zero-ODP Molecule for Energy Efficient Polyurethane Foam Insulation Blowing Agent, Solvents, and Heat Transfer (abstract) Morristown NJ
2015 Yes Hybrid Coating Technologies/Nanotech Industries Hybrid Non-Isocyanate Polyurethane/Green PolyurethaneTM (summary and picture) Daly City CA
2015 Yes LanzaTech Inc. LanzaTech Gas Fermentation Process (summary and picture) Skokie IL
2015 No Licht, Stuart; George Washington University A Solar Chemical Process to End Anthropogenic Global Warming: STEP Generation of Energetic Molecules (abstract) Washington DC
2015 No Light Curable Coatings High Performance Solvent-Free Coating Technology (abstract) Valley View OH
2015 No Linde North America Development of Vapormate as a Replacement for Methyl Bromide Fumigants (abstract) Murray Hill NJ
2015 No Modular Genetics, Inc. Greener Synthesis of Surfactants (abstract) Cambridge MA
2015 No Phyllom BioProducts grubGONE!®, beetleGONE!® and boreGONE!®, Biological Insecticides with Low Impact on Humans and the Environment Yet Effective Against Destructive Beetle Pests (abstract) Oakland CA
2015 No PROSOCO, Inc. PROSOCO R-Guard: High-Performance Phthalate-Free Air and Water Resistive Barrier Sealant and Sealant Coating System (abstract) Lawrence KS
2015 Yes Renmatix The Plantrose® Process: Supercritical Water as the Economic Enabler of Biobased Industry (summary and picture) San Francisco CA
2015 No Sagamore-Adams Laboratories, LLC PLATech, Green Chemistry Universal Adhesive-Sealing Technology (abstract) Chicago IL
2015 No Siluria Technologies, Inc. Cleaner Transportation Fuels and Commodity Chemicals from Methane (abstract) San Francisco CA
2015 No Sirrus, Inc. 1, 1-Disubstituted Alkenes (abstract) Loveland OH
2015 Yes Soltex (Synthetic Oils and Lubricants of Texas) A Novel High Efficiency Process for the Manufacture of Highly Reactive Polyisobutylene Using a Fixed Bed Solid State Catalyst Reactor System (summary and picture) Houston TX
2015 No VF Corporation VF Corporation: CHEM-IQSM (abstract) Greensboro NC
2015 No Voorhees, Kent; Colorado School of Mines Bacteriophage-Based Bacterial Identification and Antibiotic Resistance Test (abstract) Golden CO
2015 No ZAPS Technologies, Inc. An Application of Hybrid Multispectral Analysis; Real-Time Wastewater Process Control (abstract) Corvallis OR
2015 No Zhang, Yi-Heng Percival; Cell Free Bioinnovations Inc Ultra-High Energy Density Metal-Free Sugar Biobattery (abstract) Blacksburg VA
2016 No 3M Alternative to Sulfur Hexafluoride Enables up to 99% Greenhouse Gas Emission Reduction (abstract) St. Paul MN
2016 No AECOM Green Nanotechnology Product and Processes for Cleaning Up Contaminated Soil and Groundwater (abstract) Atlanta GA
2016 No Alliance Finishing Plating on Plastics (abstract) Oxnard CA
2016 No Biosynthetic Technologies Estolides: A Low-Cost, High-Performance Renewable Fluid Certified for Motor Oil (abstract) Irvine CA
2016 No Bristol-Myers Squibb Discovery, Development and Implementation of New Chemical Technology toward a Novel Commercial Synthesis for the HIV-Attachment Inhibitor, BMS-663068 (abstract) New Brunswick NJ
2016 No Calgon Carbon Corporation FLUEPAC® activated carbon products for superior mercury control from flue gas and green re-use of coal combustion residuals (abstract) Moon Twp PA
2016 No Calysta Disruptive Methantropic Technology for Sustainable Food, Fuel and Products: Green Chemistry Innovation Enabling US Global Competitiveness in Low-Carbon, New Economy (abstract) Menlo Park CA
2016 Yes CB&I; Albemarle AlkyClean® Technology: An Inherently Safer Technology for the Production of Gasoline Alkylate (summary) Amersfoort TX
2016 Yes Chirik, Paul J., Princeton University Catalysis with Earth Abundant Transition Metals (summary) Princeton NJ
2016 No Collaborative Aggregates, LLC Delta STM: An Environmentally Benign and Worker Safe Asphalt Rejuvenator (abstract) Wilmington MA
2016 No Compact Membrane Systems, Inc. Membrane Dehydration for Solvent Recovery and Reuse (abstract) Newport DE
2016 No Covestro LLC Dream Production – CO2 as a new building block for high-tech plastics (abstract) Pittsburgh PA
2016 Yes Dow AgroSciences LLC Instinct® Technology – Making Nitrogen Fertilizers Work More Effectively for Farmers and the Planet (summary) Indianapolis IN
2016 No Dow Chemical Company, The Dow Polymeric Flame Retardant (abstract) Midland MI
2016 No Dow Chemical Company, The SOLDERONTM BP Lead-free Solder Plating Chemistry (abstract) Marlborough MA
2016 No Dow Microbial Control KathonTM 7 Tl Antimicrobial for Water Treatment Applications (abstract) Collegeville PA
2016 No DuPont Creation, Integration, and Engineering of the World’s Largest Cellulosic Ethanol BioRefinery Production Platform (abstract) Wilmington DE
2016 No Elinor Specialty Coatings; Bierwagen, Gordon; North Dakota State University; Akzo Nobel Aerospace Coatings Mg rich primer for Chrome free protection of Aluminum and its alloys (abstract) Fargo ND
2016 No Floral Soil LLC Floral Soil: A Green Chemistry Alternative to Phenol Formaldehyde Foams for Floral & Horticulture Industries (abstract) Everett WA
2016 No H-O-H Water Technology, Inc. Cooling Tower Water Conservation and Chemical Treatment Elimination (abstract) Palatine IL
2016 No Huang, Yu; University of California, Los Angeles Surface Engineered High-performance Catalysts for Fuel Cell Applications (abstract) Los Angeles CA
2016 No Instrumental Polymer Technologies, LLC Evolution Polymerization To Produce Sustainable Polycarbonate Dendrimers (abstract) Westlake Village CA
2016 No International Flavors & Fragrances Inc. (IFF) A Greener Process for the Fragrance Veridian and Development/Implementation of IFF’s Green Chemistry Tool (abstract) Union Beach NJ
2016 No ISCA Technologies, Inc. SPLAT® VERB: An Insecticide-Free, Green Repellent for Bark Beetle Pests of North American Forestry (abstract) Riverside CA
2016 No Kiverdi Carbon Engineering Platform (abstract) Hayward CA
2016 No Lygos, Inc. Integrated Production of Sustainable Biobased Malonic Acid for Significant Source Pollution Reduction, Cost, and Performance Advantages (abstract) Emeryville CA
2016 No Marrone Bio Innovations GRANDEVO® advanced bioinsecticides (abstract) Davis CA
2016 No Marrone Bio Innovations ZEQUANOX® (abstract) Davis CA
2016 No Meredian Holdings Group (Meredian, Inc. and DaniMer Scientific) Degradable Polymers for Fracking Applications (abstract) Bainbridge GA
2016 No Midwest Refrigerants, LLC -- a Missouri Limited Liability Company The Recovery of Organic Halides from Waste Streams by the Chemical Reaction of Hydrogen and Carbon Dioxide (abstract) Shoreline WA
2016 No Miller, Stephen; U of Florida; U.S. Bioplastics, LLC Replacing Packaging Plastics with Sustainable Bioplastics from Megacrop Waste (abstract) Gainesville FL
2016 Yes Newlight Technologies, LLC AirCarbon: Greenhouse Gas Transformed into High-Performance Thermoplastic (summary) Irvine CA
2016 No Novvi, LLC (a joint venture of Amyris, Inc. and Cosan S.A. Industria e Comercio) Renewable Oils for High Performance Lubricants (abstract) Emeryville CA
2016 No Ohio Soybean Council Bio-Derived Oligomer Technology to Replace Bis Phenol-A (BPA)-Based Thermoset Coatings: A Practical Solution for BPA-Free Metal Can Coatings for Beer, Beverage, and Food Containers (abstract) Worthington OH
2016 No OMNOVA Solutions Inc. SunCryl HP 114, an Environmentally Friendly Release Coat (abstract) Akron OH
2016 No Pfizer A Green, Energy Efficient, Chemoenzymatic Process to Manufacture Pregabalin (abstract) San Diego CA
2016 No Procter & Gamble Company, and DuPont Company Cold-Water Enzyme: Reducing the Environmental Footprint of Residential Laundry through Low Temperature Cleaning (abstract) Palo Alto CA
2016 No Rennovia Inc. Breakthrough Catalyst Technology Enables Cost Competitive Drop-in Bio-Based Nylons and Polyurethanes (abstract) Santa Clara CA
2016 No Rivertop Renewables Rivertop Renewables - Sugar Oxidation Process (abstract) Missoula MT
2016 No Sabatini, Jesse; US Army Research Laboratory (ARL) Environmentally Friendly Colored Pyrotechnic Illuminants (abstract) Aberdeen Proving Ground MD
2016 No SiGNa Chemistry, Inc.; Dixie Chemical Company, Inc. Input and Waste Associated with the Isomerization of Linear Alpha Olefins (abstract) New York NY
2016 No Sun Pharmaceuticals, Inc. Environmental protection reagents from MSW: one-step quantitative resourcing municipal solid waste (abstract) San Diego CA
2016 No UOP LLC, A Honeywell Company A Feedstock Flexible Process to produce Diesel and/or Jet Fuel from Renewable Resources (abstract) Des Plaines IL
2016 Yes Verdezyne Renewable Nylon through Commercialization of BIOLONTM DDDA (summary) Carlsbad CA
2016 No Virox Technologies Inc. Accel 5 RTU, an Accelerated Hydrogen Peroxide® (AHP®) based cleaner-disinfectant that provides a sustainable and safer choice for infection prevention and control (abstract) Oakville WI
2016 No Vitaworks, LLC Atom-Efficient Process for Producing Taurine (abstract) North Brunswick NJ
2017 No Aequor, Inc. Novel Active Agents Inhibit Bacterial Biofilm Formation and Fouling (abstract) San Diego CA
2017 Yes Amgen Inc. and Bachem Green Process for Commercial Manufacture of Etelcalcetide Enabled by Improved Technology for Solid Phase Peptide Synthesis (summary) Cambridge MA
2017 No Aqua Metals AquaRefining (abstract) Alameda CA
2017 No Ashland Specialty Ingredients G.P. Green and Sustainable Processing for the Fractionation of Botanicals for Cosmetic Use: Zeta FractionTM Technology (abstract) Ossining NY
2017 No Bell, Alexis T.; UC Berkeley A Condensation Chemistry-Inspired Biorefinery to Produce Superior Low Carbon Fuels and Lubricants (abstract) Berkeley CA
2017 No Catalytic Innovations, LLC Molecular Catalysts for Sustainable Wastewater Electrolysis (abstract) Adamsville RI
2017 No CF Industries Holdings, Inc. Infrared Spectroscopic Determination of Oil in Anhydrous Ammonia with Solid State Extraction (abstract) Sergeant Bluff IA
2017 No Clean Chemistry, Inc. PeroxyMAXTM a safer and less toxic alternative to chlorine oxidants (abstract) Boulder CO
2017 No Croda The More Sustainable Choice: 100% Renewable Ethoxylates (abstract) Edison NJ
2017 No Dow Building Solutions BLUEDGETM Polymeric Flame Retardant (FR) Technology for Extruded and Expanded Polystyrene Foams (abstract) Midland MI
2017 Yes Dow Chemical Company, The; Koehler Breakthrough Sustainable Imaging Technology for Thermal Papers (summary) Collegeville PA
2017 No Dow Coating Materials CANVERATM Polyolefin Dispersions (abstract) Midland MI
2017 No Eastman Chemical Company Efficient Industrial Scale Production of 2,5-Furancarboxylic Acid (FDCA): Bio-Based Alternative to Purified Terephthalic Acid (PTA) (abstract) Kingsport TN
2017 No Eastman Chemical Company; AlterEcho EASTMAN 168TM: The Societal Impact of Plastics Improvement (abstract) Kingsport TN
2017 No Faraday Technology Inc. FARADAYIC® HF-FREE ElectroPolishing Process for Niobium Superconducting Radio Frequency (SRF) Cavities (abstract) Englewood OH
2017 No French Creek Software, Inc. Software Models Lead and Copper Solubility and Corrosion in Municipal Water Distribution Systems To Minimize Lead and Copper Contaminants, Predict the Impact of Changes (abstract) Phoenixville PA
2017 No Garg, Neil; UCLA Catalytic Couplings Mediated by Non-Precious Metal Catalysis (abstract) Los Angeles CA
2017 No Global Green Products LLC Saving Water In Oil And Gas Production (abstract) Palos Heights IL
2017 No GreenLight Biosciences A green chemistry platform for synthesis of double-stranded RNA: First market application in insect control (abstract) Medford MA
2017 No Harper & Hopkins, LLC - DBA Eco Sheep® Eco Sheep® AquaSheepTM Washable Bicycle Chain Lubricant (abstract) Cranberry Township PA
2017 No Kurti, László; Rice University Transition Metal-Free Heteroatom-Transfer Reactions Utilizing Bio-renewable and Multifunctional Reagent Scaffolds (abstract) Houston TX
2017 Yes Merck Research Laboratories Letermovir: A Case Study in State-of-the-Art Approaches to Sustainable Commercial Manufacturing Processes in the Pharmaceutical Industry (summary) Rahway NJ
2017 No Niwayama, Satomi; Texas Tech Highly efficient and practical monohydrolysis of symmetric diesters (abstract) Lubbock TX
2017 No Ohio Soybean Council; Roof Revivers Roof Maxx Shingle Sealer (abstract) Worthington OH
2017 No Preferred Proppants, LLC FloPRO®: A Multifunctional Proppant Coating Technology Delivers Exceptional Solutions for Numerous Hydraulic Fracturing Challenges (abstract) Radnor PA
2017 No Resinate Materials Group, Inc. Building Multi-Functional Polyols Using Recycled Raw Material Streams (abstract) Plymouth MI
2017 Yes Schelter, Eric; University of Pennsylvania Simple and Efficient Recycling of Rare Earth Elements from Consumer Materials Using Tailored Metal Complexes (summary) Philadelphia PA
2017 No Sylvatex Inc. Green Renewable Nanoparticles (abstract) San Francisco CA
2017 No Synalloy Chemicals The Development of SynBurst OB-ECO (abstract) Cleveland TN
2017 No U.S. Water PhosZeroTM Scale & Corrosion Inhibitor (abstract) St. Michael MN
2017 Yes UniEnergy Technologies, LLC The Uni.SystemTM: An Advanced Vanadium Redox Flow Battery for Grid-Scale Energy Storage (summary) Mukilteo WA
2017 No Zhang, Yi-Heng Percival; Virginia Tech Green Biohydrogen Production from Renewable Carbohydrates and Water via in vitro Synthetic Enzymatic Pathways (abstract) Blacksburg VA
2019 No Baker Hughes Bio-molecular or Enzymatic Hydrogen Sulfide Scavenging in the Oil and Gas Industry (abstract) Sugar Land TX
2019 No Baker Hughes Chlorophyll: A green polymer breaker for hydraulic fracturing (abstract) Sugar Land TX
2019 Yes Banerjee, Sanjoy; CUNY Alkaline Zn-MnO2 Batteries for Grid Storage Applications (summary) New York NY
2019 No Brutchey, Richard; USC Baddour, Frederick; NREL; Maolmstadt, Noah; USC Continuous Flow Synthesis of Colloidal Nanoparticles as an Economical, Safe, and Sustainable Nanomanufacturing Method (abstract) Los Angeles CA
2019 No Evolved by Nature, Inc. Activated Silk (abstract) Medford MA
2019 No Hydrodec of North America, LLC Used Transformer Oil Re-Refining, an environmentally responsible and sustainable technology (abstract) Canton OH
2019 Yes Merck Innovating for a Greener Future: Development of a Green & Sustainable Manufacturing Process for Ceftolozane Sulfate (summary) Rahway NJ
2019 No Origin Materials The NaturALL Bottle Alliance: First-to-market poly(ethylene terephthalate) bottle derived from feedstocks that do not compete with food (abstract) West Sacramento CA
2019 Yes Kalion Microbially Produced High-Purity Glucaric Acid for Diverse Uses (summary) Milton MA
2019 No Solugen BioperoxideTM (abstract) Houston TX
2019 No SUEZ Water Technologies and Solutions E.C.O.Film Technology (abstract) Trevose PA
2019 Yes Washing Systems, LLC TruPath® (summary) Loveland OH
2019 No Nlebedim, Ikenna C.; Iowa State Acid-Free Dissolution Recycling of Rare Earth Elements and Cobalt (summary) Ames IA
2020 No Armstrong World Industries, Inc. A Clear, Waterborne Class A Fire Retardant Coating System for Wood Substrates (abstract) Lancaster PA
2020 No Battelle Soy-Based Surfactant (abstract) Delaware OH
2020 No Lin, Song; Cornell University Electrocatalytic Technology for Sustainable Organic Synthesis (abstract) Ithaca NY
2020 No Corteva Agriscience Inatreq™ Active – Improving Cereal Crop Production While Reducing Environmental Impact (abstract) Indianapolis IN
2020 No Dow ECOFAST™ Pure – Sustainable Textile Treatment (abstract) Midland MI
2020 No Dow Breakthrough Sustainable Solventless release coating for hygiene paper (abstract) Auburn MI
2020 No Dow A Breakthrough Corn-based Hair Styling Agent: MaizeCare™ Style Polymer (abstract) Collegeville PA
2020 No DSM Coating Resins Decovery® - High performing biobased binders for decorative and industrial use (abstract) Wilmington MA
2020 Yes Skerlos, Steven; University of Michigan and Fusion Coolant Systems Pure-Cut® (summary) Ann Arbor MI
2020 Yes Genomatica, Inc Biobased butylene glycol eliminates carcinogens and slashes greenhouse gases, with industrial scale production transforming worldwide market (summary) San Diego CA
2020 No Itaconix Water Soluble Zinc Polyitaconate for Odor Neutralization (abstract) Stratham NH
2020 Yes Johns Manville Biobased , Formaldehyde-free Thermoset Binder Formulation (summary) Littleton CO
2020 No Koch Agronomic Services, LLC CENTURO™ Nitrification Inhibitor (abstract) Wichita KS
2020 No McTron Technologies Non-Formaldehyde Bio-renewable Packaging Resin (abstract) Greenville SC
2020 Yes Merck & Co. A Green Solution to the ProTide Synthesis Problem: Design of a Multifunctional Catalyst That Stereoselectively Assembles ProDrugs (summary) Rahway NJ
2020 No Nexus Molecular Recycling (abstract) Atlanta GA
2020 No Nouryon New range of efficient crude oil demulsifiers with excellent environmental profile (abstract) Bridgewater NJ
2020 No Pfizer A Green, Energy Efficient, Chemoenzymatic Process to Manufacture Glasdegib (abstract) Groton CT
2020 No PPG ENVIROCRON™ Extreme Protection Dielectric Powder Coating (abstract) Allison Park PA
2020 No PPG Binder ChemistryforSafer and Better Battery Cathode (abstract) Allison Park PA
2020 No RiKarbon, Inc. Bio-Based Renewable Oils for Cosmetics and Lubricants with a better Eco-Toxicological Footprint (abstract) Newark DE
2020 No RSC Bio Solutions Inherently Stable Environmentally Acceptable Lubricant Systems from Novel Renewable Base Oil Technology (abstract) Indian Trail NC
2020 No Sironix Renewables Bi-Functional Eosix® Surfactants for greener & better performing laundry detergents (abstract) Seattle WA
2020 No SOLUGEN, INC Oxidized sugars for corrosion and scale control in produced water handling systems (abstract) Houston TX
2020 No Sylvatex, Inc. MicroX: A Green Chemistry Approach to Producing a Low Carbon, Low Emissions Alternative Diesel Fuel (abstract) Sunnyvale CA
2020 No The Goodyear Tire & Rubber Company Soybean Oil Technology for Tire Applications (abstract) Akron OH
2020 No Denmark, Scott E. University of Illinois at Urbana-Champaign Harnessing the Power of the Water-Gas Shift Reaction for Organic Synthesis and Precious Metal Recovery (abstract) Urbana IL
2020 Yes Vestaron SPEAR® Insecticide: First Member of a New Class of Biopesticides which show Efficacy comparable to Synthetic Insecticides (summary) Kalamazoo MI

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, AccuprilTM. The resulting process employs more efficient chemical transformations with dramatic environmental and worker safety improvements. Process yields have increased by 30%; process throughput has quadrupled. The process has eliminated methylene chloride and dicyclohexylcarbodiimide. Operations that caused loss of yield due to the intermolecular cyclization of quinapril HCl have been minimized.

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

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

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

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

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

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

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

A Practical and Green Chemical Strategy for the Manufacture of Neurokinin 1 Antagonist, LY686017: Eli Lilly and Company developed an innovative, environmentally benign route for the commercial production of an investigational new drug candidate. This candidate, LY686017, is an antagonist of the Neurokinin 1 (NK1) subtype of tachykinin receptor. It has undergone Phase II clinical trials for the treatment of anxiety and irritable bowl syndrome (IBS). LY686017 is Lilly"s name for {2-[1-(3,5-bis-trifluoromethylbenzyl)-5-pyridin-4-yl-1H-[1,2,3]-triazol-4-yl]-pyridin-3-yl}-(2-chlorophenyl)-methanone. The improved route of manufacture delivers LY686017 in exceptionally high purity (greater than 99.9 percent), despite its complex structure.

Eli Lilly and Company uses a metric called "e-factor" internally that is similar, but not identical to, Sheldon"s E-factor. The e-factor measures the total mass of all raw materials (including water) that are used to produce each kilogram of active pharmaceutical ingredient (API). Overall, the new route for LY686017 has a net e-factor of 146 kilograms per kilogram API, which is an 84 percent reduction relative to the original route designed for Phase I clinical trials. Key technology developed includes a chemoselective SNAr reaction that has potential broad impact within the pharmaceutical industry. For example, industry-leading antidepressants ProzacTM and CymbaltaTM use SNAr chemistry in key manufacturing steps. In addition, COX-2 inhibitors such as pyrazolopyridines can potentially be prepared by this novel green methodology. Using the novel SNAr chemistry to manufacture these large-volume drugs could eliminate over 100 million pounds of processing waste per year.

Eli Lilly demonstrated the selected commercial route for LY686017 on a pilot plant scale during 2006 in Indianapolis, IN. Two prior synthetic routes have been executed at pilot plant scale at Eli Lilly"s Indianapolis, IN and Mount Saint Guibert, Belgium facilities, respectively. Improvement of key green chemistry parameters across the evolution of these routes demonstrates the power of technical innovations and is a testimonial to the importance of incorporating green chemistry into the design and definition of synthetic processes.

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

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

This preproduction system for re-refining used oil reached the pilot plant stage during 2005. The pilot plant has the capacity to process 30 liters per hour of used oil in a continuous process; it has all the components of a larger commercial system. Members of the National Oil Recyclers Association have expressed interest in this technology.

A Safer, Environmentally Superior, High-Performance Acid Inhibitor Designed to Protect Metallic Infrastructure during Industrial Cleaning: Since the early 1900’s, additives have been used to prevent base-metal attack by acids during industrial cleaning. These additives have made cleaning highly efficient through reductions in acid use, base-metal attack, and hydrogen generation, but early acid inhibitors were very toxic. Typical current products include heterocyclic amines and sulfur compounds, benzyl sulfonium salts, formaldehyde, naphthalene and pyridine derivatives, thioureas, propargyl alcohol, and alkylphenol ethoxylate surfactants (APEs), combined with solvents isopropanol or methanol and water.

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

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

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

A Safer, Less Toxic, Reliable, and Green Water Treatment by Smart Release® Technology: Smart Release® Technology is a controlled-release technology designed to prevent scale, corrosion, and microbial proliferation in water systems through the revolutionary delivery and application of existing chemical treatments. Initially, the technology focused on controlling corrosion and scale in cooling towers using tablets coated with a patented polymer that releases the treatment chemicals over a specified time period. In 2010, Dober expanded its Smart Release® product line to include biocides in solid granular form by creating a patent-pending canister membrane that also releases the chemicals over a specified time period, often 30 or 60 days.

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

Because the concentration of active ingredients is so high, 100 pounds of Smart Release® chemicals equate to 600 pounds of standard liquid chemicals. The simplicity and reliability of Smart Release® technology means that less service time is required. Smart Release® technology has been endorsed by two of the leading water treatment companies in the United States and a leading global supplier of cooling towers, fluid coolers, and evaporative condensers. During 2010, Dober created an enhanced corrosion and scale-inhibitor tablet that contains no phosphate. Due to increased regulations limiting phosphate products, Dober expects this product to have large sales in the future.

A Systematic Methodology for the Design and Identification of Environmentally Benign Chemicals: Hydrofluorocarbon emissions from the refrigeration and air conditioning sector in the U.S. currently amount to approximately 13 million metric tons of carbon equivalent and are expected to grow to 38 million tons by 2010. Retail food refrigeration accounts for 25% of these emissions: a typical supermarket leaks about 1 ton of refrigerant every year. The fundamental scientific goal of the nominated project is to reduce these major sources of environmental pollution by designing environmentally benign refrigerants. Using his pioneering optimization methods, Professor Sahinidis has invented a powerful way to search the astronomically large space of possible compounds and identify the entire set of compounds that are potentially suitable automotive refrigerants.

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

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

The end result, ASE® 350, is an automated system that greatly reduces the amount of organic solvent required to extract analytes. ASE® technology significantly reduces solvent waste, solvent vapors, and solvent exposure to laboratory personnel. With the introduction of the ASE® 350 system, users can reduce the amounts of solvent even further by activating the Solvent Saver ModeTM. This mode can save up to an additional 33 percent of solvent during each extraction. As one example, the amount of solvent required to analyze a year’s worth of 10 g samples is 49 L for the ASE® 350 system in the Solvent Saver ModeTM and 3,120 L for the traditional Soxhlet method. This is a significant decrease in the amount of organic solvent waste generated and the amount of solvent vapors released into the environment. Dionex introduced its ASE® 350 system in 2008.

ACCOLADETM Synthetic-Based Drilling Fluid System: In 2001, Halliburton introduced a revolutionary synthetic-based drilling fluid (SBF) called the ACCOLADETM system. ACCOLADETM is the first SBF to couple superior environmental compliance with exceptional drilling performance, allowing operators to drill with high efficiency while they minimize environmental impact in sensitive offshore areas. Halliburton formulated ACCOLADETM to exceed U.S. EPA’s environmental criteria for sensitive areas; ACCOLADETM is the highest rated of all drilling fluids for its low toxicity and high biodegradability. The system far exceeds all regulations governing discharge of cuttings generated with SBF for drilling offshore in the Gulf of Mexico.

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

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

Through 2005, 20 different operators had used ACCOLADETM to drill over two million feet of holes for more than 190 oil wells in the Gulf of Mexico. In 2005, ACCOLADETM also had its first international use, in Venezuela.

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

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

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

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

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

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

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

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

The Rhein Chemie insulation system comprises an ethoxylated soy polyol mixed with a common polyester, chain-extended with an isocyanate and modified with Rhein Chemie additives (such as Stabaxol® P 200 and Addocat® 102) to form a "green" polymer. The Stabaxol® additive, a carbodiimide, scavenges the acid groups on the biopolyols and improves both the reactivity and the hydrolytic stability of the foam system. The Stabaxol® additive also minimizes the deactivation of the catalysts by reacting out the acids that lead to variable reactivity. By 2004, only two years after Rhein Chemie developed this technology, its additives were being used in low-density insulated spray foams for industrial, commercial, and residential insulation.

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

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

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

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

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

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

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

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

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

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

Because Sepracor implemented the more efficient process early during the development cycle, the company will receive the environmental and economic benefits for the entire product lifecycle. Sepracor developed this chemistry during 2006 and 2007; the company subsequently used it to produce 75 kilograms of high quality material at plant scale.

AeroClay®: A Green Aerogel for Industry: Expanded polystyrene (EPS) is made from polystyrene (PS), a petroleum product. It is used as a packaging material, thermal insulator, and acoustical insulator. PS is foamed into EPS beads using pentane, a volatile organic compound (VOC), as the blowing agent. The EPS beads are expanded and molded into blocks, which are then cut into specific shapes as required for various applications. Of the 2.62 million tons of polystyrene generated in 2008, only 0.8 percent were recycled and less than 1 percent were incinerated for energy.

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

AeroClay® eliminates worker exposure to styrene, a suspected carcinogen, and does not require any blowing agents. Instead, AeroClay® uses poly(vinyl alcohol) and clay, which are essentially nontoxic, nonhazardous materials that would not harm workers who are currently exposed to chemicals during EPS manufacture. AeroClay® would also reduce the amount of waste in landfills. Because it is biodegradable, AeroClay® does not take up space in landfills or cause pollution during production or incineration. AeroClay® is also less flammable than EPS, while providing similar mechanical properties in packaging and insulating applications. During 2010, Aeroclay, Inc. established a pilot facility in Cleveland, Ohio, to produce and test prototypes and to produce small batches.

AGROTAIN® N-(n-butyl)Thiophosphoric Triamide: Urea is now the favored form of solid nitrogen-containing fertilizer and is rapidly displacing anhydrous ammonia in the nitrogen fertilizer market. The market share of world nitrogen consumption has risen from 5% in 1962 to 37% in 1986 for urea. There are many reasons for this increase. Urea is a source of nitrogen for crop fertilization that is easily handled and transported, higher in nitrogen content than other common solid nitrogen fertilizers, and can be readily bulk blended with other fertilizer components such as potassium chloride, diammonium phosphate, and other materials to prepare multinutrient fertilizers.

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

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

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

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

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

Commercial coatings systems based on aldimine-isocyanate chemistry have been developed and are finding widespread acceptance as a solution to VOC restrictions. Current applications exist in the automotive refinish business where aldimines are used to make coatings containing only 20 to 25 percent volatile solvents, replacing products that have 40 to 50 percent volatile solvents by weight. Since the introduction of this technology in 1995, old technology resin systems requiring more than 100,000 kilograms of additional organic solvent have been displaced.
This volume will triple in 1996 and approach one million kilograms in 1997. More importantly, the volume of organic solvents displaced as other market areas adopt this technology is expected to increase dramatically. Additional benefits of this technology include: allowing low VOC coatings to be developed, resulting in large solvent savings for a given application without transferring environmental liability to production or use; it is already in significant commercial use, and will become a high volume product line by the end of the century, resulting in nontrivial source reduction of organic solvent emissions; it is compatible with existing and future coatings systems; it does not require significant capital investment to employ; and it increases productivity.

Alkyl Polyglycoside Surfactants: Henkel Corporation"s alkyl polyglycoside (APG®) surfactants are a class of nonionic surfactants that have been pioneered and marketed to the detergent and personal care industries under the Glucopon® and Plantaren® trade names since 1992 and 1990, respectively. APG® surfactants are manufactured from renewable resources including fatty alcohol, derived from coconut and palm oils, and glucose, derived from corn starch. APG® surfactants are more innocuous to the environment than petrochemical-based technologies, are readily biodegradable, and have very low ecotoxicity.

APG® surfactants are highly efficient cleaners and have led to a significant reduction in overall chemical consumption in cleaner formulations and ultimately the amount of chemicals released to the environment. APG® surfactants also permit the formulation of concentrated cleaners that require less consumer product packaging and consequently reduce packaging waste. APG® surfactants are considerably less toxic and safer to humans and the environment than other major surfactants. APG® surfactants permit the formulation of less irritating and safer consumer products and significantly reduce the possible environmental impact associated with an accidental spill. Henkel Corporation"s 50 million pound per year APG® surfactant plant has been operating in Cincinnati, Ohio, since 1992. A second plant was started up in Dusseldorf, Germany, in 1995, by Henkel Corporations"s parent company, Henkel KGaA.

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

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

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

They are applied exogenously, preferably in water-efficient, drip irrigation systems. Stoller serendipitously discovered that these products not only enhance crop yield and quality (the original objective), but also strongly suppress damaging nematodes, resulting in much larger and more nutritious crops. Stoller has done extensive testing and intuitive modeling to determine which combination of ingredients among 20 minerals, dozens of plant hormones, and hundreds of small molecules is most effective. In 2006, Stoller tested a wide range of its products and noted universal effectiveness. In all cases, crop canopy increased, root mass increased, and nematodes were reduced to varying degrees, but always with very desirable yields and crop quality. Additional studies are in progress.

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

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

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

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

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

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

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

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

The U.S. Food and Drug Administration cleared this technology for sale in the United States and STERIS commercialized it under the brand name, ResertTM XL HLD High Level Detergent during 2008.

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

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

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

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

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

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

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

STERIS developed Prolystica® Ultra Concentrate cleaning chemistries and introduced them in 2006 as an innovative, green alternative. The product line includes a neutral pH enzymatic presoak and cleaner, a neutral pH detergent, and an alkaline detergent with lower alkalinity. All three formulations are phosphate-free. They contain surfactants that are biodegradable, as well as biodegradable corrosion inhibitors (biodegradable polycarboxylic acid), chelating agents (an iminodisuccinate and a methyl glycine diacetate), and sequestering agents (including inulin derived from chicory).

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

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

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

The new synthesis for duloxetine was demonstrated on a pilot plant scale in 2002; Eli Lilly is now developing its pilot plant process into an improved commercial process. The new synthesis for atomoxetine is currently being used at an Eli Lilly production facility.

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

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

Dow’s new technology uses an alkaline hydroxide solution with an added oxidant, which behaves isotropically like the HF–nitric acid bath and delivers equivalent or better performance while significantly reducing the health, safety, and environmental negatives of the current technology. This alkaline texturizer is compatible with existing equipment configurations. The process also reduces the cost of ownership by reducing operational costs including process energy and waste treatment. The makeup chemistry for the new solution requires about 8-percent active ingredients compared to 45-percent for the HF–nitric acid bath. The HF system requires replenishment with three times more reagents than does the new system. The new technology consumes substantially fewer materials, which results in significant cost savings and less chemical waste. Dow will be alpha-testing its new, multicrystalline texturizer in January 2010 and expects to make it available commercially later in 2010. There are no other suitable replacements for HF–nitric acid on the market today or described in the literature.

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

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

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

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

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

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

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

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

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

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

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

Professor Maffia has focused on the production of collagen nanofibrils in ongoing research over the past 20 years. Over the past 5 years, he has shifted the starting material to ground bovine corium, a low-value byproduct of the meat-processing industry. Two patents have been issued for this technology. This technology received a Lindbergh Award in 2004 as an example of the balance between technological advancement and protection of the environment. Some small businesses (including Catalyx, Inc.) and government agencies are investigating the technology.

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

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

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

The U.S. Food and Drug Administration granted accelerated approval to PrezistaTM on June 23, 2006. With its improved, scaled-up process, Johnson & Johnson reduced raw materials and hazardous waste by 46 tons, reduced hydrogen gas by 4,800 cubic meters, and eliminated 96 tons of methylene chloride in 2006.

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

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

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

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

On average, GM now recycles or reuses more than 97 percent of its waste materials and converts the remaining less than 3 percent to energy, replacing fossil fuels at waste-to-energy facilities. Within the United States, 13 facilities are landfill-free: they recycle, reuse, or convert to energy all wastes from their normal operations. During 2010, these facilities diverted over 385,000 tons of waste from landfills and avoided emissions equivalent to 2.1 million metric tons of carbon dioxide (CO2e). Currently, GM’s process is part of 76 global automotive manufacturing operations that reuse, recycle, or convert to energy all the waste they generate. During 2010, GM recycled or reused 2.5 million tons of byproduct materials worldwide.

Because environmental cross-industry collaboration and community stewardship are important, GM directs its engineers to mentor other companies, industries, and communities. For example, during the 2010 Gulf of Mexico oil spill, GM assembled an engineering team to recycle oil-soaked, absorbent polypropylene booms recovered from the Alabama and Louisiana coasts. To retain the chemical value of these booms, GM processed them into parts for the Chevrolet Volt. To date, this technology has prevented over 100 miles of oil booms and the oil retained in them from entering American landfills. It has also prevented 70 metric tons of CO2e from entering the atmosphere.

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

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

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

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

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

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

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

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

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

The water-based Aquence® autodeposition coating technology developed by Henkel recently set a new industry precedent by coating an entire vehicle body in assembly. Aquence® customers can realize a 40-percent footprint reduction, reduced capital expense and paint shop complexity, decreased energy consumption, elimination of heavy metal sludge, and improved inside-out corrosion performance. Henkel launched its Aquence® 925G epoxy-acrylic coating for industrial primers and automotive body primer in 2007 and its Aquence® 930 epoxy-acrylic coating for improved cyclic corrosion resistance in the frame and chassis market in 2008. Aquence® is in trials globally at over 150 locations.

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

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

Hach Company has developed an arsenic-free SPADNS reagent and commercialized it as SPADNS 2. In place of sodium arsenite, the new method uses a proprietary, nontoxic reducing agent. The waste from using SPADNS 2 can be disposed of safely without the special handling required for arsenic. The arsenic-free SPADNS 2 Hach Method 10225 outperforms both EPA-compliant methods (EPA Method 340.1 and Standard Method 4500-F D) in reagent water and matrix spike recovery and precision.

Apart from this change, the core chemistry of the new test is identical to traditional SPADNS. The new SPADNS 2 reagent can be used with any instrument, test procedure, and calibration curve currently used to measure fluoride with the original Hach SPADNS method. Although the SPADNS 2 reagent continues to be acidic and should be handled with care, its use generates no arsenic hazardous waste and operators have no risk of exposure. Hach commercialized this technology during 2007.

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

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

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

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

Irgalube F10 passed the ASTM fuel economy test procedure, registering a fuel economy improvement of 1 to 1.5% over the standard test oil. A fuel-efficiency improvement of 1% could have an annual impact of reducing carbon monoxide by 1.2 billion pounds, Ox emissions by 240 million pounds, and particulate matter emissions by 17 million pounds (based on National Air Quality and Emissions Trends Reports, 1996).

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

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

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

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

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

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

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

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

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

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

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

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

Moreover, they are currently considered for therapeutic applications such as the development of new vaccines against pathogenic, multidrug-resistant bacteria and as cytotoxic agents against human cancer cells. VH Biotechnology has developed a novel, green bacteriocin composition for use as a microbicide in commercial applications including pulp and paper mills, fuels, biofuels, cooling water systems, and poultry farms. The bacteriocins are obtained by standard fermentation using lactic acid bacteria. Two paper mills using these bacteriocins showed much lower bacterial counts. In diesel fuel, bacteriocins reduced microbial levels by 99.95 percent over controls; in gasoline, the reduction was 89 percent. When used to sanitize water on poultry farms, bacteriocins at 100 grams per cubic meter of water were able to match the performance of chlorine at 12 grams per cubic meter. VH Biotechnology developed this technology in 2008 and filed a U.S. patent application for it in March 2010.

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

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

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

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

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

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

The BPXTM process is currently in use at ten plants managed by Broin. In May 2005, Broin started up BFRACTM and BPXTM operations at a retrofitted 50-million-gallon-per-year ethanol biorefinery in Coon Rapids, IA. Broin is currently marketing the majority of its over-40-percent protein distillers grains from the BFRACTM and BPXTM processes as Dakota Gold HP (HP = high protein). This low-fat, high-fiber, high-protein product is opening new markets to distillers grains in the swine and poultry feeding industries.

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

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

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

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

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

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

The potential of starch and cellulose as drying agents for fuel alcohol was reported in Science in 1979 and scaled up for industrial use by 1984. Ground corn is used in an adsorption process that replaces azeotropic distillation to dry approximately 750 million gallons of fuel ethanol annually. The corn-based adsorbent proved to save energy while avoiding the need to use benzene as the drying agent. The fundamental research and demonstration of the potential of starch- and cellulosebased adsorbents for desiccant air coolers, is an on-going research project at Purdue University that evolved from the first application of corn grits to the drying of fuel alcohol.

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

BioBased Tile®: A Non-PVC Flooring Made with Rapidly Renewable Resources: Historically, resilient vinyl composition tile (VCT) flooring has been manufactured with binders derived from fossil fuel. Poly(vinyl chloride) (PVC) is the primary binder used to combine plasticizers, processing aids, stabilizers, limestone, and pigments into resilient flooring. Other binders include polyolefins, ethylene acrylic resins, and synthetic rubbers. In 2008, Armstrong commercialized BioBased Tile® flooring, a revolutionary flooring product that uses natural limestone and a proprietary polyester binder made from rapidly renewable materials. Armstrong developed BioBased Tile® specifically to provide a PVC- and phthalate-free alternative to VCT for K-12 education applications.

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

Each year, replacing VCT with BioBased Tile® flooring could save 140 million pounds of virgin limestone, eliminate 336,000 pounds of volatile organic compounds (VOCs) from manufacturing, capture 44 million pounds of carbon dioxide (CO2) from the atmosphere in biobased components, and reduce energy consumption equivalent to 475 billion Btu (or 56 million pounds of CO2). BioBased Tile® flooring is certified by Floor Score with no detectable VOCs. It contains no materials listed in the table of Chronic Reference Exposure Levels (CRELs) established by California’s Office of Environmental Health Hazard Assessment (OEHHA). For green building initiatives, BioBased Tile® contributes up to four points toward LEED certification and will be NSF 332 certified in January 2012.

Biocatalytic and Biomimetic Process for the Synthesis of Nitroaromatic Intermediates and Destruction of Nitrocompounds, Including Explosives: Nitroaryl and nitroheterocyclic compounds—found in antibiotics, radio sensitizers, explosives, dye intermediates, herbicides, and pesticides—require a technology to synthesize and destroy nitrocompounds. The massive stockpiles of explosives alone and the contamination they cause in water, soil, and sediment around the world pose a serious threat to humankind, health, and the ecology. Currently, there are no acceptable technologies or resources to demilitarize aging stockpiles and clean up their contamination. Current stockpiles of energetic materials requiring resource recovery or disposition (RRD) weigh in at about 449,308 tons. Through 2001, over 1.2 million tons will pass through or reside in the RRD account (Joint Ordnance Commands Group, 1995).

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

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

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

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

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

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

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

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

The resulting nontoxic, biodegradable product has excellent properties as a UV-A and UV-B absorber, free-radical trap, and antioxidant, making it a superior substitute for conventional petroleum-based sunscreen active agents and skin care ingredients. Human sensitivity skin testing of SoyScreenTM has confirmed its safety and lack of allergic response. In November 2005, iSoy Technologies constructed a pilot plant for commercial synthesis. It plans to introduce SoyScreenTM into the market in a variety of skincare products in 2006.

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

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

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

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

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

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

During 2007, Organic Recovery constructed a 60-ton-per-day, full-scale processing facility in Florida. It also filed for a patent on its technology.

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

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

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

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

Biodegradable Copolyester: An integrated resource management approach to the use of materials such as paper, metals, and plastics considers the entire life of a product from raw materials to final disposition. After the useful life of some products, the final disposition depends on various options. The products can enter the municipal solid waste (MSW) stream to a landfill, an incinerator, or an incinerator with electricity/steam production. They also can be discarded on land or at sea, be recycled by industry, or be reused for another purpose by the consumer. One growing option, which Eastman Biodegradable Copolyester 14766 is designed to complement, is composting.

This is a process that essentially mimics nature"s biodegradation process (i.e., carbon cycle) and has been used over the ages to various degrees. The process is now recognized to have various benefits, one of which is the reduction of the amount of waste to landfills or incinerators (both of which are expensive to build and maintain, not to mention the problems inherent with siting a new one). In addition, the compost resulting from biodegradation is a soil amendment that adds water retention and other benefits to soils. In fact, such a compost is more beneficial to agricultural soil regeneration than chemical fertilizers. Eastman Biodegradable Copolyester 14766, a patented aliphatic/aromatic copolyester of adipic acid, terephthalic acid, and 1,4-butanediol, was engineered to decompose under proper conditions into water, carbon dioxide, and biomass.

This innovative new product also exhibits such features as low cost, tensile properties similar to low density polyethylene (LDPE), and a soft feel, and is blendable with natural polymers such as starch. Extensive biodegradation and toxicity evaluations demonstrated definitively that Eastman"s new product biodegrades completely at rates comparable to paper without negatively impacting the ecosystem. The material can be extruded into blown film, extrusion coated, and spun into fiber. A plethora of applications is envisioned for Eastman Biodegradable Copolyester 14766 including compost bags, personal hygiene items, medical products, and coated paper and board.

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

Mater-BiTM is a product technology that offers enormous advantages for dealing with the problems of solid waste disposal. Disposal of conventional plastic products, which constitute the largest share of disposable products, has a significant negative impact on the environment. Typically, disposal products are landfilled and rapidly diminish landfill capacity. Being compostable, disposable products made of Mater-BiTM are fully recyclable. Biodegradable food serviceware, for example, presents a significant opportunity for reducing the volume of the solid waste stream. In 1994, nearly 39 billion pieces of disposable cutlery (knives, forks, and spoons) were used in the United States.

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

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

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

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

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

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

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

Using AVAIL® polymers with granular or fluid phosphorous fertilizers greatly increases phosphorous availability in soils, resulting in 80–90 percent of the phosphorous being available to crops. Benefits include reduced phosphate accumulation in soil, reduced phosphate runoff, and reduced contamination and eutrophication of waterways. AVAIL® produces an average increase of 10–15 percent in crop yields at minimal cost. This technology lowers the environmental impact of biomass-derived fuel such as ethanol, butanol, and biodiesel. Because the phosphorus supply is much more energy-efficient, far less fuel is consumed to grow useful biomass and produce plant-derived liquid fuels. AVAIL® has been marketed in the United States and Canada since 2004. Currently, SFP is selling 40 million tons of AVAIL® per year internationally.

Bio-Derived Green Primary Polyvinyl Chloride Plasticizers with Improved Thermal Stability and Plasticization Efficiency: Globally, over 13 billion pounds of plasticizers are produced annually with 90 percent of all plasticizers being used to soften or flexibilize PVC for use in myriad applications such as vinyl flooring, films, blood bags, wall paper, inks, plastisols, shoes and others. Additionally, 90 percent of all plasticizers are phthalates, certain classes of which have come under severe scrutiny due to their suspect endocrine disruption activity. In July 2005, the European Union permanently banned the use of phthalates in all children’s articles.

In October 2007, the California Assembly AB1108 signed into law banning the use of phthalates in certain applications. President Bush signed the Consumer Product Safety Improvement Act (CPSIA) in August 2008, which led to the banning of three phthalate ester plasticizers in toys. Thus there is an immediate need in the PVC industry to replace phthalates with cost effective and safe "green" plasticizers based on renewable resources. Besides the health concerns surrounding the phthalate plasticizers, vinyl resins tend to have poor thermal stability that would typically require the use of metallic heat stabilizers, any of which have their own environmental concerns. Several of these new bioplasticizers provide improved thermal stability and may result in a reduction or elimination of these metallic stabilizers, another environmentally friendly benefit. Replacing 25 percent of the global plasticizer production with a bio-based product derived from renewable resources offers significant energy savings in the range of 5 trillion Btu per year with reduced carbon dioxide emissions of about 1 lb less of CO2 emission per pound of plasticizer consumed.

Battelle patented technology addresses the need for a safe and cost effective alternative to phthalates. Battelle has developed several novel plasticizer compounds based on extensive modeling studies to identify chemical structures derived from renewable feedstock to optimize compatibility of the plasticizer molecule with PVC resin to enhance thermal stability and plasticization efficiency. In 2008, the patented technology was licensed to PolyOne, based in Ohio and Nexoleum, based in Brazil, respectively. In 2009/2010, PolyOne working with their partner Archer Daniels Midland successfully scaled up and introduced to the industry reFlexTM 100, a first generation bio-derived green plasticizer for PVC.

This product has been sold commercially for use in plastisol formulating (liquid vinyl systems) as a co-plasticizing accelerator replacing fast-fusing plasticizers such as BBP (butylbenzyl phthalate) and DBP (dibutyl phthalate). Nexoleum has sold several hundred tons of bio-derived NexoTM E1 plasticizer in Brazil. Market feedback indicates that the new bio-plasticizers are nearly a "drop-in" replacement for phthalates in many applications requiring minimal, if any, changes to current practices in the PVC industry. In 2010, a new 200 ton/ month plant was commissioned in Brazil to meet the growing demand for the new bioplasticizer.

Bioderived Solvents, Surfactants, Fuel Additives, and Monomers: Many applications of renewable resources require the transformation of these resources into platform molecules, which then are readily converted into commercial products. Levulinic acid is one such platform molecule. Biofine, Inc. (winner of the 1999 Presidential Green Chemistry Challenge Award in the Small Business Category) discovered a manufacturing process to make levulinic acid from cellulosic biomass. This process is currently moving toward large-scale commercial production. DuPont is taking the next step by developing commercially viable processes to convert levulinic acid into a host of desired products. DuPont uses novel catalytic transformations along with other techniques of green chemistry to develop products derived from levulinic acid that can replace petroleum-derived solvents, monomers, and transportation fuels.

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

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

These products include a biodegradable deicer, which has low corrosivity and ice-melt properties equivalent to NaCl. There is a family of succinate-esters that functions as a biodegradable, recyclable degreaser for machinery. Another formulation enhances the efficacy of certain herbicides, allowing less to be used on the fields. The process is being actively implemented, with a 150,000 L fermentation demonstration scheduled for early 2002. This platform has developed from an active collaboration by all parties. The combination of biotechnology, efficient separation technology and novel chemical synthesis provides economics enabling commercialization of a broad range of products.

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

This increased frequency would greatly increase the operation expenses for the scrubber as well as expose operations to greater risks of caustic burns resulting from the increased handling requirements. As an alternative to caustic treatment, biofiltration was investigated as a possible solution. In biofiltration, micro-organisms supported on a stationary porous media bed are used to destroy pollutants from waste gases flowing through the bed. The micro-organisms commonly occur in nature, and various media are excellent candidates for sustaining the micro-organisms and harboring their nutrients. In July 1993, a pilot biofilter was set up to test its effectiveness on hydrogen sulfide removal.

The pilot biofilter proved that biofiltration was a technically feasible and economically attractive alternative to the 12C-20 caustic scrubber for hydrogen sulfide removal from the vent gas stream. Due to this success, a fullscale biofilter, 12C-1022, was installed in December 1995 to replace the 12C-20 caustic scrubber.

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

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

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

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

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

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

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

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

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

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

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

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

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

BioTrans® 1000 Soybean-Based Transformer Fluid: BioTrans 1000 is a transformer dielectric fluid based on soybean oil. The viscosity and volatility of vegetable oil triglycerides are naturally suited for use as a dielectric fluid and provide extremely low volatility leading to reduced flammability. The oil is hydrogenated to tailor the fatty acids in the triglyceride to optimize oxidative stability and low temperature fluidity. Chemical factors, which negatively impact the dielectric performance of BioTrans 1000 were identified. Processing, beyond that normally used for food grade vegetable oil, was developed to minimize their impact on insulating properties. The base oil is further formulated with an additive package specially designed to maximize the low temperature fluidity and minimize toxicity to marine life.

The ester functionality of the triglyceride in BioTrans 1000 enables the remarkable extension of transformer life relative to that found for a petroleum oil fluid. Transformer life is limited by paper degradation – which is catalyzed by water present in the paper itself. The ability of BioTrans 1000 to solubilize water, thus dehydrating the paper extends the paper life by four times.

Naturally derived properties, special formulation, and optimized processing are combined to provide a safe, biodegradable, and non- toxic fluid with significant performance advantages in BioTrans 1000.

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

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

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

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

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

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

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

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

TecTalis is an environmentally sustainable technology that eliminates pretreatment sludge, reduces landfill requirements, and simplifies wastewater treatment. The conversion coating is free of phosphate, volatile organic compounds (VOCs), and carbon dioxide (CO2) equivalent emissions. The process operates at ambient temperature, reducing utility and natural resource requirements. Henkel’s TecTalis has been in use in the United States and internationally since 2007.

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

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

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

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

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

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

n customer formulations, Burn-OutTM FR compounds offer potential cost savings of 20-50 percent compared to current FRs containing halogen and PBDE–antimony. Performance is equal to or exceeds that of other products. Burn-OutTM FR reduces landfill disposal costs associated with hazardous materials. Burn-OutTM FR may be used in virtually all aqueous systems and many polymer systems. Applications include paper, corrugated packaging, woven and nonwoven textiles, insulation, ceiling tiles, construction materials (e.g., wood, urethane insulation, and steel intumescent coatings), adhesives, paints, and other FR coatings, especially in the automotive, military, and marine markets. Performance Chemicals is planning to test Burn-OutTM FR in bedding and mattresses. Performance Chemicals commercialized Burn-OutTM FR in 2011.

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

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

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

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

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

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

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

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

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

Catalytic Treatment of Hydrogen Peroxide in IBM Semiconductor Wastewater: Semiconductor manufacturing produces a large ammonia and hydrogen peroxide wastewater stream that requires treatment. Through 2009, the industry standard for treating this wastewater stream was to reduce the hydrogen peroxide with sodium bisulfate then to neutralize it with sodium hydroxide. The next step was separating ammonia by distilling the wastewater to remove ammonium hydroxide. The added sodium bisulfite and sodium hydroxide contributed high levels of total dissolved solids (TDS) to IBM’s wastewaters and final effluent discharge, and both were also becoming increasingly expensive. In 2003, IBM’s East Fishkill plant (EFK) began an initiative with the New York State Department of Environmental Conservation to reduce the TDS in the site’s effluent discharge to a small receiving stream.

Over the next six years, IBM EFK investigated alternative technologies to remove sources of TDS from its manufacturing wastewaters and wastewater treatment processes. In early 2009, IBM qualified a catalytic enzyme process to replace the existing sodium bisulfate process for removing hydrogen peroxide from the ammonia wastewater. This process uses a small quantity of a catalase derived from Aspergillus niger fermentation to decompose peroxide into water and oxygen. It does not contribute TDS to the site’s effluent discharge and costs a fraction of the previous treatment. The new process incorporates existing building equipment as much as possible and integrates flawlessly into the existing treatment system.

IBM started and completed design and construction of the full-scale peroxide treatment system in 2009, with startup continuing through March 2010. Annually, this new process eliminates the use of 510,000 gallons of 38 percent sodium bisulfite and 135,000 gallons of 50 percent sodium hydroxide for acid neutralization. It reduces chemical costs by $675,000 per year. The catalytic reduction of hydrogen peroxide process has been online continuously since the beginning of 2010 and is currently patent-pending.

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

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

Two environmental advantages of ZeaChem’s technology are reduced fossil-derived carbon dioxide (CO2) emissions and smaller land-use footprints. The ZeaChem route generates roughly 1.45 pounds of fossil-derived CO2 per gallon of ethanol compared to 3.63 pounds and 12.54 pounds of fossil-derived CO2 per gallon of ethanol from sugarcane and corn dry milling, respectively. Projections on the combination of ZeaChem’s high-yield factory technology with high-yield energy farms and improvements in automobile efficiency suggest that as much as 30 percent of America’s light-duty fuels could be produced from the amount of agri¬cultural land currently used to produce corn ethanol. Such projections fundamentally change the policy debate on the environmental aspects of ethanol as a liquid transportation fuel. Dur¬ing 2008, ZeaChem began construction of a 10-ton-per-day cellulosic ethanol facility.

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

DuPont Cerenol® is a family of high-performance poly(ether diols) made in a sustainable, unconventional, self-condensation polymerization process that primarily uses a renewably sourced ingredient, 1,3-propanediol (Bio-PDOTM). The process uses a soluble acid catalyst at less than one percent by weight that is subsequently removed during purification. The benefits of the Cerenol® platform include (1) a large number of polymers and products from renewably sourced polyols, (2) high-value uses for agricultural feedstocks, and (3) manufacturing processes that not only eliminate hazardous chemicals and process conditions but are also more energy-efficient and generate reduced levels of greenhouse gas emissions versus competing petroleum-based products. Although it has no in-kind competitors, Cerenol® has a significantly lower environmental footprint than does the related petroleum-based compound, poly(tetramethylene ether glycol), as determined by an ISO 14000-compliant life cycle analysis (LCA). From cradle-to-gate, Cerenol® provides 30-percent savings in nonrenewable energy and a 40-percent reduction in greenhouse gas (GHG) emissions.

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

C-FREETM Pulp Ozone Bleaching Project: For decades, ozone has been acknowledged as the most promising alternative to chlorine in the bleaching of wood pulp in the forest products industry for the protection of our environment. Despite this recognition, no satisfactory technology was commercially available that met both cost and quality criteria of pulp producers until the early 1980’s. Union Camp Corporation, a world leader in pulp and paper production, embarked on a research and development program to solve the problems identified with ozone delignification, including the erection and operation of a $6 million, 25 TPD pilot plant. Based on the results of its R&D and pilot plant studies, Union Camp became convinced that an environmentally friendly bleaching process could be developed on a commercial scale.

The result was the full scale implementation of the world’s first high consistency ozone OZ(EO)D bleach line for kraft pine pulp in Union Camp’s Franklin, Virginia, fine paper mill during the fall of 1992. The ozone pulp bleaching process is patented under the trade mark C-Free TM. While the C-FreeTM pulp bleaching technology has significantly lower bleaching costs at equivalent product quality compared to conventional chlorine based bleaching, the most important benefit is the significant reduction in effluent properties, volume and fresh water requirements. The effluent biological oxygen demand (BOD), chemical oxygen demand (COD), color, absorbable organic halides (AOX) and chloroform have been reduced by 73 percent, 83 percent, 98 percent, 99 percent, and 99 percent respectively compared to conventional chlorine CEDED bleaching. In addition, dioxin and the 28 chlorophenols identified by the EPA are nondetectable.

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

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

In 2008, Professor Mascal and his group described a process that meets all three objectives. Their method involves digestion of cellulose in a biphasic aqueous acid–organic solvent reactor to give remarkably high yields of the novel organic platform chemical, 5-(chloromethyl) furfural (CMF). The method works equally well on raw biomass, producing not only CMF from the cellulose of the feedstock, but also furfural itself from the C5 sugar fraction (i.e., hemicellulose). It uses all of the carbohydrate in the biomass without requiring that lignin first be stripped from the lignocellulose.

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

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

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

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

SABIC has commercialized these environmentally sustainable products under the trade names Valox iQTM and Xenoy iQTM resins. These resins have up to 65-percent carbon content from recycled waste. The environmental benefits of Valox iQTM and Xenoy iQTM resins include up to 55–75-percent reduction in both carbon dioxide emissions and process energy. These benefits are accomplished without sacrificing the quality of the final product. During 2008, the first full year of commercialization, the materials were used successfully in more than 20 applications, generating $3.5 million in sales.

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

The user-friendly French Creek Software Calculation Engine provides scale prediction, corrosion modeling, and dosage optimization for cooling water treatment. Before French Creek Software introduced its line of software in 1990, few tools were available to predict scale and corrosion problems or to optimize treatment. The available tools such as simple indices and rules-of-thumb contained inaccuracies that resulted in operation at lower-than-desired concentration ratios, in increased water use within plants, and in higher-than-necessary discharges of treatment chemicals to the environment.

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

In 2006, one of the largest water treatment service companies used the Calculation Engine to save over 21 billion gallons of water by implementing an award-winning automated cooling system controller and companion software. Through applications by other major companies and approximately one-third of the smaller regional companies, French Creek’s commercial and private-label programs are estimated to have saved additional billions of gallons of water. In typical applications, French Creek technology has optimized dosages of water treatment chemicals and reduced treatment rates by up to 50 percent.

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

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

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

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

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

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

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

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

Its lower use rates mean less pesticide gets into the environment with a corresponding reduction in the exposure of workers and the public. Chlorantraniliprole’s proven safety to bees and other beneficial arthropods allows its use in integrated pest management (IPM) programs. In addition, its mode of action provides an important new tool for managing insecticide resistance. DuPont manufactures chlorantraniliprole in a convergent commercial process that minimizes organic solvents, recovers and recycles the solvents it does use, minimizes waste, eliminates regulated waste products, and establishes inherently safer reaction conditions. Chlorantraniliprole is rapidly displacing less desirable products from many key markets. In 2011 alone, more than 20 million farmers and 400 crops benefitted from insect control by chlorantraniliprole.

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

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

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

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

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

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

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

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

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

This is the first oxygen enrichment technology to simultaneously reduce both Ox (by 15%) and particulates (by 60%). It is an all-in-one, in-cylinder treatment that solves the emissions problem at the source, does not drain engine power (in fact, increases gross power by 18%), and improves fuel efficiency (2 to 10% improvement in brake-specific fuel consumption across the entire load range in a locomotive notch schedule). This breakthrough technology will be important to diesel engine manufacturers, who are faced with helping their customers meet lowered regulatory standards beginning in model year 2002.

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

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

CleanGredientsTM presents carefully selected information on chemical raw materials including performance properties, environmental fate, human and environmental health, safety, and sustainability in a format that helps formulators easily identify candidate ingredients for environmentally preferable product formulations. CleanGredientsTM lists only chemicals that have been characterized adequately and meet key human and environmental characteristics. Formulators can search the database by general ingredient information and physical properties to identify suitable candidate ingredients for particular applications. The first CleanGredientsTM module (surfactants) was launched in 2006. Within 2 months, 11 raw material suppliers and 50 formulators had subscribed to list ingredients or access information. Modules for solvents, chelating agents, and other product classes are under development.

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

In 2001, the FDA approved the use of ozone as a disinfectant in food plants. Ozone is a potent oxidizer; compared to chlorine-based disinfectants, ozone has higher atom efficiency and is used at lower concentrations. Replacing only conventional disinfectants with ozone was not a commercial success, however, because cleaning and sanitation still required significant plant downtime and the ozone equipment was expensive.

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

Used as directed, WhiteWaterTM ozone does not expose workers or the environment to hazardous levels of ozone gas. Discharge from a food plant using WhiteWaterTM ozone contains water, oxygen (O2), and oxidized bacteria and organics that are more readily biodegradable and less likely to contain chlorinated organic compounds such as chloroform. Ozone International’s most recent patent was issued in 2007. WhiteWaterTM ozone is in use by approximately fifty food-processing facilities nationwide.

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

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

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

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

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

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

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

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

NXT Z® silane is a new coupling agent designed to improve the wear, traction, and rolling resistance of silica tires, without the ethanol emissions imparted by traditional silanes during tire manufacture and use. It builds on previous discoveries of blocked mercaptosilanes. NXT Z® silane contains both mercaptan and thiocarboxylate functionalities linked by high-boiling diols in place of the ethanol-derived alkoxy groups used in traditional silanes. The high-boiling diols have similar or faster hydrolysis rates than ethoxy groups, depending on whether they are bound to one or two silicon atoms. Once hydrolyzed, however, the high-boiling diols remain in the rubber compound, presumably bound to silica. NXT Z® silane also helps reduce manufacturing costs through hotter, harder, faster processing; single-step mixing; long-shelf-life silica compounds; and lower use levels. Several major tire companies tested NXT Z® for fast-track commercialization during 2006.

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

In 2011, BASF’s Biodegradable Polymers Group successfully made a completely compostable multilayer food packaging structure with high barrier properties. The structure consists of six layers: an Ecoflex® and Ecovio® outer layer, Joncryl SLX (printing ink layer), Epotal P 100 ECO (adhesive coating), a metallization layer, Versamid® (pre-met primer), and an Ecoflex® and Ecovio® inner layer. Ecoflex® is a bioplastic copolyester and Ecovio® is a compound of Ecoflex® with polylactic acid (PLA). This packaging structure meets the barrier requirements for a large number of packaged consumer goods.

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

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

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

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

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

Concrete-FriendlyTM Powdered Active Carbon (C-PACTM) to Remove Mercury from Flue Gas Safely: Coal-fired power plants emit 45 tons of gaseous mercury into the air and produce 65.5 million metric (MM) tons of fly ash annually in the United States. Fly ash has a composition similar to that of volcanic ash and is an excellent replacement for cement in concrete. Currently, about half the concrete produced in the United States contains fly ash. Of the 65.5 MM tons of fly ash generated in 2008, more than 11.5 MM tons were used in concrete and 16.0 MM tons were used in structure fills, soil modification, and other applications.

According to EPA’s 2008 report to Congress, federal concrete projects used 5.3 MM tons of fly ash in 2004 and 2005 to replace cement, saving about 25 billion megajoules of energy, saving 2.1 billion liters of water, and reducing carbon dioxide (CO2) emissions by about 3.8 MM tons. Powdered activated carbon injection (ACI) is a conventional technology that injects mercury sorbents into flue gas in power plants and captures the mercury-laden sorbents in fly ash. Although this reduces mercury emissions, the resulting fly ash is unsuitable for concrete and requires disposal in landfills.

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

Continuous Processing Enables a Convergent Route to a New Drug Candidate: LY2624803*H3PO4: The commercial production of LY2624803*H3PO4, an investigational new drug candidate currently in phase II clinical trials, illustrates the importance and impact of designing green processes. Lilly acquired this drug with its purchase of Hypnion, Inc. The original synthesis enabled early development, but was not amenable to large-scale manufacture. Lilly identified several major environmental and safety issues with the original chemistry. Among them were: (1) dimethylformamide/sodium hydride (DMF/NaH) in step 1, (2) methylene in various steps, (3) a molten step with observed self-heating, (4) an aldehyde purification that would be unsafe at increased scale, (5) phosphoryl chloride (POCl3) in large excess, (6) chromatographic purification.

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

The original route had a PMI of over 1,000 before chromatography. Lilly’s new route has a net PMI of 59, representing a 94 percent reduction (96 percent reduction including chromatography). This PMI is extraordinary given the complexity of the drug and its nine-step synthesis. Lilly implemented its new route for LY2624803*H3PO4 on a pilot-plant scale in Indianapolis, Indiana, during 2009 and on a commercial scale in Kinsale, Ireland, during 2010. Lilly’s application of green chemistry, as well as its development and use of flow chemistry, led to an efficient, convergent synthetic route and a significantly improved manufacturing process.

Convergent Green Synthesis of Linezolid (ZyvoxTM), an Oxazolidinone Antibacterial Agent: Pfizer has developed a novel, convergent, green, second-generation synthesis of linezolid, which is the active ingredient in ZyvoxTM. Approved by the U.S. Food and Drug Administration in 2000, ZyvoxTM is the only member of the oxazolidinone class of antibacterials. This is the first new class of antibacterials approved in over 30 years. ZyvoxTM is approved for the treatment of antibiotic resistant gram-positive bacterial infections, including vancomycin-resistant Enterococcus faecium (VREF), methicillin-resistant Staphylococcus aureus (MRSA), and multidrug-resistant Streptococcus pneumonia (MDRSP). These antibiotic-resistant bacterial infections have become an ever-increasing threat to public health.

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

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

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

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

This plant can potentially ferment the equivalent of about 5 dry tons of biomass per day to produce 100,000 gallons of biogasoline per year. The on-site conversion to biogasoline includes dewatering the fermentation salt product by evaporation and drying, thermally converting it into ketones, and catalytically converting the ketones into alcohols and hydrocarbons. Terrabon has successfully produced good-quality gasoline at this plant. In 2011, the company will begin constructing a 220 dry ton-per-day biorefinery at the Waste Management landfill in Alvin, Texas. This plant will convert MSW into 5 million gallons of gasoline per year.

Conversion of the Herbicide, Metolachlor, to S-Metolachlor in the U.S. Marketplace: Metolachlor, a racemic mixture of two diastereoisomers, was used in the US for over 20 years on > 30 crops at about 65MM lbs./yr. Syngenta discovered increased herbicidal activity of the optically active S-isomer pair in the 1980s (US patent 5,002,606). A practical synthesis route could not be found until the mid-1990s, when Syngenta discovered a chiral diphosphine catalyst route for enantioselective hydrogenation of an imine intermediate for S-metolachlor synthesis (US patents 5,463,097; 5,563,309; and RE37344E). Syngenta developed an optimized process and designed and constructed a high volume manufacturing plant capable of supporting commercialization. All metolachlor products have been replaced, at equal grower cost, with 35% reduced-rate S-metolachlor products.

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

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

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

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

Converting Pollution to Profits: Valuable Chemicals & Energy: Sulfur-containing molecules are found in many different industrial sectors and are usually desulfurized by combustion to SO2 or hydrogenation to H2S because they are toxic, corrosive, strongly malodorous, involved in the formation of particulates and are responsible for acid rain. H2S and SO2 emissions are typically converted to elemental sulfur and gypsum sludge and are disposed in landfills. Clearly, these pollution control approaches don’t result in valuable chemical products or energy that generate monetary incentives for industry to minimize environmentally undesirable sulfur emissions.

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

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

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

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

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

The NRTL-SAC technology offers a first-principles-based engineering solution, enabling chemists and engineers to design greener processes that deliver required drug purity and yield, minimize solvent use, generate less hazardous solvent waste, consume less energy, and decrease overall cost. AspenTech has been using NRTL-SAC in its products since 2005. Its collaborators include Eli Lilly, AstraZeneca, and Bristol-Myers Squibb.

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

Cortec Corporation (derived from corrosion technology) began to evaluate sugar beet glucoheptonate as an anti-icing road additive in 1994 when electrochemical screening indicated it could prevent metal corrosion in salt water. Cortec hypothesized that gluconic acid derivatives could protect rebar in concrete from corrosion; after tests were successful, the company began to develop this product. Cortec now sells eleven corrosion-control products based on natural oils, six based on gluconates, one based on soy protein, and three films based on polylactic acid. Its most successful product uses gluconic acid derivatives from sugar beets as components of migratory corrosion inhibitors to protect the reinforcing steel (i.e., rebar) in concrete from corrosion by salt.

An independent study by American Engineering Testing concluded that MCI 2005, a product derived from gluconates, delayed the onset of corrosion in steel embedded in concrete beams; when corrosion developed, MCI 2005 reduced the corrosion current and the extent of corrosion. The study involved 56 cycles of 3-percent sodium chloride (NaCl) ponding, drying the concrete beams for two weeks, and repeating the 3-percent NaCl ponding. The test measured corrosion by electrochemical measurements on the embedded rebar in the concrete blocks midway through each cycle.

Cortec has been awarded six patents covering the use of gluconates to protect rebar in concrete and has been successful in selling these products worldwide. In 2008, sales of these products were 6 percent of Cortec’s total sales; this figure increased to over 7 percent in 2009.

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

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

In Crosslink’s protection system, the onset of corrosion forms a local galvanic couple that triggers release of the inhibitor from the EAP. Released inhibitor molecules then diffuse to the corroding site and inhibit the anodic or cathodic reaction. In this sense, these coatings are "smart": they release the inhibitor only when corrosion occurs. A nontoxic inhibitor, 2,5-dimercapto-1,3,4-thiadiazole, forms the basis of one new chromium-free primer. Incorporation of Crosslink’s EAP system into paint systems such as epoxy and polyurethane could eliminate the need for chromium-based primer coatings and their associated environmental and safety risks. Crosslink has identified a business partner to commercialize its technology during 2007.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(2) converting of alkynes to alkynilides;

(3) reaction of alkynilides with aldehydes or imines.

All three steps generate stoichiometric amounts of waste, as well as require inert atmosphere and anhydrous organic solvents. Within the last several years, we have developed various catalytic direct addition of alkynes to aldehyde and imines in water and under solventless conditions. We have also developed the first direct catalytic enantioselective three-component-addition of alkdehyde, alkyne, and amine in water and under solventless conditions. The results have been published in J. Am. Chem. Soc. (2002, 2003) and Proc. Nat. Acad. Sci. (2004 in press) etc. and were cited in C& EN (2002, 2003).

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

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

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

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

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

In 2007, Professor Ragauskas published his recent work in the Journal of Organic Chemistry and in Tetrahedron Letters.

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

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

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

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

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

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

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

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

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

Estolides are viable for the most severe lubricant and industrial applications, including PCMOs, hydraulic fluids, greases, gear oils, metal working fluids, and dielectric fluids. Estolides have the potential to displace a significant portion of the lubricant market, reducing emissions and the release of hazardous chemicals into the environment. Test results show that oleic estolide esters may also have advantages in performance and fuel efficiency over petroleum-based PCMOs. LubriGreen is currently working with the world’s largest formulators, lubricant distributors, and others to commercialize its products during 2013.

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

From 1986 to 1992, LMTAS produced mainly F-16 fighter aircraft at a rate of 220 to 350 aircraft per year. Throughout the 6 years, LMTAS used a general purpose wipe solvent containing 85 percent CFC-113 by weight throughout the manufacturing process. The use of the CFC-113 solvent blend resulted in the emission of approximately 255 tons per year of CFC-113 and 45 tons per year of volatile organic compounds (VOC) The implementation of DS-104 at LMTAS has reduced wipe solvent VOC emissions to 7 tons per year in 1993, 3 tons per year in 1994, and 2 tons per year in 1995, with no CFC emissions. After the LMTAS implementation, other companies and military operations throughout the United States have implemented this technology.

Additionally, this technology has been implemented in several countries, such as Australia, Canada, Greece, Israel, Mexico, the Netherlands, South Korea, Taiwan, and Turkey. Several other European countries will implement this technology in 1997. These cleaners were developed primarily for aerospace; however, they have found cleaning applications in many industries such as: automotive, bubble gum removal in movie theaters and universities, various ink removal industries, postal operations, electronics, building maintenance, steel industry, and nondestructive testing methods. EPA has recognized this technology in the Aerospace National Emission Standard Hazardous Air Pollutants and the proposed Aerospace Control Technology Guideline.

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

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

RBI has developed and applied a powerful, new biodiversity search technology to scan natural sources for new enzymes. Once the best enzyme that nature has to offer for a particular application is identified, RBI applies additional high throughput technology to optimize the enzyme to make it more useful in a chemical plant. This new technology already has produced more than 150 new, robust biological catalysts for the chemical process industry and will generate more than 3,000 by 1997.

Development of a Nickel Brightener Solution: Historically, electroplaters of duplex nickel had to use formaldehyde and coumarin-bearing nickel plating solutions to obtain a nonsulfur nickel deposit, which is essential to the duplex nickel process, for maximum corrosion protection of external automotive trim and bumpers. The Watts" bath, introduced in 1916, made it possible to increase the speed of nickel deposit by a factor of ten by increasing the electrical current density.

This development lead [sic] to the bright nickel plating baths known today, which use organic and inorganic additives. Organic aromatic sulfonic acid was later introduced to the Watts" bath to achieve the first practical bright nickel plating solution. In 1936, formaldehyde was added to the solution followed in rapid succession by other additives. Coumarin, along with formaldehyde, became the important ingredients in a variety of nickel plating baths referred to as 'semibright". Today, semibright nickel plating occupies an important position in plating. Benchmark Products has developed a nickel brightener solution that, while improving the performance of electroplating, also significantly reduces the environmental impact by eliminating two toxic ingredients, formaldehyde and coumarin, and substituting nonhazardous ingredients.

Development of a Practical Model and Process to Systematically Reduce the Environmental Impact of Chemicals Utilized by the Textile and Related Industries: It was discovered in the early 1980s that discharges from textile dyeing and finishing operations were adversely impacting publicly owned waste treatment facilities. The results of early toxicity reduction evaluations pinpointed toxic and poorly degraded textile chemicals and surfactants as culprits. It was decided that elimination of toxic agents prior to formulation was an important long-term objective to provide for a sustainable textile industry in the United States. To achieve products "Designed for the Environment," a means to inexpensively screen chemicals and raw materials and communicate results internally and externally to consumers and regulators was needed.

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

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

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

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

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

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

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

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

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

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

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

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

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

It also eliminates the use of a stoichiometric amount of base if applicable substrates contain no acidic protons. Their novel technology has the additional benefit of rapid reaction times, ease of operation, and use of readily available catalysts and ionic liquids. These features should make this newly developed chemistry of great benefit to humans and the environment. The United States Patent and Trademark Office has granted four patents to Novartis for these novel inventions. In addition, leading peer-reviewed journals have accepted six publications. By the end of 2004, these papers had been cited thirty times by other scientists, confirming the utility and value of these inventions.

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

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

Since 2004, Pace Technologies, a major worldwide distributor of polishing consumables, has been distributing Ventana’s lapping fluid to manufacturers of hard drives as well as manufacturers of other products that require precision polishing such as optical lenses and flat-panel displays. In 2005, Ventana received a Phase II Small Business Innovation Research (SBIR) grant from the National Science Foundation to continue developing its polishing fluid. Ventana has also developed a series of new corrosion inhibitors and paint primers from its phytochemical precursors and spun them off as a separate technology.

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

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

In 2005, Nike produced about 170 million pairs of shoes worldwide that contained some of its new rubber formulations, representing approximately 25,000 metric tons of environmentally preferred rubber.

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

A PCT application [1] defining this new composition of matter was filed August 12, 2003, and all claims were approved without dispute. U.S. EPA funded TechSolve, Cincinnati, OH, to conduct toxicological testing, and determination of characteristics for use as "green" metal working fluids. Results of these studies have been published as an interactive CD (EPA/600/C-03/063), which have concluded that these polymers are environmentally benign and exhibit superior metal working fluid characteristics. LCP Tech, a small business company, was created to commercialize these polymers as metal working fluids, and pursue other applications, such as fire retardants, fuel cells, and intelligent membranes.

Development of Two Unique Processes for Manufacturing High-Purity Cyclopentane from Dicyclopentadiene: The team working in Baytown Texas developed two unique processes for manufacturing high-purity cyclopentane from dicyclopentadiene. Cyclopentane replaces ozone-depleting substances (ODS"s) such as CFC-11 or HCFC-141b foaming agents used in the manufacture of rigid polyurethane or polyisocyanurate insulation. Cyclopentane has the necessary physical properties including low vapor thermal conductivity and vapor pressure to make it a viable replacement for ODS"s but was not commercially available in sufficient quantity due to lack of an economic manufacturing process. This team"s invention (US Patent 5998683) is employed in a manufacturing facility started up in December 1998 located at Sarnia Ontario. That facility was built primarily to support the conversion of US insulation manufacturers from the use of ODS"s to the green cyclopentane substitute. US consumption of ODS"s in polyurethane and polyisocyanurate insulation amounts to about 100 Mlb/yr, all of which may be replaced by cylopentane.

Development of Water-Based Materials for Post-it® Super Sticky Notes: In the late 1980s, 3M developed a prototype of a new, enhanced Post-it® Notes product for use on vertical and hard-to-stick surfaces. This prototype used solvent-based adhesive formulations. At the same time, 3M launched an initiative to reduce volatile organic compound (VOC) emissions by 90 percent by the year 2000. Rather than install pollution control equipment to control the VOC emissions from the proposed manufacturing process for the new Post-it® Notes, 3M delayed introducing the product until it could develop a new, water-based adhesive formulation. 3M finally introduced Post-it® Super Sticky Notes in 2003.

The new water-based microsphere materials that 3M uses in its Post-it® Super Sticky Notes yield the desired performance, generate fewer air emissions, have a reduced environmental risk profile, and are less expensive to manufacture than the original, proposed, solvent-based formulations. The formulations are trade secrets, but they are based on acrylate polymers. They do not contain any fluorochemicals, alkylphenol ethoxylates, poly(vinyl chloride), phthalates, or heavy metals intentionally added or present as impurities above de minimus levels. The new formulations reduce annual VOC emissions by 33,400 pounds (with pollution controls) or 2,170,000 pounds (before pollution controls) and Toxic Release Inventory (TRI) emissions by 20,500 pounds (controlled) or 1,024,000 pounds (before control) compared with the projected emissions of the proposed, solventbased process.
The water-based system eliminates the need for a thermal oxidizer to control VOC emissions, reducing 3M’s emissions of CO2 from fuel combustion. It also increases worker safety and reduces the possibility of fire, chemical release, or explosion. The waterbased system also generates significant cost savings. 3M’s Post-it® Super Sticky Notes are an excellent example of the benefits of green chemistry and the importance of integrating 3M’s core values into decision-making. Following its success with Post-it® Super Sticky Notes, 3M added water-based formulations to Post-it® Sticky Picture Paper for printing digital pictures and to other specialty applications in 2005.

Device and Method for Analyzing Oil and Grease in Wastewaters without Solvent: The 1974 Clean Water Act lists oil and grease together as one of five conventional pollutants. All National Pollution Discharge Elimination Systems (NPDES) permits, all pretreatment permits, and all Industrial Effluent Guidelines require measurements of oil and grease. Millions of analyses for oil and grease are done annually in the United States. Following the Montreal Protocol in 1989, EPA replaced a Freon extraction method for oil and grease testing with an n-hexane extraction method (EPA 1664; EPA 1664a). This created several problems: (1) n-hexane is a hazardous, flammable liquid; (2) n-hexane is a known neurotoxin; and (3) testing generates millions of liters per year of n-hexane waste that require disposal. Thus, the current methodology is inconsistent with the intent of the Clean Air Act and Clean Water Act, both of which identify n-hexane as a hazardous pollutant.

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

The membrane does not absorb IR light in the spectral regions of interest; after drying, the device can be put into an IR spectrophotometer to determine the amount of oil and grease. This patent-pending technology has successfully completed ASTM (American Society for Testing and Materials International) multi-laboratory validation and received ASTM method number D7575. EPA is currently considering replacing method 1664 with this one. This replacement would save one million liters of hexane annually and produce estimated benefits to the U.S. economy of $50–$60 million. OSS is actively commercializing this technology worldwide.

Diesel DeOx Catalyst: By 2014, EPA will implement more stringent standards restricting emissions from heavy-duty diesel vehicles. These standards are creating a market for products that reduce diesel emissions.

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

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

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

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

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

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

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

Detailed analysis demonstrates that the MCC-based process meets all commercial and quality criteria; in addition, it reduces the use of valuable resources and greatly decreases the process liquid waste streams. The traditional synthesis required 260 kg of input material and 194 kg of solvent per kg of product. The mass intensity of the MCC process is approximately 20 kg of input material per kg of product, an incredibly low number for a pharmaceutical product. The MCC process uses only 19 kg of solvent per kg of product, with potential for further recovery. GlaxoSmithKline performed a pilot study on medium-to-large scale in-house MCC equipment during 2003. At peak production, GlaxoSmithKline calculates that the MCC process could reduce the overall waste load by 5,000 metric tons per year.

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

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

The guidance information in "DOE Methods" also helps minimize the number of analyses and saves time and money. Guidelines are provided on how to (1) efficiently develop a sampling and analysis program, (2) effectively and efficiently sample waste, (3) handle radioactive samples safely, and (4) select appropriate analytical methods. Cross references allow the users to select from currently available standard methodologies. "DOE Methods" has been available for both DOE and commercial use since 1992. It is updated every 6 months, thereby accelerating the release of new technology to speed EM [sic] operations.

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

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

Other researchers have studied doped nanocrystals as alternatives to heavy-metal-based quantum dots since the 1980s, but they have not discovered reaction schemes that achieve pure dopant emission at high fluorescence quantum yield. Often, a large portion of the nanocrystals were undoped, resulting in emission peaks from both the undoped and doped nanocrystals.

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

Professor Peng has filed a patent for this technology. During 2007, NN-Labs launched its first two doped nanocrystal product lines, Yellow and Orange D-dotsTM. It is developing a full spectrum of D-dotTM emitters.

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

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

Second, some aqueous lubricants can promote microbial growth.

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

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

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

PCE is a suspected carcinogen, petroleum-based solvents are flammable and smog producing, and CFC-113 is an ozone depletor and targeted to be phased out by the end of 1995. Health risks due to exposure to cleaning solvents and the high costs of implementing and complying with safety and environmental restrictions and regulations, have made dry cleaning a much more difficult business in which to achieve profitability. Solvents are suspected of contaminating ground water, air, and food products (i.e., in nearby markets). For these reasons, there is an ongoing search for alternative, safe, and environmentally friendly cleaning technologies, substitute solvents, and methods to control exposure to dry cleaning chemicals.

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

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

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

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

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

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

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

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

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

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

Faced with a shrinking supply of petroleum wax and a rise in restrictions on wood-burning fireplaces by air quality districts (particularly in the Western states), the company has focused on developing manufactured firelogs using materials that are both cleaner burning and recycled or renewable. In 2004, Duraflame introduced a new all-natural firelog made from recycled biomass products such as wood sawdust, ground nut shells, recycled cardboard, and plant waxes (to replace petroleum wax) as a combustible binder.
Standard petroleum wax–sawdust firelogs produce approximately only one third of key air pollutants associated with residential wood combustion compared to an equivalent natural wood fire. In contrast, Duraflame’s new all-natural firelogs produce approximately one quarter of the emissions of an equivalent natural wood fire. The Duraflame® All-Natural Firelog is now available in supermarkets across the United States and Canada.

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

The conventional brands had significantly higher levels of 1,4-dioxane. The highest were Tide® with 55 ppm, Ivory Snow® with 31 ppm, and Tide® Free with 29 ppm. OCA has confirmed in their latest report for 2010 that ECOS® Laundry detergent by Earth Friendly Products was free of 1,4-dioxane. Since June 2008, Earth Friendly Products has successfully scaled up its formulas to produce natural products that do not contain any harmful chemicals, including 1,4-dioxane. The company uses a blend of coconut oil with anionic fatty acid chains that make excellent surfactants due to their dual hydrophilic and lipophilic properties. There is no sodium chloride salt added or used in any step of manufacturing or production of the company’s laundry products. Each product is made with sustainable, plant-based ingredients that are studied to ensure minimal environmental impact before and after production. This ensures that all of the company’s products are not only biodegradable, but also free of phosphate, caustic, formaldehyde, petrochemicals, chlorine, synthetic perfume, and ammonia.

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

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

EarthTec®: Green Water Treatment: EarthTec® is an EPA-registered algaecide and bactericide (EPA Number 64962-1) that is certified by the National Sanitation Foundation (NSF) Standard 60 as a drinking water additive. It uses no chlorine and contains less copper than competing products. The proprietary copper formulation made by EarthTec® is 99.9-percent-suspended cupric ions (Cu(II)); its proprietary base product, ET-3000, keeps the copper biologically active and suspended. The copper remains fully dissolved indefinitely, thereby insuring long-term organic control as well as less environmental release. EarthTec® is not an organic compound.

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

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

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

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

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

Tennant is the first in its industry to harness the cleaning power of water for cleaning hard floor surfaces and to use electrically charged water on a mobile platform. Tennant plans to make its patent-pending processing units available on several models of its cleaning machine platforms. Tennant launched its product during 2007; it has a number of patents pending.

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

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

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

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

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

Toxic chemicals are a health hazard. The paint produced in the United States during 2001 contained almost 5 million kilograms of VOCs. The origin of many respiratory conditions in the U.S. population is unknown, but it is, in the company’s opinion, related to toxic chemicals in the atmosphere. Airborne toxic chemicals may also be related to the high incidence of liver and pancreatic cancers in the United States.

Innovative Formulation has created a completely safe antimicrobial paint that is virtually free of hazardous chemicals. No other paint company in the United States can legitimately and accurately make such representations. Innovative Formulation has been producing its Clear Coat since December 2005 at a plant in Tucson, AZ. A major fast food chain is currently using Clear Coat and a major hotel chain is testing the product.

Ecomate® Environmentally Benign Blowing Agent for Polyurethane Foams: Traditionally, chlorofluorocarbons (CFCs) were the preferred blowing agents for polyurethane foams. Foams blown with CFCs had good insulating and structural properties for use in refrigerators, building construction, and spray foam. CFCs were removed from polyurethane foam in the 1990s, however, due to their potential to destroy the ozone layer. Hydrochlorofluorocarbons (HCFCs) have a lower Ozone Depletion Potential (ODP) and are currently replacing CFCs, but were scheduled for phase out by 2010 in the United States. Ecomate® (methyl formate) is a zero-ODP, zero Global Warming Potential (GWP) blowing agent designed to replace CFCs, HCFCs, and hydrofluorocarbons (HFCs). Ecomate® is also VOC-exempt, meaning it does not contribute to smog.

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

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

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

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

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

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

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

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

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

Since the first field-scale project in 2004, EHCTM has been used to treat approximately 100 locations around the globe.

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

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

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

This efficient transfer eliminates the unnecessary transport and accidental release of fuming 35 percent HCl. NSR’s single plant eliminated the production of 2 million pounds of Cl2 during 2011; at full capacity, it would eliminate the production of 10 million pounds of Cl2 per year. NSR’s technology could potentially eliminate the production of billions of pounds of unnecessary Cl2 each year.

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

The metal residue, fission products, and transuranic elements from the spent fuel can be immobilized in highly stable waste forms for disposal in a geologic repository. Compared with conventional processing, electrometallurgical technology holds promise for significantly reduced costs, greatly decreased volumes of high-level radioactive waste, and negligible volumes of secondary or low-level wastes. This technology could facilitate the environmentally sound processing of most of the more than 2000 metric tons of spent fuel accumulated within the Department of Energy complex. This technology also has potential spin-off applications for industry, such as the treatment of enrichment tailings from nuclear plants and the disposal of nontoxic wastes (e.g., barium-contaminated slats) from industrial processes.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Commercial Fluid Power is taking steps to reduce the use of industrial hard chrome or engineered chrome in the fluid power market. The company is developing and marketing Nitro-tuff tubes as safe, environmentally friendly replacements for chrome-plated tubes. Nitro-tuff tubes are ferritic nitro-carburized steel. During their manufacture, the surface of the steel is converted to a nonmetallic epsilon iron nitride (e-Fe3N) in an atmosphere of ammonia and carrier gas. Following nitriding, an oxidizing atmosphere is introduced to produce a thin, corrosion-resistant, black surface film of Fe3NO3-4. The iron nitride layer is the basis for the steel’s extraordinary wear and corrosion resistance.
Advances in mechanical properties, size, and finish control now allow Nitro-tuff tubes to substitute for chrome-plated tubes without losing quality or strength. These efforts are reducing the use of hexavalent chromium. Recent research, development, and testing have overcome earlier challenges and opened new markets for Nitro-tuff tubes and bars. In conjunction with NitroSteel and Nitrex, Commercial Fluid Power continues to strive to bring an eco-friendly, cost-effective solution to the fluid power market.

Elimination of Ozone-Depleting Chemicals in the Printed Wire Board and Electronic Assembly and Test Processes: IBM-Austin is a manufacturing and development facility. Operations include the manufacture of printed wire board (PWB) in the Panel Plant facility and electronic circuit cards in the Electronic Card Assembly and Test (ECAT) facility. In 1992, IBM-Austin completely eliminated the use of CFCs and other ozone depleting substances from its PWB and ECAT processes. This elimination program resulted in 100 percent reduction of CFC-113 (1988 peak usage of approximately 432,000 pounds) and 100 percent reduction of methyl chloroform (1988 peak usage of approximately 308,000 pounds) from IBMAustin’s PWB and ECAT processes.

These accomplishments were achieved by converting to an aqueous-based photolithographic process in the PWB facility in 1989, an interim aqueous cleaning process in the ECAT facility in 1991 and 1992, and a final No-Clean process (eliminating the aqueous cleaning process) in the ECAT facility. Changing from a solvent-based photolithographic process to an aqueous-based process eliminated methyl chloroform (MCF) from PWB panel manufacturing (1988 usage of 181,000 pounds). The interim process changes to aqueous cleaning eliminated MCF from manufacturing processes in ECAT (1989 peak usage of 196,000 pounds) and were largely responsible for eliminating CFC-113 from all manufacturing processes at the IBM site. Although CFC-113 was eliminated from the site in 1991 and MCF was eliminated in 1992, ECAT’s ultimate goal was to convert all ECAT processes to No-Clean manufacturing processes.

Elimination of Ozone-Depleting Chemicals Through the Use of a Water Soluble Adhesive "Green Wax": MEMC Electronic Materials, Inc., a silicon wafer manufacturer, undertook to eliminate all Class I Ozone Depleting Chemicals (ODCs) from manufacturing operations in 1992. Over 80 percent of the target ODCs used by MEMC were in direct silicon processing steps like slice mounting, polishing, slice demounting, and slice dewaxing. The mounting of silicon slices prior to polishing was performed with a material known as "wax" which was capable of controlled viscosity and thickness application.

The old wax formulation contained trichloroethylene (TCE), while the old block cleaning method utilized 1,1,1-trichloroethane (TCA), and the old slice dewaxing process utilized Freon 113. The wax formulation was changed to a water soluble one ("green wax"), that utilized a commercially available water soluble resin (a modified maleic resin in solution with ammonium hydroxide and water). Slice mounting (block cleaning) and dewaxing were modified to use a dilute basic solution (such as ammonium hydroxide) instead of TCA and Freon 113. The flatness, particle count, and metal concentration of slices produced with green wax are equal to or better than the old wax. It is estimated that, since 1993, MEMC has avoided the production of almost 5 million pounds of ODC emissions worldwide through the use of green wax.

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

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

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

Elimination of PFOS and PFOA in IBM Semiconductor Manufacturing Processes and Development of Photoacid Generators Free of Perfluoroalkyl Sulfonates: In 2002, EPA restricted new applications of perfluorooctane sulfonate (PFOS) compounds because scientific evidence showed that PFOS persists and bioaccumulates in the environment. Because semiconductor manufacturers demonstrated limited release and exposure for PFOS, however, EPA allowed PFOS compounds "as a component of a photoresist substance, including a photoacid generator or surfactant, or as a component of anti-reflective coating, used in a photolithography process to produce semiconductors or similar components of electronic or other miniaturized devices."

Voluntarily, IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA). In 2006, IBM issued a Corporate Directive to eliminate PFOS and PFOA from all manufacturing processes by 2010. IBM worked with chemical suppliers to identify and qualify a non-PFOS replacement for the PFOS surfactant in buffered oxide etch (BOE) chemicals. In 2008, after a multiyear investigation and extensive qualifications, both IBM fabrication plants finished replacing the PFOS surfactant in all BOE chemicals with perfluorobutane sulfonate (PFBS), for which EPA has fewer environmental concerns. IBM also sought replacements for specific photoresists and antireflective coatings (ARCs) that contained PFOS or PFOA as a surfactant or photoacid generator (PAG).

In January 2010, after significant investment and qualification of replacement chemistries across many wet etch and photolithography processes, IBM completed its conversion to non-PFOS, non-PFOA lithographic chemicals. This change eliminates approximately 140 kilograms of PFOS and PFOA annually. Total annual PFOS consumption by the semiconductor industry worldwide is estimated at 8,000 kilograms. IBM believes it is the only company in the world to eliminate PFOS and PFOA compounds completely from semiconductor manufacturing. IBM has also developed PAGs free of perfluoroalkyl sulfonates (PFAS) for both dry and immersion 193-nm semiconductor photolithography processes, with equivalent performance in 45-nm and 32-nm semiconductor technology. IBM is pursuing technology transfer opportunities to commercialize its PFAS-free PAGs for a wider range of applications.

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

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

Enabling Technology for Methacrylic Acid Production using Isobutane as the Feedstock: Methacrylic acid (MAA) and its methyl ester, methyl methacrylate (MMA), are high-volume commodity chemicals that are building blocks for polymers used widely in the construction, automobile, appliance, and coating industries. Since the 1930s, the production of MAA and MMA in the United States has used the conventional acetone–cyanohydrin (ACH) process, whose feedstocks are acetone and highly toxic hydrogen cyanide (HCN). The production of one ton of MAA requires at least 0.31 ton of HCN along with 1.6 tons of concentrated sulfuric acid as both solvent and catalyst. It also generates 1.2 tons of ammonium bisulfate requiring disposal. In 2005 alone, the U.S. production of 1.82 billion pounds of MAA and MMA consumed at least 558 million pounds of HCN, used and regenerated about 2.88 billion pounds of concentrated sulfuric acid, generated and disposed of 2.16 billion pounds of ammonium bisulfate, and generated tens to hundreds of billion pounds of aqueous waste discharges.

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

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

Seeking more sustainable process conditions, Dow Process Research and Development identified the synthesis of VME as a prime candidate for reactive distillation technology. Reactive distillation combines chemical reaction and distillation in a single step. This technology is part of the separations roadmap supporting Vision 2020 for the U.S. chemical industry because it can significantly reduce the energy consumption of separation processes.

Applying reactive distillation to the VME process meant replacing one reactor and four distillation columns with a single reactive distillation column. The new process requires less steam, leading to energy savings equivalent to 54,000,000 kWh each year. This is enough energy to provide electricity for approximately 4,800 homes per year based on average 2007 household consumption reported by the Department of Energy. The primary aqueous waste stream from the VME process using reactive distillation contains much less byproduct and is efficiently cleaned by a wastewater treatment plant, eliminating chemical pretreatment. In addition, careful selection of plant location reduced the transit distance between the VME plant and its sister derivatization plant from 1,200 to 500 miles, which lowered fuel use per transported railcar by 60 percent as an added benefit. A VME plant based on reactive distillation was built at a contract manufacturing facility in early 2009; the conventional VME plant closed later that year.

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

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

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

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

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

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

RMC received a U.S. patent for its technology in March 2009 (Patent No. 7,507,697).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Environmentally Advantaged Formulations for Aircraft Ice Control: During the 1992–1993 deicing season, the 20 largest airports in the United States used over 11 million gallons of aircraft deicing fluids (ADFs). The large quantities of effluents that are released into the environment during aircraft deicing operations have resulted in several reportable incidents of environmental damage in the vicinity of airports throughout the world. This damage is caused by the high biological oxygen demand (BOD) of current ADFs that deplete oxygen levels in receiving waters sufficiently to distress and kill aquatic life. Airports are now required to obtain National Pollutant Discharge Elimination System (NPDES) permits to discharge ADFs into storm water sewers. Regulations under development by the U.S. EPA are expected to be much more restrictive. In addition, treatment costs of current ADFs are between $12 and $20 per gallon of deicing fluid, several times the purchase price of approximately $5 per gallon.

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

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

Environmentally and Toxicologically Safe Firefighting Gel: Liquid firefighting gel had its genesis in the 1990s, when John Bartlett, President of Barricade International, Inc., observed that used, disposable baby diapers survived a house fire in which even the appliances melted. The superabsorbent polymer and water content of the diapers prevented their combustion. Mr. Bartlett, a professional firefighter, realized that a superabsorbent polymer might change the way fires are fought. He then looked for liquid forms of the superabsorbent polymer that might be easily introduced into firefighting water to produce a fire retardant and suppressant gel. In the late 1990s, Mr. Bartlett identified a printing paste thickener used in the textile industry that produced a thickened water gel that significantly improved fire extinguishing and prevention. Barricade’s competitors now use that product, but it contains two components, petroleum distillate and nonylphenol ethoxylate (NPE), that have environmental and health concerns.

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

Barricade II is more effective at fire prevention than its NPE–petroleum distillate competitor. In aerial applications, Barricade costs only about half as much as traditional retardants and is effective at about 1/18 the application rates. The U.S. Forest Service has placed Barricade II on its Qualified Products List. A U.S. patent has been allowed, and Barricade International has begun full-scale commercial production of this product. California’s Department of Forestry used Barricade II in aerial applications during the 2006 fire season with spectacular results.

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

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

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

The MLI chemistry has led to development of a wide array of products, many of which are now in or near commercial use. These products reduce the nation’s reliance on petroleum, assist the commercialization of biofuels, and reduce impacts on health and the environment relative to traditional glycol-based fluids. The MLI biomass-based fluids are infinitely soluble in water, are nontoxic, and act as corrosion inhibitors for ferrous metals. During 2005, MLI received a patent for D/A agents made from byproducts of biodiesel manufacture. Also in 2005, MLI released Caliber® FC-B antifreeze and Caliber® SBA-2 additive for chloride D/A products in collaboration with Archer Daniels Midland. Current sales of MLI D/A agents are 15 million gallons per year. Applications for these products include aircraft-related uses, airport runways, roadways, bridges, facilities, landscape, and consumer markets.

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

The technique takes full advantages of the solution enzymatic synthesis method but overcome its limitations by immobilizing the enzyme on a solid support as a catalyst. The stability of the enzyme is significantly increased through the immobilization process. Furthermore, the catalyst enzyme can be easily recovered and reused with the immobilizing technique. Since the solid support is used, it is ideal to fabricate an enzymatic reactor for polymer synthesis. Most importantly, the newly developed technology in this research makes the biological route for polymer synthesis become usable and practical in commercial production process. A patent application for this new technology was filed at USPTO in year 2001.

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

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

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

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

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

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

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

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

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

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

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

Commercial airports and military bases are increasingly concerned about the quality of storm water runoff and the effect of deicing chemicals on receiving waters. If storm water drains directly from runways and taxiways into a body of water, discharge permits require regular monitoring to determine BOD, contaminants, and other properties. Due to its low BOD, METSS ADF-2 can help airport managers achieve environmental compliance. METSS ADF-2 meets all requirements of the SAE AMS 1424D for aircraft deicing fluids. The U.S. Air Force, the Federal Aviation Administration, and Transport Canada have all approved METSS ADF-2; this product has been in commercial use since October 2003.

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

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

With products that are much safer to handle, environmentally beneficial, better performing, and less expensive, IER has been growing very rapidly into the wastewater treatment market. Currently, IER is exploring other processes that require pH buffering as markets for its green chemical antacid formulations. It is developing new Amalgam® formulations to replace caustic soda in the recovery of chromium in the tanning process and to increase the yield of ethanol in the fuel ethanol industry. Since 2004, IER has constructed two manufacturing plants and a pilot plant. It has also filed a patent for its technology.

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

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

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

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

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

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

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

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

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

In 1990, Congress passed the Pollution Prevention Act, which introduced the concept of pollution prevention through proper waste disposal, waste treatment, source reduction and source prevention. In this regard, bismuth compounds are particularly attractive candidates for use as reagents in synthetic organic chemistry for several reasons: Bismuth is the least toxic of the heavy metals. The biochemistry, toxicology and environmental effects of bismuth compounds have been well documented. The majority of bismuth compounds are relatively non-toxic (e.g., the LD50 (g/kg) of BiOCl is 22 and that of Bi2O3 is 5 (compared with a LD50 of 3.75 for NaCl). Bismuth and several of its compounds are commercially available and are relatively inexpensive. This project is aimed at developing new applications of bismuth compounds in organic synthesis.

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

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

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

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

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

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

The process eliminates water use, requires little excess methanol feedstock, and significantly improves glycerin quality to low-ash, technical grade with over 97 percent purity. The soap-free, enzymatic biodiesel process improves separation between biodiesel and glycerin phases because the emulsifier (soap) is not present. The new process also uses less energy than the current process or other second-generation processes (e.g., metal oxides). Piedmont’s biodiesel meets ASTM (American Society for Testing and Materials International) standards and is economically viable for existing biodiesel processors. During 2011, Piedmont Biofuels and Novozymes A/S will commercialize this process.

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

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

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

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

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

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

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

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

Genencor has begun commercial production and now has industrial-scale quantities of the enzymes available under the trade name DEFENZTM. The enzymes will be sold to companies that produce and sell fire-fighting foams, sprays, and other potential matrices. These companies will formulate the enzymes into products for purchase by fire departments, HazMat groups, and other first-responders. Kidde Fire Fighting introduced the first such commercial product, All-ClearTM, in August 2005.

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

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

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

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

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

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

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

Because chlorine is reduced, the amount of AOX is similarly reduced by up to 95%. Since its commercial introduction in 2002, Equinox® has treated over 36 billion gallons of paper mill water, eliminating the use of an estimated 2.4 million pounds of chlorine and preventing the generation and release of over 128,000 pounds of AOX into the environment. Equinox® is now used in paper mills throughout the U.S. and Europe. Equinox® has other uses as well, but in the papermaking industry alone it has the potential to eliminate the formation of 3.3 million pounds per year of AOX pollutants. By reducing the amount of toxic AOX compounds released into the environment, Equinox® provides an environmentally safer alternative to the historically high use levels of chlorine biocides.

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

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

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

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

Tandus’s patented, closed-loop process can also recycle postconsumer carpet with ethosTM backing and other manufacturing waste into new floor coverings. Initially, Tandus successfully introduced a six-foot-wide ethosTM cushion backing, Powerbond, to meet the needs of Kaiser Permanente for high-performance, PVC-free, soft-surface flooring. In November 2009, the company introduced ethosTM modular. Its production has increased 18-fold in the last two years. Every square yard of ethosTM modular replaces approximately 5.25 pounds of PVC in carpet backing. To date, Tandus has recycled more than 10 million pounds of PVB into flooring products, keeping PVB from landfills, and potentially replacing 52 million pounds of PVC.

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

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

The starting materials remain dissolved, but the imine crystallizes out of solution as it forms. Although traditional methods often drive reactions forward by removing water, Professor Bennett’s method drives the reaction forward by removing the product through crystallization. To date, she and her undergraduate research students have synthesized nearly 200 imines using this method; her students in teaching labs have made more than half of these in a green chemistry project. In summary, the ethyl L-lactate method is faster, usually results in higher purity and yield, uses less energy, uses less solvent, generates less waste, and uses a more benign solvent than published methods. A patent application for this method was published in 2011. Professor Bennett is now studying these imines in biological and other applications. All are fluorescent and some are photochromic. Several show promise as fluorescent cell markers and antibacterial agents.

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

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

These reactions consume both starting materials, leaving no side products. Successes include highly enantioselective syntheses of common NSAIDs, such as ibuprofen, naproxen, flurbiprofen, and fenoprofen, from the corresponding styrenes and ethylene. Cyclic and acyclic 1,3-dienes also undergo efficient enantioselective addition of ethylene. Syntheses of several 1-vinylcycloalkenes and 1-substituted-1,3-butadienes achieve yields up to 99 percent. Professor RajanBabu has found expeditious routes to biologically relevant classes of compounds including bisabolanes, herbindoles, trikentrins, steroid D-ring 20S- or 20R-derivatives, (-)-desoxyeseroline, pseudopterosin A–F, G–J, and K–L aglycones, and helioporins. These syntheses require fewer steps than traditional methods and produce uncommon configurational isomers. In 2010 and 2011, Professor RajanBabu published five papers on this work.

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

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

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

Alowood offers an environmentally friendly alternative: an exotic look and performance using fast-growing plantation softwoods impregnated with the Everdex formulation, an innovative green chemistry. Everdex is a polymeric formulation made from urea, glyoxal, and starch in water along with environmentally friendly dyes and pigments; it does not contain any formaldehyde. Softwoods, particularly sustainably grown, plantation softwoods, are impregnated with dilute solutions of Everdex by a vacuum-pressure treatment. Next, the impregnated wood is heated, causing the starch polymer to cross-link with the wood cellulose through the urea-glyoxal groups. This creates Alowood: a denser, harder, more workable wood product akin to a natural hardwood. During 2007, Alowood received GREENGUARD Indoor Air certification and class A fire retardant certification.

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

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

ExSact solves these problems by replacing dangerous liquid acids with a noncorrosive, environmentally friendly, solid acid. This breakthrough catalyst is safe enough to be held in hand and is benign in the open environment. Previous solid acid catalysts have not been commercially successful because they tend to deactivate rapidly by coking during alkylation. Exelus has engineered every aspect of its new catalyst to reduce coke formation. It has optimized both the distribution and strength of the acid sites and has chosen a pore structure that creates the proper reaction environment near the active sites. Its ExSact technology represents the first commercially viable solid acid alkylation process in the world. Exelus has successfully demonstrated the ExSact technology in a 1,000-hour pilot program and has licensed its technology to a European refiner. The first commercial plant is expected to start up in early 2008.

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

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

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

Perhaps the single biggest benefit to society, however, is a massive reduction in energy use. This process would save up to 186 trillion British thermal units per year (Btu/yr) in the United States alone, cutting CO2 emissions by 4.34 billion kg per year. These savings represent over 5 percent of the U.S. greenhouse gas reductions stipulated by the Kyoto Protocol. In addition, the hydrogen byproduct of the reaction can be used as fuel to produce all of the heat of reaction and most of the distillation energy for the process without generating any CO2. Exelus has demonstrated its technology at the bench scale and expects to begin pilot plant tests in mid-2007.

Fertilizer From Photowaste: More than 100 million gallons of photographic wastes are generated in the United States annually. According to U.S. Environmental Protection Agency studies in the early 1990’s, these wastes represented approximately 40 percent of all liquid toxic waste produced by American industry. This waste is a significant environmental hazard to the nation’s bodies of water because photographic wastes contain silver and other heavy metals. Silver is potentially toxic to fish and other aquatic life. The waste, from photo finishers, photo labs and studios, X-ray laboratories, and printers, is dumped into the environment without pre-treatment, although rules are being tightened in many states and municipalities to curtail this or to require more intensive treatment.

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

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

With the advent of the Montreal Protocol eliminating production of ozone-depleting substances, the search for substitute materials for common items including air-conditioning and fire extinguisher fluids has to be intensive. Work at the U.S. Army Edgewood Research, Development, and Engineering Center was directed at finding filter leak test materials that were not destructive to earth’s stratospheric ozone layer and were capable of rapidly identifying filter assembly problems. Materials investigated included several hydrogenated fluorocarbons (HFCs) of differing volatility. HFCs do not contain chlorine or bromine, which have been implicated as potent stratospheric ozone destroyers. Two HFCs were identified as substitute filter leak test vapors: 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-4310mee) for in-service filters and 1,1,1,2-tetrafluoroethane (HFC-134a) for new filters. These materials have been adopted by the U.S. Army to test the integrity of filters used to provide respiratory protection against chemical warfare agents.

FIREBLOCKTM Intumescent Resin: Composites used to manufacture interior and exterior parts for applications in trains, tramways, subways, and other rolling stock must meet fire retardant specifications. Traditional chemicals used in fire retardant composites are decabromodiphenyl ethers and antimony trioxide, which are carcinogens, mutagens, and reproductive toxins. The manufacturing of these fire retardant composites requires handling highly toxic substances. In case of accidental combustion, polybrominated aromatic compounds release free radicals that act in synergy with antimony trioxide to produce bromide radicals and toxic fumes. Intumescent coatings swell with heat, offering passive fire protection. Intumescent coatings have been known for years, but these products were very difficult to formulate and apply. In 2008, CCP Composites developed a breakthrough product, FIREBLOCKTM intumescent unsaturated polyester resins (UPRs), which can be molded with glass fiber to manufacture fire retardant parts. In the intumescence mechanism, high temperatures cause ammonium polyphosphate to release an acid that simultaneously reacts with melamine in the resin to liberate a gas. The gas diffuses into small bubbles and carbonizes the carbon-rich polyalcohol.

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

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

GE Plastics has invented and commercialized ten grades of flexible poly(arylene ether) resins that substitute for PVC in coatings and coverings for wire and cable. They market them as Flexible NORYL* resins. GE’s Flexible NORYL* resins are based on proprietary compositions containing poly(arylene ether), polyolefin, and a nonhalogenated flame retardant. Flexible NORYL* resins totally eliminate halogenated compounds, heavy metal stabilizers, pigments, and phthalates. Moreover, Flexible NORYL* resins may facilitate the reuse of wire coating to benefit the environment. Wire coatings made with Flexible NORYL* resins have helped the consumer electronics and automotive industries meet stringent environmental initiatives, such as the European Union’s ISO 14020 and ISO 14024 and EcoMark in Japan.

For the consumer electronics industry, wire coatings made from Flexible NORYL* resins offer better heat performance, increased flame retardant properties, and lower costs due to reduced weight. In the automotive industry, NORYL* resins can improve vehicle performance by improving abrasion resistance, improving heat performance, and allowing more compact electronics. The light weight of Flexible NORYL* resins and their outstanding abrasion resistance enable ultrathin wall wire construction. They may reduce an automobile’s wire-resin weight by as much as 25 percent. Flexible NORYL* resins can make a significant contribution to helping global automotive manufacturers meet end-of-life and take-back requirements including the European Union’s Restriction of Hazardous Substances and End-of-Life Vehicle directives, Japan’s Automobile Recycling Law (2005), and the Japan Automobile Manufacturers Association (JAMA) guidelines.

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

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

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

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

They use only 19 percent of the embodied energy of today’s products because the manufacturing process requires less energy and regionally integrated manufacturing minimizes transportation costs. Products made from today’s wood composites have a $100 billion market. e2e is replacing those products with higher performing, safer, more efficient, and more cost-effective biocomposite-based products. These products complement its proprietary biocomposite core with green, cost-effective coatings. Following successful pilot production in 2011 and responding to strong demand for its commercial office furniture products, e2e recently announced a 100,000 square foot manufacturing expansion.

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

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

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

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

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

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

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

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

The Formula 1TM Laundry System has been in commerce since January 2004; there are currently over 1,000 users in North America. If half of the over 50,000 potential user locations in North America used the Formula 1TM Laundry System, they would save 8.2 billion gallons of water, 47 million therms of natural gas, and 5 million pounds of plastic each year.

From Waste-to-Energy: Catalytic Steam Gasification of Poultry Litter: UTSI’s poultry litter gasification concept is based on the Exxon’s Catalytic Coal Gasification Process. In this concept, poultry waste or any other animal waste is mixed with the other biomass waste and suitable source of additional potassium. The resulting mixture is gasified in "as-is" or slurry form at 1300-1500 °F and at 50-150 psi pressure in a suitable gasifier. The steam for gasification can be produced externally and supplied to the gasifier or can be produced in-situ from the wet/slurried feedstock. Depending upon the pressure, the resulting fuel gas will be rich in CH4 or in CO and H2 and after separating from the solid/char residue can be used as a fuel for heating purpose or to produce electricity. The solid/char residue is significantly small in volume (by a factor of 5 to 10) than the starting waste, and therefore, can be used in cement/concrete manufacturing or as fertilizer to provide concentrated source of K and P-bearing salts. Potassium present in poultry and certain animal wastes such as from swine, cows, horses, and sheep can provide the necessary catalyst. If necessary, additional supplemental potassium can be obtained from other cheap sources such as langbeinite and feldspar.

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

To meet this challenge, ABB, a major worldwide electrical equipment manufacturer, initiated a R&D program in 1995. Agriculturally based oils were considered the best choice. However, none of the vegetable oils commercially available were found to be suitable for immediate use because of the presence of undesirable components, poor oxidation stability, and high level of conducting impurities. The research project focused on 1) selection of a suitable base oil, 2) refining of the oil to electrical-grade purity, and 3) providing oxidation stability for long-term use when exposed to air periodically.

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

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

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

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

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

Biodiesel is a methyl ester of vegetable oil fatty acids. Its production has increased dramatically in the last few years to support America’s national strategic intent to diversify its fuels. This catalyst technology is positioned to capitalize on the megatrend toward biodiesel by using biodiesel to make high-value, high-performance, biodegradable, and safe surfactants. During 2006, Huntsman began manufacturing fatty methyl ester ethoxylates at its plant in the United States; the product name is SURFONIC® ME530-PS surfactant.

GEL-COR®: A New, Environmentally Compatible, Bullet-Trapping Medium for Small-Arms Firing Ranges: In 2003, there were approximately 12,000 small-arms firing ranges in the United States. In 2001, the U.S. EPA estimated that approximately 6.4 million pounds of lead go onto these ranges each year. Containing and recovering lead and other heavy metals in a safe, environmentally acceptable manner is vital to controlling soil and groundwater pollution from ranges.

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

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

Super Trap received two patents for this technology in 2006; it holds an exclusive license to the technology, developed under a Cooperative Research and Development Agreement with the U.S. Army.

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

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

In this use, the nominated technology could replace silica fillers. Finally, the GRAS coating can be used as a matting agent, which cures into the finished film and enhances the UV-curing process. Combined with other biobased additives, the GRAS coating can produce a rough surface that resists water and grease migration. In 2010, Ecology Coatings filed a patent application for this technology.

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

It offers a solution to printers who want to increase productivity without compromising the health and safety of their employees. BRIGL is the only wash on the market that effectively cleans conventional, heat-set, ultraviolet, electronic-beam, and co-cure inks, so that printers can use only one wash for an entire pressroom instead of the usual four to nine solvents. More important, unlike other "green" blanket and roller washes, BRIGL is easily implemented into the print production environment. Since BRIGL’s introduction in October 2006, over 50 full-time users have switched to it, and the list keeps growing. Premier printers who took part in Amerikal’s trial phase of BRIGL reported prolonged roller life, reduced overall consumption, a reduction in pressroom odors, and essentially no hazardous waste streams from blanket and roller washes.

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

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

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

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

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

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

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

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

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

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

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

Using Genencor’s enzyme formulation, Huntsman developed the GPB technology. Introduced in March 2009, GPB perfectly prepares cotton and elastane blends for dying. GPB enables low-temperature, neutral pH bleaching of fabrics and replaces harmful chemicals such as caustic soda. Gentler processing yields softer, bulkier, higher-quality fabrics than traditional bleaching and also reduces cotton loss during processing by 50 percent. An environmental lifecycle assessment (LCA) shows that GPB has a marked advantage over traditional textile bleaching for cotton fabrics. Lower treatment and rinsing temperatures and fewer rinse baths can result in water and energy savings of up to 40 percent for GPB. The LCA results demonstrate at least a 20 percent benefit in most categories, including climate change, human health, ecosystem quality, and water use, relative to a traditional bleaching system.

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

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

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

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

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

Ashland expects GEOSET NEO® binders to have a profound impact not only on foundries, but also on the environment. Substituting organic binders with inorganic binders can reduce a foundry’s emissions by up to 90 percent and assist in compliance with environmental regulations. GEOSET can eliminate most nuisance odors and smoke that would otherwise drift into communities near a foundry. Due to the rising price of petroleum, inorganic binders are comparable in cost to organic binders. During 2006 and 2007, Ashland implemented and cultivated joint development programs with customers.

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

Dow AgroSciences had already developed spinosad, a new reduced-risk insecticide active ingredient that was successful in spray applications. Dow AgroSciences combined its project management, industrial manufacturing, quality control, and formulation science skills with USDA’s knowledge of fruit fly biology and behavior. Together, Dow AgroSciences and USDA developed a superior bait technology, GF-120 NFTM, to protect fruits and vegetables from the Mediterranean fruit fly and similar pests. This is the first bait plus active ingredient (spinosad) that contains only organically acceptable components; it is so attractive to flies that farmers need less than 0.003 pounds of spinosad per acre. Between 2000 and 2004, farmers used GF-120 NFTM to treat over six million acres. GF-120 NFTM is now the fruit fly bait of choice in much of the world.

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

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

Methodologies of most of the tools are published in peer-reviewed scientific journals. Tools such as the Solvent Guide, FLASCTM, or the Green Technology Guide are first in their class and are recognized by academic and industrial groups for their innovation as leading the green design of pharmaceuticals. GSK continues to update the toolkit to integrate new scientific advances and regulatory information.

GSK routinely uses the toolkit to develop new products. During 2006, the mass percent of chemicals of concern across all products decreased nine-fold and the estimated average lifecycle impacts were reduced four-fold as compounds moved to the last stage of development.


Glycerin to Epichlorohydrin Process: How Green is my Epichlorohydrin?: Epichlorohydrin is a large-volume, commodity chemical used mostly to manufacture liquid epoxy resins. Estimated worldwide capacity for epichlorohydrin was two billion pounds in 2006. The predominant manufacturing process today is a multistep route using petrochemical-derived propylene and electrochemically generated chlorine as the primary feedstocks. This route has significant environmental issues including the formation of chlorinated byproducts and large amounts of wastewater. Further, the route incorporates only one of the four chlorine atoms it uses into the final product; the other three appear as aqueous chloride waste or hydrogen chloride.

The Dow Glycerin to Epichlorohydrin (GTE) process exploits the increasing availability of low-cost glycerin, which is a byproduct of biodiesel production from renewable seed oils. Likewise, it uses hydrogen chloride, a byproduct from several commodity-scale manufacturing processes such as the incumbent epichlorohydrin process, vinyl chloride, or isocyanate manufacture; hydrogen chloride is often neutralized and wasted. The GTE process uses a simple, two-step route with a carboxylic acid catalyst to synthesize epichlorohydrin. The key innovation is the use of hydrogen chloride at elevated pressure. The resulting elevated liquid-phase hydrogen chloride concentration drives the reaction to high conversions to the desired dichlorohydrins without removing the coproduct water from the reaction. Water in the reaction prevents the formation of chlorinated byproducts.

The GTE route has additional environmentally desirable attributes, including more efficient use of chlorine, formation of fewer chlorinated byproducts, and less production of aqueous chloride waste. The process will reduce wastewater by over 70 percent and reduce the formation of organic byproducts by over 75 percent. It is significantly more energy efficient: it uses 30-percent less steam and uses less energy to make chlorine and caustic. Commercialization of this economically and environmentally advantageous process is planned for 2011, when it will produce up to 150,000 metric tons per year of highly pure epichlorohydrin.

Glycerol tert-Butyl Ether (GTBE): A Biofuel Additive for Today: Current petroleum-based additives for boosting octane in gasoline improve the miles-per-gallon (mpg) of vehicles, but not significantly. The traditional fuel additive, methyl tert-butyl ether (MTBE), has been phased out in many states due to its toxicity and has no obvious replacement. Glycerol tert-butyl ether (GTBE) is a high-value, biobased fuel additive that improves the combustion and efficiency of petroleum and biobased fuels. CPS Biofuels has developed a process to make GTBE from waste glycerol, a low-value, high-volume byproduct of biodiesel production. CPS makes GTBE by acid catalysis of glycerol and isobutylene or other appropriate olefins followed by fractional distillation. Sulfuric acid is the preferred acid catalyst. Although GTBE can have up to three ether linkages, it is preferable to have at least one or two free hydroxyl groups to hydrogen-bond with ethanol and help lower its vapor pressure. GTBE is a biobased, nontoxic, biodegradable alternative fuel oxygenate and octane booster that helps fuel combust more completely and improves fuel efficiency with cleaner resulting emissions.

It both improves gas mileage and reduces greenhouse gas (GHG) emissions; with petroleum diesel fuels, it reduces up to 35 percent of particulates. It is useful as a fuel system icing inhibitor (FSII) in military (JP-8) and commercial (Jet A) kerosene-type jet fuel. GTBE can replace PRIST®, the existing jet fuel FSII, which is severely detrimental to human health. CPS is focusing on improving the efficiency of the E10 and E15 blends of biofuels for the existing energy infrastructure. GTBE fuel additives are compatible with the U.S. energy infrastructure, providing tremendous advantages over alternatives that require new production facilities or new engines for vehicles. CPS recently completed manufacturing trials, and testing of GTBE showed extremely efficient, essentially emission-free combustion and an octane rating over 120. GTBE has been commercially available as CPS PowerShotTM since January 2011.

Green Card: A Biopolymer-Based and Environmentally Conscious Printed Wiring Board Technology: Printed wiring boards (PWBs) have become ubiquitous in our society and are found in an ever-expanding range of industrial and consumer products including computers, VCRs, cameras, and automobiles. The demand for PWBs is increasing rapidly- the world market for PWBs has increased at an average rate of $2 billion per year since 1983 to a current value of over $25 billion. PWBs are composites that are generally formed from an epoxy or novolac resin coated on fiberglass or paper sheets that are laminated in multilayer stacks that are interleaved with suitably patterned copper sheets. PWBs provide both the substrate for physically attaching electrical components, as well as copper traces that provide electrical connectivity between the components. Due to the use of highly crosslinked thermosetting resins, the laminates form intractable composites that cannot be recycled by melting and reforming in the same manner as thermoplastic polymers.

Of increasing concern is the manufacture and disposal of the more than 150 million square meters of laminate that are produced globally each year. The resins currently in use for PWB manufacture are generated entirely from petroleum-based stocks. Natural products, especially if used in a form similar to that in which they occur in nature, generally take less energy to produce than their petroleum-based counterparts, hence replacement of part or all of the current raw materials could result in significant energy savings. Both energy and effluent (solid, liquid, or gaseous) reductions may be possible by choosing appropriate biobased raw materials.

New resin compositions that incorporate wood or plant resources (available in commercial quantities) were investigated. The technical objectives of this program culminated in the development and optimization of the use of lignin- a waste byproduct of paper manufacture- for the fabrication of several PWB demonstration vehicles to prove manufacturing feasibility. Resins that included as much as 50 to 60 wt% lignin were formulated to meet the primary requirements for printed circuit board physical and electrical properties. The utility of lignin in epoxy-based resins was demonstrated for a range of current and advanced applications. Pilot scale manufacture of resin and laminates using these formulations was accomplished on standard manufacturing equipment using current processing techniques and chemicals. In addition, the lignin/epoxy formulations have financial incentives that increase their desirability due to the inexpensive nature of lignin as a raw material.

A lifecycle analysis was performed, showing that the environmental benefits of a lignin-based resin system included reductions in energy usage, solid wastes, air and waterborne emissions, and "greenhouse gases" such as CO2from petroleum based sources, methane, and nitrogen oxides. Due to the lower energy requirements for production of natural raw materials, fuel usage for resin production can be cut by up to 40% by converting from standard epoxies to lignin-based resins. Lignin resins can be cast from ketone/alcohol or ketone/propylene glycol methyl ether acetate solvents, which would reduce the usage of methyl ethyl ketone (a SARA listed chemical) and acetone in PWB manufacture. Disposal concerns are also reduced, as incineration will produce reduced levels of greenhouse gases, and boards submitted to compost/landfill will have increased opportunity for biodegradation due to fungi potentially present in that environment that can break down lignin.

Green Chemistry for Energy Conservation and Indoor Environmental Quality: Ultraviolet photocatalytic oxidation (UVPCO) mimics naturally occurring atmospheric processes to improve indoor environmental quality (IEQ) by reducing levels of volatile, particulate, and biological contaminants. In UVPCO modules, UVC light activates nanoparticles of a titanium dioxide catalyst coated on a pleated flexible mesh support to initiate photocatalytic reactions. These reactions oxidize volatile organic compounds (VOCs), primarily to water and carbon dioxide (CO2); they also agglomerate fine particles and inactivate bioaerosols. UVPCO modules are integrated with air filters and instrumental controls into customized engineered systems that are more energy- and cost-efficient than conventional processes, such as carbon adsorption or particulate filtration. The scientific validity of UVPCO technology has been proven in environmental test chambers and at field test sites.

UVPCO technology is expected to replace carbon adsorption, which requires media derived from carbonization of petroleum feedstocks at high temperatures. UVPCO can destroy contaminants both in air circulated within buildings and in air exhausted to the atmosphere. Because UVPCO systems reuse indoor air for more cycles, they reduce the introduction of contaminants from outside air to indoor air. This broadly applicable technology offers benefits to human health and the environment by treating building environments to reduce air contaminants, thereby reducing ventilation demands and conserving energy.

Ingenuity IEQ, a small business in Midland, MI, incorporates UVPCO modules manufactured by Genesis Air into customized engineered systems that they design, install, and maintain in a variety of new and existing buildings. Genesis Air, Inc., a small business in Lubbock, TX, develops unique UVPCO modules that are generally applicable to healthcare, homeland security, LEEDTM green building systems, and ASHRAE High-Performance buildings in institutional, commercial, and governmental facilities within the United States. Ingenuity IEQ is positioning UVPCO, marketed as GAPTM technology, into new and existing systems to ensure proper residence time and effectiveness for optimized air purification.

Green Chemistry for Industrial Coatings: The conventional industrial coating process is pollution-, time-, space- and energy-intensive. In a departure from both solvent-based traditional coatings and newer powder coatings that require substantial heat to cure, Ecology Coatings’s LiquidNTM coatings are sprayable, 100 percent solids formulations that cross-link to form a durable barrier when exposed to ultraviolet light. They offer abrasion resistance, moisture resistance, and durability equal to or better than that of conventional waterborne, solvent-based, or powder coatings. The LiquidNTM coatings can be precision-sprayed at ambient temperatures, enabling them to integrate easily into existing finishing processes. Requiring only a few seconds of light exposure to cure, these pioneering coatings reduce time up to 99 percent, energy use up to 75 percent, and space on the manufacturing line up to 80 percent. These solvent-free coatings also virtually eliminate emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs), in turn reducing associated regulatory burdens.

In addition to presenting Ecology Coatings with clear economic and environmental advantages over conventional industrial coatings, LiquidNTM coatings have unique characteristics that enable them to serve an entirely new spectrum of applications. Because the coatings contain no liquid and do not require heat to cure, they are particularly well-suited for consumer electronics and other sensitive products. Unlike existing coatings that are generally limited to one or two applications, LiquidNTM coatings are suitable for plastics, metals, composites, paper, biodegradable materials, and more. Ecology Coatings’s innovative coatings technology is capable of propelling the coatings market, an integral piece of the U.S. manufacturing industry, into America’s greener future. Ecology Coatings has licensed its technology to DuPont Performance Coatings and Red Spot, which is a leader in the field of UV-curable coatings.

Green Chemistry in Action: A Remarkably Efficient and Sustainable Synthesis of the HIV Integrase Inhibitor, RaltegravirTM: ISENTRESS® (raltegravirTM) is the first medication to be approved in a new class of anti-retroviral therapies called integrase inhibitors. It represents a critical advance for the treatment of HIV/AIDS. Merck developed the initial route to raltegravirTM rapidly in response to a fast-paced clinical development program. This route produced enough of the drug for development and initial commercial launch. As Merck required quantities of this drug in the thousands-of-kilograms range, however, it became clear that the company needed a more efficient and sustainable route.

Merck’s process redesign resulted in a remarkably efficient, environmentally sustainable, eight-step process for raltegravirTM. The revised process combines a highly innovative, atom-economical Michael addition/cycloisomerization sequence used in the first-generation route with exceptional streamlining of the final steps. The improved process increases overall yield by 35 percent, reduces total waste by 70 percent, eliminates toxic reagents, and reduces the manufacturing cost. The process replaces methyl iodide, a well-known carcinogen, neurotoxin, and respiratory toxicant, with trimethylsulfoxonium iodide, an innovative, substantially less toxic substitute. The optimized process requires no special equipment.

Overall, Merck reduced the e-factor or process mass intensity (PMI) from 314 for the original process to 97 for the new process. This is a remarkable reduction of 12 PMI per step. The waste reduction is equal to 217 metric tons per metric ton of raltegravirTM manufactured. Given the required dose of 800 milligrams per person per day of ISENTRESS®, the waste reduction translates to 140 pounds per person per year compared to the original manufacturing route. Merck completely developed the revised process and introduced it into production at manufacturing scale in April 2008. Because Merck converted to its new optimized route shortly after it launched ISENTRESS®, the benefits of the greener process will accrue throughout the lifecycle of this important medicine.

Green Chemistry in the Manufacture of Thioglycolic Acid: Arkema Inc. has manufactured thioglycolic acid (TGA or mercaptoacetic acid) at its plant in Axis, AL for over 20 years. TGA is used as an industrial intermediate, a component of cosmetics, and a component of products to treat hides and leather. Arkema’s traditional process included hydrogen sulfide (H2S) as a feedstock. H2S is a poisonous, flammable, colorless gas that is regulated as an air pollutant, a water pollutant, and a hazardous waste. Because of its requirements for high-purity H2S feedstock, Arkema was buying H2S from a source in Canada and transporting over 4 million pounds of pressurized, liquid H2S by railcar to Alabama each year.

Arkema developed and implemented a beneficial process change that replaced the H2S in its manufacturing process with sodium hydrosulfide (NaSH). NaSH is safer for workers, is subject to fewer air, water, and waste regulations, is comparable to H2S in price, and is readily available in consistently high purity. Further, changing to NaSH involved little or no change in facility air or wastewater permits or disposal methods for spent materials. The substitution of NaSH solution for H2S gas in the TGA process allowed the Alabama plant to eliminate the cross-country transportation of millions of pounds of an extremely hazardous and toxic chemical, reduce the risk of accidental release of a toxic chemical, and lessen risk management activities at the plant. The major advantages of this substitution were improved worker safety and a reduced risk of environmental releases. At the same time, Arkema realized higher production yields of 1 million pounds per year. In 2004, Arkema finished switching over to NaSH and made engineering modifications to increase its production capacity.

Green Chemistry in the Redesign of the Celecoxib Process: Pfizer has redesigned its celecoxib manufacturing process with green chemistry objectives as some of the project’s primary goals. The results are dramatic environmental and worker safety improvements in the manufacture of the active ingredient in the medicine, Celebrex®. These improvements followed the elucidation of two unprecedented reaction mechanisms responsible for the formation of isomeric impurities whose presence required a subsequent recrystallization with its concomitant loss of yield and increased expense. Celecoxib made by Pfizer’s new process is pure enough to permit final isolation directly from the reaction mixture; such isolations are very rare in the pharmaceutical industry. Pfizer’s new mechanistic understanding increases the process efficiency significantly with respect to raw materials, solvents, energy, and waste.

The environmental and safety improvements are also significant. Compared to its initial process, Pfizer’s new process (based on 2003 production volume) reduced total waste (excluding water) from 8.9 million to 2.4 million kilograms per year (waste reduced from 23.4 to 6.3 kilograms per kilogram celecoxib). In total, Pfizer has eliminated 5,200 metric tons per year of organic solvents. Pfizer has also completely removed tetrahydrofuran and 35 percent hydrochloric acid (212 metric tons per year). Organic solvent washes during isolation have been partially replaced by water. In addition, raw materials have been reduced by over 150 metric tons per year. By eliminating the recrystallization and using the heats of reaction and other temperature parameters judiciously, Pfizer saves over 4 billion Btu per year. Pfizer has also improved worker safety by reducing the number of unit operations required per batch and improving the process payload (product produced/reactor volume), resulting in the need for fewer batches to fulfill demand.

The U.S. FDA has approved Pfizer’s improved manufacturing process for celecoxib; more than 50 similar agencies worldwide have also approved the new process. These regulatory authorities now require Pfizer’s new process for all commercial pharmaceutical manufacture of celecoxib.

Green Chemistry Process for the Large-Scale Manufacture of Polyamino Acids: Polyamino acids have properties that mimic proteins and make them ideal for targeted drug delivery. They are water-soluble, selective, biodegradable, low-toxicity molecules with a wide range of molecular weights. Their production, however, involves both unstable, intermediate amino acid N-carboxyanhydrides (NCAs) and polymer processing. Traditionally, these steps require large quantities of hazardous chemicals including phosgene, hydrogen bromide–acetic acid, acetone, and dioxane. Sigma-Aldrich has developed novel manufacturing processes for polyamino acids that minimize hazardous chemicals, improve efficiency, and increase product quality.

For NCA production, Sigma-Aldrich eliminated NCA recrystallizations and reduced manufacturing runs by over 30 percent. They reduced phosgene and tetrahydrofuran by 30 percent and ethyl acetate and hexane by 50 percent, which reduced hazardous waste. Finally, they increased consistency in quality and yield. Sigma-Aldrich also applied green chemistry to manufacturing poly-l-glutamic acid, a major drug-delivery polymer, which requires hazardous operations with hydrogen bromide–acetic acid or hydrogenation as well as highly flammable solvents.

Replacing a benzyl protecting group with an ethyl group allowed them to replace hazardous chemicals with water-based chemicals, decrease cycle time by over half, decrease energy use and greenhouse gas emissions, and improve the scaleup potential 10-fold. Sigma-Aldrich achieved similar savings with new processes for polylysine polymers and polyamino acid copolymers.

For polylysine polymers, Sigma-Aldrich used only half the previous amount of hazardous chemicals (dioxane, hydrogen bromide–acetic acid, and acetone), but increased the yield from 10–30 percent to 43–53 percent. Sigma-Aldrich halved production runs, which is saving hundreds of gallons of hazardous chemicals, generating less waste, and saving energy. They also switched polyamino acid copolymer production to water-based systems that eliminate benzyl bromide, a hazardous lachrymator byproduct. Sigma-Aldrich believes its contributions will lead to efficient chemotherapeutic treatments for diseases such as cancer, multiple sclerosis (MS), and diabetes and pave the way for greener chemical industry practices.

Green Chemistry through Function-Oriented Synthesis, Step Economy, and Ideal Synthesis: For decades, Professor Wender has pioneered the development of chemical methods for preparing biologically important molecules and has advanced the concepts of ideal synthesis and step economy. Recently, he has developed Functional Organic Synthesis (FOS), a multi-faceted, inclusive approach. FOS simplifies biologically active natural products to create new target structures that are amenable to preparative organic synthesis with greater efficiency and less waste while maintaining or improving their original activity. Professor Wender has revolutionized the preconceptions of other chemists by inventing new synthetic reactions that rapidly and efficiently raise the complexity of simpler starting materials to product-like intermediates in just a few steps. Professor Wender has impressed the chemistry community with his arene-olefin photocycloaddition, cyclopropane and other rearrangements, and numerous so-called "impossible" annelation reactions (e.g., [5+2], [2+2+2+2], [5+2+1], [4+4]).

FOS has not only guided the design of improved drug-like targets and their more efficient syntheses, but has also led to new reactions that achieve those goals better and with less waste. Recent examples of FOS from his laboratory include (1) simple arenes that modulate protein kinase C and mimic the more complex phorbols; (2) simplified enediyne compounds for cancer treatment; (3) simplified bryostatin analogs that contain only key pharmacophores, but have improved potency; (4) laulimalide analogs with simplified structures that remove the inherent functional instability of natural laulimalide, thus rendering them more desirable as drug candidates; (5) the design, synthesis, and optimization of polyarginine drug transporters to improve potency and circumvent multidrug resistance pathways in cancer cells; and (6) an efficient "reverse" process to transform a more plentiful natural product, phorbol, into prostratin, an important HIV drug adjuvant that activates the latent virus rendering it more available to conventional drug therapy. Professor Wender’s FOS concept has many facets, any of which can lead to greener chemistry in drug discovery.

Green Chemistry Through the Use of Supercritical Fluids and Free Radicals: Professor Tanko explored the use of supercritical carbon dioxide (SC-CO2) as a replacement for many of the toxic and/or environmentally-threatening solvents used in chemical synthesis. This research demonstrated that SC-CO2 is a viable, environmentally benign alternative to a variety of health or environmentally hazardous solvents and that there are also numerous advantages from a chemical perspective associated with the use of SC-CO2 . The research led to the development of a new, environmentally friendly chemical process for hydrocarbon functionalization and C-C bond formation. SC-CO2 is especially attractive because its critical parameters (temperature and pressure) are moderate, thereby permitting access to the supercritical state without a disproportionate expenditure of energy. The newly developed hydrocarbon functionalization accomplishes (in a single, high-yield step) a transformation which would normally require multiple steps and the use of toxic reagents or strong acids and bases. This reaction should scale up readily for large-scale (or industrial) applications.

Green Composites: Environment-Friendly and Fully Sustainable: Fiber-reinforced composites have many applications due to their favorable mechanical properties. Most composites on the market today, however, use nondegradable polymeric resins and fibers derived from petroleum. Professor Netravali uses plant-based, yearly renewable feedstocks to fabricate fully sustainable and environmentally friendly green composites. His chemically modified soy proteins have mechanical and thermal properties that make them suitable for use as resins. He reinforces these resins with plant-based fibers, yarns, or fabrics to make fully sustainable, environment-friendly, green composites. After use, his green resins and composites biodegrade fully during composting.

Soy protein is commercially available as isolate (SPI), concentrate (SPC), and flour (SF); it contains 18 amino acid residues, many of which have reactive amine, hydroxyl, or carboxyl groups. Soy protein can be processed into a lightly cross-linked resin, mainly through its cystine residues. Dehydroalanine residues formed from alanine can react with lysine and cystine to form additional cross-links. The resulting resin is too weak and brittle, however, for use in composites.

Professor Netravali has chemically modified SPC and SPI with Phytagel®, a linear D-glucose/D-glucuronic acid/L-rhamnose (2:1:1) tetrasaccharide, to form complex, interpenetrating network-like (IPN-like) structures that are also strongly hydrogen-bonded. Phytagel® forms a strong cross-linked gel with soy protein by ionic and hydrogen bonding in the presence of the mono- or divalent ions (ash and mineral) present naturally in soy protein. The resulting structure has excellent mechanical properties. Professor Netravali has obtained even better mechanical and thermal properties by dispersing exfoliated nanoclay particles in the IPN-like resin to form nanocomposite resins whose properties are better than those of common epoxy resins. He has used his modified soy resins with plant-based fibers such as flax and ramie to form green composites with excellent mechanical properties. Currently, Professor Netravali is working with Nissan, USA to mass manufacture green composite panels for automobile interiors.

Green LogicTM: Chitosan-Enhanced Paint Detackifier: GREEN LOGICTM is a liquid, chitosan-containing, paint denaturant technology that provides an alternative to traditional chemistries based on melamine–formaldehyde or acrylic acid. Paint denaturants, also referred to as "paint detackifiers", are added to the water curtain circulating in downdraft, water-washed paint spray booths to render oversprayed paint non-sticky. In traditional, wet paint spraying operations used in automotive original equipment manufacturing (OEM), only 50–80 percent of the paint is transferred to the vehicle; the residual 20–50 percent remains in the air until it is trapped in the circulating water curtain. The chemicals added to the water curtain detackify, coagulate, and flocculate this oversprayed paint, allowing it to be removed from the water later. The available melamine–formaldehyde-based detackifiers contain small amounts of free formaldehyde, a known carcinogen. The alternative acrylic acid based paint denaturants rely on two nonrenewable petroleum-based feedstocks: ethylene and propylene.

PPG derives its GREEN LOGICTM technology from the chitin of crab, lobster, and shrimp shells that are waste products of food production. Chitosan, the main component of GREEN LOGICTM technology, is poly(glucosamine), a glucosamine polysaccharide structurally similar to cellulose. PPG’s technology requires less overall tackification chemical and reduces the use of sodium hydroxide by 87 percent. Chitosan has been demonstrated to have antimicrobial properties and, therefore, it decreases the use of hazardous biocides. GREEN LOGICTM exhibits superior foam control, which reduces environmental stack emissions. The GREEN LOGICTM technology has performed as well as and in some cases better than traditional products used in this area while providing significant cost savings to customers and reducing their carbon footprints. Financial data from a number of customers show a 40-percent savings in wastewater treatment (approximately 5.5 million gallons per year per plant) and a 28-percent overall process savings. Seventeen automobile manufacturing plants in the United States are currently using this technology.

Green pH Electrodes: Glass tubing containing 20–30 percent lead is traditionally used to manufacture pH electrodes as it has the ideal workability and coefficient of expansion to easily fuse to the glass pH membrane tips. The solder used to join the electrodes’ cables and connectors contains lead as well. Mercury–mercurous chloride reference systems are also currently used in some pH electrodes. Both lead and mercury create problems with electrode disposal; they are known to be detrimental to the environment and, thus, products containing these heavy metals must be disposed of as hazardous waste.

Thermo Fisher Scientific is now using a lead-free glass and lead-free solder to create completely lead-free pH electrodes. The replacement glass uses a nickel–iron alloy metal seal instead of lead to achieve the necessary properties. The cost of this lead-free glass decreased recently so that it became a feasible replacement for lead-containing glass without increasing the cost of the electrode. Eliminating lead from all pH electrodes in the world market would save more than 2,000 kilograms of lead annually.

Some pH electrodes contain a mercury–mercurous chloride reference junction that is known to be very stable, even in difficult sample matrices. Testing has shown that a silver–silver chloride reference held in a stable polymer-based electrolyte gives the same performance, thus eliminating the need for mercury in the electrode. Eliminating mercury from electrodes prevents them from requiring disposal as hazardous waste and also prevents the risk of exposing the user to mercury if the electrode breaks.

These new pH electrodes will have performance and cost comparable to current lead- and mercury-containing electrodes, but will be disposable as regular trash. Thermo Fisher Scientific manufactured and tested its first prototype pH electrodes using completely lead-free glass in 2007.

The main raw materials for Green PolyurethaneTM are polyoxypropylene triols and epoxidized vegetable oils. NTI also uses primary aliphatic diamines prepared by biomimetic synthesis in its production of Green PolyurethaneTM. Green PolyurethaneTM is a potential replacement for current, isocyanate-based polyurethanes, especially those polyurethanes in foams and coatings that contain free isocyanates in aerosol form after polymerization. Green Polyurethane’sTM unique formulation combines the best mechanical properties of polyurethane with the chemical resistance properties of epoxy binders. Green PolyurethaneTM coatings contain no volatile organic compounds (VOCs).

They are solventless, 100 percent solids-based, 30–50 percent more resistant to chemical degradation, 10–30 percent more adhesive with some substrates, and 20 percent more wear-resistant. These coatings can also be applied on wet surfaces and will cure in cold conditions. Insulating foam made from Green PolyurethaneTM provides energy savings of more than 30 percent, has one of the highest R values per inch of all insulation materials, does not require a primer, and has greater adhesiveness. In 2010 EPA added Cycloate A, a key binder ingredient in Green PolyurethaneTM, to the Toxic Substances Control Act (TSCA) Inventory following Premanufacture Review. NTI submitted a Premanufacture Notice under TSCA for its proprietary hydroxyalkyl urethane modifier (HUM). Also in 2010, Nanotech Industries began commercializing its hybrid non-isocyanate polyurethane UV-resistant coating technology.

Green Primaries: Environmentally Friendly, Sensitive Explosives: Initiating devices use primary explosives (i.e., primaries) to detonate main charge explosives. The synthetic chemistry "holy-grail" in energetic materials has been the search for environmentally benign alternatives to replace toxic mercury fulminate, lead azide, and lead styphnate in primaries. Detrimental effects on the environment and personnel safety from primaries based on toxic mercury and lead have made their replacement essential.

Dr. Huynh at Los Alamos has created green primaries based on 5-nitrotetrazolato-N2-metalates that contain iron or copper. These green primaries are coordination anions charge-compensated by environmentally benign cations. They combine superior explosive performance with greatly improved health and safety conditions during synthesis, manufacturing, and use. They have many national security and commercial applications.

The U.S. Department of Defense requires environmentally friendly primaries to meet six criteria. They must be insensitive to moisture and light, sensitive to initiation but not too sensitive to handle, thermally stable to at least 200 °C, chemically stable for extended periods, and devoid of toxic metals and perchlorate. Dr. Huynh’s green primaries are the only primaries known to fulfill all six criteria. Green primaries give quantitative yields without purification or recrystallization, so they can be manufactured quickly with lower expenses for waste disposal.

The benefits of green primaries include safe, inexpensive manufacture and transport; elimination of mercury and lead contamination; great versatility in, and control over, initiating sensitivities and explosive performance; elimination of toxic waste; and release of only innocuous byproducts upon detonation. The benign detonation byproducts prevent chronic lead exposure to civilians and military personnel. Green primaries are safely prepared in, and desensitized by, water or ethanol, so toxic fumes and solvents are eliminated during preparation. Green primaries eliminate the potential for accidental explosions, saving lives. Finally, they reduce costs for specialized safety equipment, transportation, and liability insurance.

Three patent applications have been filed; all three will be licensed exclusively so that commercialization can begin.

Green Process of Unfolding Soy Protein Polymers for Green Adhesives: About 20 billion pounds of adhesives are used annually in the United States for applications including wood products, foundries, packaging, and labeling. These adhesives are mainly petroleum-based. Industry is seeking biobased adhesives and coatings, but enabling technologies are lacking. On the other hand, the byproducts of the current annual production of soybean biodiesel and corn ethanol include about 90 billion pounds of low-cost, protein-based meals aside from food and feed uses.

Most proteins contain both hydrophobic and hydrophilic regions. Hydrophobic interactions are a dominating factor in protein folding, unfolding, aggregation, gelling, self-assembly, adhesion, and cohesion. Hydrophobic regions are often buried inside the complicated protein molecule, however.

Professor Sun’s technology unfolds protein molecules with 0.5–5 percent nonhazardous agents such as urea, detergents, organic–inorganic salts, and pH-adjustment agents such as sodium hydroxide (NaOH) and hyrdrochloric acid (HCl). As the proteins unfold, some of their covalent and hydrogen bonds break and form individual polypeptides. Because hydrophobic groups are now exposed on their surfaces, the resulting polypeptides become surface-active and interact with other hydrophobic polymers, cross-linking agents, and chemicals. Potential applications include adhesives; surfactants; coatings; medical materials such as tissue engineering, drug delivery, and pharmaceuticals; thickeners and binders for food and animal feed; and cosmetic products. This technology makes high-value products from the coproducts of biofuel production and, thus, can have great impacts on bioenergy and the environment. It will replace at least 6 billion pounds of hazardous materials including adhesives based on formaldehyde, vinyl acetate, isocyanine, and acrylic acid. The performance of Professor Sun’s adhesives is superior or similar to urea–formaldehyde, phenol–formaldehyde, and many other synthetic, latex-based adhesives.

Dr. Sun’s adhesive technologies are in the pipeline for commercialization. Biodegradable, edible feed containers for livestock were commercialized in 2007. One company has licensed the technology for pet food binders; others are evaluating samples for a variety of uses.

Green Product and Munitions Compliance Analytical Systems: Until recently, manufacturers and regulatory agencies were restricted to qualitative, generic, and intuitive considerations of green chemicals and products (e.g., less harmful to human health and the environment) because no one had defined quantitative criteria for them. Chemical Compliance Systems has overcome this deficiency by compiling more than 75,000,000 data elements for over 210,000 chemicals and 250,000 products over the past 20 years.

They have synthesized these data into quantitative green chemical and product ratings with their Green Products Compliance Analytical System (GP-CAS) and their Green Munitions Analytical Compliance System (G-MACS). G-MACS also uses the MIDAS munitions characterization database from the U.S. Army Defense Ammunition Center. Both GP-CAS and G-MACS are based upon 46 green chemical criteria, each normalized on a scale of 0% (least green) to 100% (most green). These criteria encompass a broad spectrum of ecological, health, and safety hazards.

Both of these systems also identify which of 475 state, federal, and international regulatory lists include each chemical constituent of a product. Both systems can complete green analyses in 10-30 seconds. Any industry, facility, or location can utilize these systems, which have been available on the Internet since November 2003. GP-CAS and G-MACS can reap economic benefits throughout the product lifecycle. Chemical Compliance Systems can readily customize either system for special requirements and maintain confidentiality. Incorporation of these green analyses into complementary analytical systems is underway (e.g., their MSDS retrieval and manufacturing–import–export systems). No other capabilities of this type currently exist.

Green Sense? Concrete: Concrete is the most widely used, versatile building material in the world. It uses raw materials such as Portland cement and water (cement paste) as glue to hold fine and coarse aggregates together, creating a solid material for constructing buildings, houses, and roadways. Portland cement manufacturing requires so much energy that it produces a reported 5 percent of the world’s carbon dioxide (CO2) emissions according to the Portland Cement Association. Although the CO2-equivalent emissions, or carbon footprint, of products like concrete are often used as the only measure of environmental impacts, this information alone may produce misleading conclusions because the mining of aggregates also depletes natural resources. Considering several environmental impacts and rigorously measuring the comprehensive environmental impact and lifecycle costs of products allow more informed and science-based decisions on the most sustainable solutions.

BASF has developed a series of Glenium® chemical admixtures for use in concrete for multiple applications. The Glenium® chemical admixtures are engineered and carefully formulated products containing an aqueous solution of dispersants based on polycarboxylate ether chemistry. The aqueous Glenium® admixtures are nontoxic, nonhazardous, and nonflammable. These admixtures, when combined with alternative raw materials in concrete mixes, make up Green Sense? Concrete. Glenium® admixtures allow BASF to replace CO2-intensive Portland cement with traditional waste materials such as fly ash, slag, and cement kiln dust.

BASF also developed its Eco-Efficiency Analysis (EEA) tool for concrete. EEA is a third-party validated, award-winning holistic and strategic environmental lifecycle assessment methodology that focuses on multiple environmental parameters, not only CO2 emissions. With this tool, BASF can analyze each concrete mix to achieve new levels of economy and sustainability.

In 2009, BASF introduced Glenium® admixtures, Green Sense? concrete, and its EEA tool. In 2010, BASF Construction Chemicals worked with hundreds of concrete producers in the United States to optimize their concrete mixes with Glenium® admixtures and Green Sense? concrete.

Green Separation Science and Technology: Using Environmentally Benign Polymers to Replace VOCs in Industrial Scale Liquid/Liquid or Chromatographic Separations: One area of opportunity for new chemical science and engineering technology which will help meet the goals of Technology Vision 2020 is the development of new separations technologies that eliminate the use of flammable, toxic VOCs as industrial solvents. Used in conjunction with, or instead of, appropriate current manufacturing processes, such technologies would help to prevent pollution and increase safety. The nominated technologies are based on the use of water soluble polyethylene glycol polymers in either liquid/liquid (aqueous biphasic systems - ABS) or chromatographic (aqueous biphasic extraction chromatographic resins - ABEC) separations.

Two patented technologies are highlighted: a) applications in radiopharmacy to allow the use of cleaner neutron-irradiated isotopes rather than fission-produced isotopes, and b) applications in remediation where reduction of secondary waste streams or conventional technologies are anticipated. The separations approach followed in developing these technologies suggest a wider industrial application for VOC-free separations. Within a paradigm of pollution prevention and with industry participation, a tool-box approach to Green Separation Science & Technology can be developed based on the use of environmentally-benign polymers.

Green Synthesis of Nanometal Catalysts and Plant Surfactant-Based, In Situ Chemical Oxidation for Sustainable Treatment and Remediation: According to EPA’s 2004 publication, "Cleaning up the Nation’s Waste Sites", an estimated 294,000 sites will need to be cleaned up at an estimated cost of approximately $209 billion. Many of these sites contain Non-Aqueous-Phase Liquids (NAPLs). EPA also estimates that there are as many as 15,000 contaminated sites of former manufactured gas plants and coal-burning factories nationwide. Beyond digging up these sites and hauling large quantities of contaminated soils to landfills, there are extremely limited options currently available to treat NAPLs.

VeruTEK Technologies has developed a novel green reaction process called Surfactant-Enhanced In-Situ Chemical Oxidation (S-ISCOTM) to reduce the amount of NAPLs in soils. Its patent-pending S-ISCOTM technology uses VeruSOLTM (e.g., coconut oil, castor oil, citrus extracts: biodegradable, U.S. FDA Generally Recognized as Safe (GRAS) surfactants) to solubilize immiscible phase organic contaminants into groundwater where oxidation reactions readily destroy them.

Under a Cooperative Research and Development Agreement (CRADA) with EPA, VeruTEK has also produced nanometals made from simple plant extracts such as tea or other high-antioxidant plant polyphenols and dissolved metals at ambient temperature and pressure. VeruTEK has used these nanometals to catalyze advanced oxidation reactions; they have no hazardous materials in their synthesis and produce no hazardous wastes. In 2008, VeruTEK and EPA submitted a patent application for the green synthesis of these nanometals. VeruTEK has also developed green chemical reactions using plant-based co-solvents and surfactants to simultaneously solubilize and oxidize toxic, organic-phase contaminants in situ. These two processes will (1) reduce the use of toxic chemicals associated with the individual chemical reactions; (2) eliminate hazardous chemicals and wastes in the synthesis of many useful nanometals; (3) profoundly reduce the quantities of hazardous, regulated waste generated by excavating contaminated sites; and (4) eliminate the wasteful use of clean sand and gravel to backfill contaminated sites after excavation.

Green Technology for the 21st Century: Microporous Ceramics: The Green Technology for the 21st Century: Microporous Ceramics program is dedicated to both the fundamental understanding and practical environmental applications of microporous ceramic materials. These materials are typically used as thin porous films on a variety of supports for numerous applications. Such films are composed of nano particulate oxides (i.e., 0.5 to 10 nm in diameter) that are either randomly close-packed to form membranes (i.e., 30 percent porosity) or more loosely packed to form catalysts, photocatalysts, and thin film energy storage devices. Because the particle size, surface chemistry, and particle packing of these oxides can be controlled, so can the pore size, pore size distribution, and the physical-chemical properties of these materials.

As a result, the properties of these materials can be tailored for given applications which include reverse osmosis and gas separation membranes; high temperature membrane reactors; size and shape selective photolysis membranes; low temperature deep-oxidation catalysts; room temperature photocatalysts; and energy storage devices such as thin film batteries, ultracapacitors, and fuel cells. The Green Technology for the 21st Century: Microporous Ceramics program is illustrated using three examples: an indoor air cleaner for the complete oxidation of volatile organic compounds; an inorganic photoreactor for the size and shape selective synthesis of desired compounds with a minimum of waste; and, finally, an inexpensive, thin film ultra-capacitor which exceeds the U.S. Department of Energy"s near-term goal for this type of energy storage device.

GreenEarth® Cleaning, Dry Cleaning with Silicone Solvent: Historically, solvents used for dry cleaning fabrics have been hazardous to soil, groundwater, air, and industry employees. GreenEarth Cleaning (GEC) has developed and patented a process using cyclic siloxane (decamethylcyclopentasiloxane) that is a safe and viable alternative. Commercial drycleaners license the use of this process in their independent operations. Prior to commercializing this process, GEC conducted beta testing at 27 retail dry cleaning sites in the United States over a 10-month period.

During this period, two million pounds of clothing were processed, and independent, certified testing laboratories performed more than 26,000 test measurements on air and waste streams, proving the process is safe for the environment and employees. Beta-test sites also reduced the volume of their solid waste by 40–65 percent. The GEC silicone does not influence air quality because it is not volatile. Tests confirm that it will not impact soil or groundwater, as it degrades to SiO2, CO2, and H2O within 28 days. GEC has licensed this process at 481 locations in the United States and over 500 locations in ten other countries, with growing acceptance based on its health, safety, and environmental profile, as well as its operational advantages.

Greener by Design: An Efficient, Multiobjective Framework Under Uncertainty: Professor Diwekar and her group have developed an efficient, integrated framework for computer-aided green process design that combines chemical synthesis with process synthesis, design, and operation. Even in the presence of multiple, conflicting objectives, her framework uses new, efficient, optimization algorithms to provide cost-effective, environment-friendly designs that also explicitly identify trade-offs. The framework quantifies and characterizes uncertainties inherent in group contribution methods for chemical synthesis and in environmental impact assessments and includes them in the design process.

Because the property data needed to assess environmental impacts are not available for many molecules, scientists have turned to computational chemistry and molecular simulations to predict these properties. Previous simulations have, however, been computationally intensive and have produced large errors in predicted properties. Professor Diwekar’s new framework reduces computational intensity and predictive errors for environmental property prediction by an order of magnitude compared to other molecular simulations. Her framework has wide applicability ranging from molecular simulations to designing profitable greener chemicals, chemical processes, environmental control technologies, and energy systems. It can also be used for effective environmental management and operations including nuclear waste disposal and renewable energy systems.

In the last five years, Professor Diwekar’s work has resulted in 25 research papers in peerreviewed journals (including five invited papers), three invited chapters (one in The Encyclopedia of Chemical Technology), two American Institute of Chemical Engineers (AIChE) graduate research awards (a 2001 Separations Division Award and a 2002 Environmental Division Award), a patent application, industrial implementation, and several conference and invited presentations. Results of Dr. Diwekar’s work are currently being used in both continuous and batch chemical production and in energy systems. This is the first framework that considers chemical synthesis, process synthesis, and design under uncertainty together when confronted with multiple and conflicting objectives encountered in the selection of environment-friendly chemicals and technology designs for large-scale systems.

Greener Chemistry for Nitrate Analysis: Enzymatic Reduction Method: The Nitrate Elimination Company, Inc. (NECi) is pioneering the migration of enzyme-based analytical methods from research and biomedical labs into the mainstream analytical chemistry community. Biotechnology enables the engineering of enzymes into dependable analytical reagents. NECi has adapted a plant enzyme, nitrate reductase, for use in nitrate analysis. NECi’s recombinant nitrate reductase has made the company’s enzymatic reduction method for nitrate analysis robust and practical. The enzyme is produced in commercial quantities with consistent performance properties at affordable cost.

Nitrate is a primary analyte under the Safe Drinking Water and Clean Water Acts. The U.S. EPA-certified method for nitrate analysis in drinking water and wastewater is based on cadmium metal reduction of nitrate to nitrite and conversion of the nitrite to a colored compound using Greiss reagents. Cadmium is hazardous to handle and ends up as toxic, persistent waste after use of this method.

In the new technology, NECi’s recombinant nitrate reductase (NaR) and the natural reducing agent beta-nicotinamide adenine dinucleotide in its reduced form (NADH) replace the first step of the cadmium reduction method. The enzymatic method is sustainable, greener, and safe to handle; it generates only minimal amounts of biodegradable waste. The enzymatic method has been validated by comparison to the cadmium method. It is ideally suited for the newer robotic analyzers, called discrete analyzers, which are beginning to be used for water analysis in the United States and the rest of the world. Between 2004 and 2006, NECi commercialized two Superior Stock Nitrate Reductases (YNaR1 and AtNaR2) for automated nitrate analysis using continuous flow analysis and discrete analyzers. Currently, NECi is submitting its NaR-based nitrate analysis methods to Standard Methods and the U.S. EPA for certification as alternatives for nitrate analysis in drinking water and wastewater.

Greener Production of Functionalized Nanoparticles: Professor Hutchison has applied the principles of green chemistry to the production of functionalized metal nanoparticles. Functionalized nanoparticles bring together the functionality of a molecular ligand shell and the novel properties of a nanoparticle core, resulting in a high degree of functionality in a nanoscale object. The unique properties of functionalized nanoparticles promise to enhance or revolutionize applications in a wide array of technological sectors including medical diagnostics and therapeutics, catalysis, electronic/optic materials, and environmental remediation.

Methods of producing functionalized nanoparticles are typically inefficient; they often require hazardous reagents. Professor Hutchison’s team developed a novel synthesis of triphenylphosphine-stabilized gold nanoparticles that eliminates the need for hazardous reagents including diborane and benzene, reduces or eliminates organic solvents in both production and purification, and improves the overall safety of the process. At the same time, the synthesis is more efficient and economical. By addressing each of three steps involved in producing functionalized nanoparticles (core synthesis, functionalization, and purification), Professor Hutchison has demonstrated that human health, environmental, and economic benefits can be realized. Further, his approach is general and can be readily extended to the production of other nanoparticle compositions.

The production of metal nanoparticles alone is forecast to reach 2 million metric tons by 2010. Given this anticipated growth, Professor Hutchison expects his approach to have a significant impact in realizing greener nanotechnology. Because his methods reduce the cost to produce functionalized nanomaterials, there is now commercial interest in them. In 2006, Dune Sciences LLC was formed to commercialize applications of nanoparticles in medical diagnostics and catalysis.

Greenhouse Gases: From Waste to Product: About 5 billion pounds of adipic acid are manufactured worldwide each year. In the United States alone, approximately 3 billion pounds of adipic acid are produced every year. Adipic acid is used in the manufacture of a large number of consumer products, including nylon for carpets, apparel, industrial fabrics, and also for urethanes, plasticizers, and food additives. Essentially all adipic acid is manufactured today by a three step process starting with benzene: the benzene is hydrogenated to cyclohexane, the cyclohexane is oxidized with air to a mixture of cyclohexanol and cyclohexanone (KA oil), and the KA oil is oxidized to adipic acid using nitric acid as the oxidant.

Waste generation is a serious environmental issue with the traditional processes used to make adipic acid: the oxidation processes produce large amounts of nitrous oxide and organic wastes that must be disposed of or destroyed. For example, with the current technology, the production of 5 billion pounds of adipic acid also results in the production of 2 billion pounds of nitrous oxide. Nitrous oxide is a known greenhouse gas with a global warming potential 300 times greater than carbon dioxide and is also a suspected ozone depleter. It has been estimated that release of nitrous oxide from adipic acid manufacture accounts for 10% of the annual releases of manmade nitrous oxide into the atmosphere worldwide.

As part of Solutia"s program to search worldwide for new technologies to reduce or eliminate waste from its operations, the company initiated a partnership with Boreskov Institute of Catalysis in Novosibirsk, Siberia, to develop an alternative method for manufacturing adipic acid. This new process recycles the nitrous oxide waste gas and uses it as a raw material in the production of phenol. This eliminates either the direct release of this greenhouse gas into the atmosphere or the use of expensive, energy intensive CO2 greenhouse gas producing abatement processes. At the same time, the yield of phenol from Solutia"s new technology is very high. Furthermore, since the cost of this alternative method of producing adipic acid is lower than the commercial method traditionally used by the chemical industry, the process is both environmentally and economically sustainable.

A pilot plant demonstrating the process on a continuous basis was started at Solutia"s Pensacola Technology Center in May 1996. The unit has operated successfully since startup and provided the data currently being used in design of the full scale commercial plant. The new plant will utilize all of Solutia"s nitrous oxide (250 million pounds per year) to produce more than 300 million pounds per year of phenol. This revolutionary process represents the first major breakthrough in the production of phenol in more than 50 years. The new efficient process saves energy and eliminates the emission of massive amounts of greenhouse gases, while greatly reducing the production of organic wastes.

Greening Atorvastatin Manufacture: Replacing a Wasteful, Cryogenic Borohydride Reduction with a Green-by-Design, More Economical Biocatalytic Reduction for a Higher Quality Product: Atorvastatin calcium is the active ingredient in Pfizer’s cholesterol-lowering drug Lipitor®. The key advanced chiral intermediate in the manufacture of atorvastatin is t-butyl (4R,6R)-6-cyanomethyl-2,2-dimethyl-1,3-dioxane-4-acetate (i.e., ATS-8, also known as TBIN). It is the control point for stereopurity and the first isolated intermediate comprising both of atorvastatin’s chiral alcohol centers. Pfizer’s traditional ATS-8 process used a NaBH4 reduction of the corresponding (5R)-hydroxy-3-ketoester (ATS-6, HK) enantiomer under cryogenic conditions to give, after quenching, the (3R,5R)-dihydroxyester (ATS-7, diol). The ATS-6 was first converted with hazardous triethylborane in situ to a diastereo-directing boron chelate, which was then reacted with NaBH4 at or below -85 °C to promote diastereoinduction. After this reaction, the boronic wastes were removed by repeated methanol quenches and vacuum distillations. The diastereoinduction was inadequate, however, and several percent of the wrong (3S) diastereomer was formed. Subsequently, the ATS-7 diol, an oil, was protected as its acetonide, ATS-8, whose diastereopurity required upgrading by crystallization, with concomitant product loss.

Codexis developed a greener, more economical process for reducing ATS-6 to diastereopure ATS-7. This process uses a ketoreductase biocatalyst specifically evolved to reduce ATS-6 with perfect diastereoselectivity under greener, aqueous, ambient reaction conditions in conjunction with a previously evolved, process-tolerant glucose dehydrogenase biocatalyst. It obviates the use of hazardous boron reagents, reduces solvent use by 85 percent, reduces waste by 60 percent, lowers energy use dramatically, and provides a higher yield of more stereopure ATS-7. The ATS-7 from this reaction is already more diastereopure than was the atorva-statin in Pfizer’s Lipitor® pills as of 2006. Codexis’s biocatalytic process is now supplying tens of metric tons per year, and growing, of high-quality ATS-8 to manufacturers of atorva-statin for geographic generic markets. During 2008, Pfizer announced the conversion of its ATS-8 manufacture to a biocatalytic reduction using a ketoreductase in-licensed from a third party.

Greening Insecticides and Parasiticides: Synthetic chemicals are the current primary means of abating and controlling invertebrate pests, but these products are flawed due to the development of insect resistance, environmental concerns, and adverse health and environmental effects. Natural plant oils are safer and have various degrees of pesticidal activity, but historically have not been as effective as nor offered as broad a spectrum of control as products based on synthetic chemicals.

TyraTech is developing proprietary insecticide and parasiticide products that incorporate unique blends of natural active ingredients. TyraTech’s proprietary development platform enables them to identify potent mixtures of plant oils that are active as insecticides and parasiticides. Their screening platform currently includes three chemoreceptors that they cloned into Drosophila cell lines: the tyramine neurotransmitter receptor (expressed solely in invertebrates) and two insect olfactory receptors. Compounds that bind to and activate these receptors have been shown to be powerful insecticides. With this platform, TyraTech can rapidly select blends of individual oils that have synergistic ability to activate multiple insect neurological and olfactory receptors.

TyraTech’s products use natural, volatile oils as the main active ingredients, ensuring that toxic chemicals do not persist in the environment and also drastically limiting the potential for unintended adverse health effects for humans and other animals. By targeting multiple chemical receptors simultaneously with natural ingredients, TyraTech’s products decrease the incidence of insect resistance that is characteristic of the synthetic chemical pesticides currently in use. Their products are highly effective and inherently safer than other current products.

TyraTech is targeting diverse pesticide markets including agricultural and horticultural applications, consumer and institutional markets, professional pest control, vector control, and human and animal healthcare applications. During 2007, TyraTech commercialized its first product, a ready-to-use broad spectrum Crawling Insect Spray for the institutional market.

Greening Montelukast Manufacture: Replacing a Stoichiometric Chiral Boron Reagent with a Green-by-Design, Economical Biocatalytic Reduction Enabled by Directed Evolution: Methyl (S,E)-2-(3-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-hydroxypropyl)-benzoate (MLK-III) is the key chiral intermediate in the manufacture of montelukast sodium, the active pharmaceutical ingredient in Merck’s bronchodilator, Singulair®. The innovator’s ketone reduction to this chiral alcohol requires at least 1.8 equivalents of the expensive, hazardous reductant (–)-ß-chlorodiisopinocampheylborane ((–)-DIP-Cl) in tetrahydrofuran (THF) at -20 to -25 °C. After quenching, an extraction is required to remove spent borate salt waste. The reduction produces the S-alcohol in 97 percent enantiomeric excess (e.e.) and requires crystallization to give 99.5 percent e.e. in 87 percent isolated yield.

Codexis developed a green, more economical biocatalytic reduction to manufacture MLK-III with a ketoreductase biocatalyst evolved to reduce MLK-II, its ketone precursor. No naturally occurring or commercially available ketoreductase shows activity toward MLK-II. Codexis used a minimally active ketoreductase it had evolved previously and evolved it further to increase its activity and stability by over 2,000-fold, replacing one-third of the amino acids in its active site in the process.

The evolved ketoreductase produces MLK-III with essentially perfect enantioselectivity under greener reaction conditions: 100 g/L in isopropanol–water–toluene and 45 °C. Isopropanol is the reductant, which the ketoreductase uses to regenerate its catalytic cofactor NADPH, producing acetone as the coproduct. The process runs as a slurry-to-slurry conversion with product precipitation driving the reaction to completion. The precipitated chiral alcohol is of high chemical purity and exquisite stereopurity. (The distomer is undetectable.) Filtration and washing then recover MLK-III. The process replaces the hazardous boron reagent, greatly reduces organic solvent use, essentially eliminates inorganic salt waste, uses less energy, and provides a higher yield of MLK-III in higher stereopurity.

With its commercial manufacturing partner, Arch Pharmalabs, Codexis has scaled up the manufacture of MLK-III using this biocatalytic reduction and has provided samples of MLK-IV to manufacturers of generic montelukast. Codexis has scheduled commercial manufacture on the multi-ton scale in 2008.

Greening the Design of Chemical Production with Microbes: Currently, chemical synthesis using energy-intensive processes and fossil-based materials produces the majority of fine chemicals. In contrast, the biosynthesis of fine chemicals from biobased feedstocks has demonstrated feasibility and promise, however, over the past few years. Blue Marble Biomaterials is developing microbial systems to lower the carbon intensity and improve the lifecycle sustainability of fine chemical production. Blue Marble has developed a proprietary combination of microbes that produce a wide variety of fine chemicals and chemical intermediates including carboxylic acids, esters, thiols, and other organosulfur compounds in a single batch.

Blue Marble’s unique polyculture fermentation uses no genetically modified organisms and resists environmental stress. This fermentation can process low-cost, nonsterile lignin, cellulose, and protein-based waste byproducts from food, forestry, and algae companies without chemical or thermal preprocessing. Using these feedstocks for fermentation prevents landfilling or burning them and abates approximately 15.28 tons of carbon dioxide equivalents (CO2 eq.) per ton of feedstock. Compared to microbial systems that use carbon- and energy-intensive virgin or preprocessed plant materials, Blue Marble’s system recycles waste biomass, capturing the carbon it contains. In 2010, the company scaled up production to a commercial facility in Missoula, MT.

This facility is currently undergoing food-grade and kosher certification. It will operate at 100 percent capacity in the first quarter of 2012. Each year, it will use 860 wet tons of feedstock to produce 414,900 kg of carboxylic acids, esters, thiols, and other organosulfur compounds. An on-site water recycling system will reuse 75 percent of the water required for fermentation, saving 574,000 gallons of water per month. Finally, all biogas from the fermentation system will run through an algae remediation system to reduce facility emissions by scrubbing CO2 and methane. Blue Marble is working with several major manufacturers in the flavoring, food, and personal care industries and with Sigma-Aldrich Fine Chemicals toward global distribution of seven compounds.

GreensKeeper® Polymer Slurries for Oil and Gas Well Stimulation: In December 2003, the major oil and gas pumping service companies (Benchmark’s customers) entered into an agreement with the U.S. EPA to eliminate diesel fuel from hydraulic fracturing fluids injected into coalbed methane production wells. This agreement arose from U.S. EPA’s concern that diesel-based slurries used for oil and gas well stimulation pose a risk to underground sources of drinking water. To respond to its customers, Benchmark evaluated many potential carriers as diesel substitutes, considering slurry quality, cost, performance, safety and regulatory concerns, toxicity, flammability, and environmental impacts. Benchmark used these nondiesel carriers to evaluate more than a thousand different suspension slurries.

In 2004, Benchmark introduced its GreensKeeper® line of environmentally friendly polymer slurries to replace diesel-based slurries. GreensKeeper® slurry products are the first ones available to the industry that are completely compliant with the requirements of the Safe Drinking Water Act. GreensKeeper® not only eliminates diesel but also contains no benzene, toluene, ethylbenzene, or xylene (BTEX), or any of the 126 Priority Pollutants identified by the U.S. EPA.

In addition to superior environmental performance, GreensKeeper® products offer exceptional slurry characteristics including stability for extended periods at temperatures of over 100 °F, pumpability under subzero (less than °F) conditions, and compatibility with all commonly used boron, titanium, and zirconium cross-linkers. Unlike diesel-based slurries, GreensKeeper® slurry products are nonflammable, thus reducing fire and explosion risk during production, transport, storage, and use. Unlike diesel, they are not DOT-regulated, thus eliminating the risks associated with transporting hazardous chemicals. Widespread acceptance of GreensKeeper® slurries was directly attributable to Benchmark’s national distribution network and transportation capabilities. By December 2006, Benchmark had produced and sold over 10 million gallons of GreensKeeper® slurry to the oil and gas industry. After only 20 months, GreensKeeper® already represents 70 percent of Benchmark’s monthly slurry sales volumes.

GreenWorksTM Natural Cleaners from the Makers of Clorox: Home Cleaning Products: GreenWorksTM Natural Cleaners set a new standard for natural cleaning. These products perform as well as conventional cleaners and are composed of over 99-percent natural, plant-based ingredients from renewable sources and minerals. The formulas optimally blend natural ingredients and naturally derived surfactants to achieve excellent cleaning performance.

One key to the GreenWorksTM technology was Clorox’s development of a novel nanoemulsion that dissolves ingredients such as essential oils in the formulation as well as dirt or soil. The reduced particle sizes provide optimized surface interactions and increase the one-phase stability region. This technology enables GreenWorksTM products to be isotropic clear upon infinite dilution, reducing the ingredients by ten-fold compared to normal all-purpose or glass cleaners. The products are biodegradable and non-allergenic, are not tested on animals, and come in recyclable containers. The manufacturing facilities used to produce GreenWorksTM have zero emissions discharge. All GreenWorksTM products perform as well as or better than leading conventional cleaners in laboratory and in blind, in-home consumer tests. This level of cleaning is important to convincing consumers to switch from traditional cleaning products. The EPA Design for the Environment (DfE) initiative has recognized the safe ingredients and cleaning performance of GreenWorksTM products, which proudly display the DfE logo.

Fossil fuels contribute significantly to greenhouse gas emissions. By switching from petrochemicals to natural ingredients in its GreenWorksTM line, Clorox achieved a savings of approximately 450,000 gallons of petroleum in the United States during 2008. In addition, plant-based renewable sources reduce emissions of carbon dioxide (CO2), a greenhouse gas, during photosynthesis.

Clorox launched GreenWorksTM Natural Cleaners in January 2008. GreenWorksTM products sell at only a modest premium over conventional cleaners, despite their use of costlier plant-based renewable ingredients, an environmentally friendly manufacturing process, and innovative science, which together offer the consumer the most natural, powerful cleaning products on the market.

Grignards Going Greener by Continuous Processing: The synthetic pathways of numerous intermediates for food additives, industrial chemicals, and pharmaceuticals have included the Grignard reaction since the start of the 20th century. Despite these successes, the acute hazards of the Grignard reaction make it one of the more challenging reactions to bring to commercial scale. These hazards include: (1) strongly exothermic activation and reaction steps; (2) heterogeneous reactions with potential problems suspending and mixing the reaction mixture; and (3) extreme operational hazards posed by ethereal solvents such as diethyl ether. Eli Lilly and Company has developed inherently safer Grignard chemistry using a continuous stirred tank reactor (CSTR) that allows continuous formation of Grignard reagents with continuous coupling and quenching operations.

This strategy minimizes hazards by operating at a small reaction volume, performing metal activation only once for each campaign, and using 2-methyltetrahydrofuran (2-MeTHF) as a Grignard reagent and reaction solvent that may be derived from renewable resources. Grignard reactions using 2-MeTHF also result in products with enhanced chemo- and stereoselectivity. Relative to batch processing, the continuous approach allows rapid, steady-state control and overall reductions up to 43 percent in magnesium, 10 percent in Grignard reagent stoichiometry, and 30 percent in process mass intensity (PMI). The continuous approach reduces reaction impurities substantially. In addition, small-scale operation at end-of-reaction dilution allows all ambient processing conditions.

Lilly is using its CSTR Grignard approach to produce three pharmaceutical intermediates. One of these is the penultimate intermediate of LY2216684.HCl, a norepinephrine reuptake inhibitor that is under phase 3 clinical investigation for treatment of depression. Lilly uses a similar approach to synthesize an intermediate for LY500307, an investigational new drug candidate under clinical evaluation to treat benign prostatic hyperplasia. Lilly anticipates commercial production on 22 liter scales that will replace the 2,000 liter reactors used in batch processes.

Guar-Based Chemistry Advances Targeted Performance of Crop Sprays by Reducing Drift and Improving Retention: It is estimated that less than 10 percent of all sprayed pesticides reach their intended targets. A major reason for the off-target movement of pesticides is the drift of the droplets and the inability of the droplets to stick to a leaf or plant surface.

Rhodia uses derivatives of guar, a naturally occurring polysaccharide, to solve this problem. Hydroxypropoxylation (HP) of guar improves its hydration, making it amenable to uses in a wide range of temperatures. Rhodia’s technology uses HP-guar to mitigate the effect of drift and improve the retention of pesticide droplets on target surfaces. Guar-based polymers can reduce drift by increasing droplet size and can improve the retention of droplets by providing a "shock absorber" effect. The results of field trials using pesticides corroborate Rhodia’s fundamental studies: when guar-based polymers are added to a fungicide against the pathogen Asian soybean rust, both the efficacy and the crop yield increase. Also, results of field tests using an herbicide show that guar-based polymers increase weed kill across the board. More importantly, a very small amount of HP-guar (0.07 percent) can increase efficacy considerably, irrespective of the active ingredient.

Rhodia sells HP-guar for agricultural applications as AgRHOTMDR 2000. Farmers currently apply AgRHOTMDR 2000 on more than 16 million acres of soybeans in the United States, which represents 15 percent of the total sprayable soybean acreage. Within the next five years, Rhodia expects to apply its technology to other crops covering more than triple the current sprayable acreage.

HCR-188C1: A.S. Trust & Holdings, Inc.'s All-New, High-Efficiency Hydrocarbon Refrigerant With No Impact on Global Warming or the Ozone Layer: Chlorofluorocarbons (CFCs) have been used as refrigerants in air conditioners and refrigerators since the 1930s, when they were hailed as a safer alternative to dangerous coolants. Yet while CFCs have the advantages of safe incombustibility, high stability, and low toxicity, they also contribute heavily to ozone layer depletion, languishing as dangerous chlorine atoms in the stratosphere for up to a century. As a result, the production and use of CFCs have been virtually abolished over the past decade, and they’ve been systematically replaced by various hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). Yet while HCFCs and HFCs are less destructive to the ozone layer, they’re also powerful greenhouse gases that present their own set of unfortunate environmental risks.

A.S. Trust & Holdings has developed a new substitute hydrocarbon (HC) formulation, HCR-188C1, that has been independently shown to have zero ozone depletion potential (ODP) and zero global warming potential (GWP). HCR-188C1 is a proprietary blend made strictly from naturally occurring substances approved for common use and available at any gas manufacturer: propane, butane, isobutene, and ethane. This substance can be used independently of CFCs and HFCs/HCFCs, and cools so effectively that only one-quarter the mass of HCR-188C1 is needed in a refrigerator or automotive air-conditioning system that would have required a full charge of the CFC R-12 or the high-GWP formula HFC R-134a. HCR-188C1 is the only approved alternative refrigerant that can act as a substitute in both system types. HCR-188C1 also features major safety improvements over other HCs, including reduced charge rates, and solves the problem of decomposition upon leakage that causes HFCs to become less efficient and require more frequent replacement. HCR-188C1’s higher molecular weight makes it less apt to leak through joints or o-rings, and it also retains its cooling properties, thus extending the lifetime of any unit that runs on it. A.S. Trust has been successfully using the original HCR-188C formulation for automotive and refrigerator cooling for more than ten years.

Heavy Metals Free, Non-Formaldehyde Fixing Agent for Direct and Fiber Reactive Dyes: Generally, a textile fixing agent is a cationic polymer, which forms a resin film covering the surface of the fiber and adheres to it. This action causes the many cationic groups in the molecule of the polymer to bond with the dye anions in the fabric to block the hydrophilic groups of the dye, thereby forming insoluble salts. Once completed, this process allows the dye to be retained in the fabric, preserving the intended color shade through the normal washing processes. The cationic charges in these types of polymers is often supplied by the positive charge of heavy metal ions such as zinc. It was NICCA’s strong commitment to the environment and recognition of the value of such green chemistry that led to the development of NEOFIX® E-117. NEOFIX® E-117 is a heavy metals free, nonformaldehyde based fixing agent for direct and fiber reactive dyes. It significantly improves wash fastness of cellulosic fabrics and their blends. Unlike many fixing agents of this nature, NEOFIX® E-117 adds the extra benefit of helping its users comply with environmental and safety regulations by removing occupational and environmentally hazardous compounds.

High CO Tolerant Polymer Electrolyte Membrane Fuel Cell Technology: Polymer electrolyte membrane (PEM) fuel cells are a paradigm shift technology in power generation because they use an electrochemical process to convert hydrogen and oxygen into electricity without combustion and combustion associated pollution. A fuel cell operating on natural gas produces less than 1 ounce of air pollutants as compared to 25 lbs. of pollution produced by conventional combustion generation. Existing PEM fuel cells, however, are very sensitive to carbon monoxide (CO) poisoning and membrane hydration. Trace amounts of CO in the fuel can reduce fuel cell performance, and a reduction in the hydration of today’s membranes can shorten the membrane life. With such a high sensitivity to CO and hydration, current PEM fuel cells are expensive to maintain, and have limited lifetime and reliability.

Under the NIST Advanced Technology Program, Plug Power, Inc. has demonstrated a high CO tolerant fuel cell technology using a novel polymer electrolyte membrane. This new membrane does not require external humidification and because it operates at high temperature (160C), this new version of a PEM fuel cell can operate with over 1% (10,000 ppm) of CO without performance degradation. The significant increase in CO tolerance and the elimination of membrane hydration have substantially improved fuel cell operational performance and greatly simplified the overall system; thereby reducing system related cost and increasing system life. A reliable and low cost PEM fuel cell system with commercial viability is now being developed based on this new technology.

High Energy Efficiency, Environmentally Friendly Refrigerants: For several decades chlorofluorocarbons (CFCs) were the most widely used refrigerant fluids because of their nonflammability, low toxicity, low cost, and reasonably high performance. Because CFCs have been implicated in stratospheric ozone depletion, their production worldwide was stopped at the end of 1995 under the provisions of the Montreal Protocol as amended in Copenhagen in 1992. The phaseout of CFCs and HCFCs and increasing concern about greenhouse gases create the urgent need for nontoxic, nonflammable, environmentally safe refrigerants with high capacity and energy efficiency. Dr. Jonathan Nimitz and his co-inventor, Lance Lankford, have discovered and patented a family of improved refrigerants based on blends containing trifluoromethyl iodide (CF3I).

CF3I has attractive physical properties, zero ozone depletion potential (ODP), low global warming potential (GWP), relatively low toxicity, and is a combustion inhibitor. CF3I can be combined with high-capacity, energy-efficient, environmentally friendly, but flammable refrigerant compounds to obtain excellent refrigerant blends that remain nonflammable. The result is an energy-efficient, environmentally friendly, safe refrigerant. The inventors and Dole Food Company have formed a new company, Ikon, Inc., to support testing and commercialization of the refrigerants.

The first formulation developed, Ikon® A, has extremely low GWP and can be used in R-12 or R-134a systems. Ikon® A has been demonstrated for over 3 years in Dole Food Company refrigerated transports, with excellent results. Ikon® A was also tested in a new R-134a domestic refrigerator, with results of 19% higher energy efficiency and 15% greater volumetric cooling capacity versus R-134a. Ikon® B was developed as a less expensive version of Ikon® A; it has been tested and demonstrated in refrigerated transport units, a 5-ton water chiller (sponsored by NASA Kennedy Space Center), and a new R-134a domestic refrigerator (sponsored by EPA). A 20% market penetration of Ikon® B by 2010 will result in a decrease in carbon dioxide emissions of approximately 4 million tons per year.

There would also be annual reductions of approximately 12 thousand tons particulate, 16 thousand tons nitrogen oxides, and 24 thousand tons sulfur oxides. The installation cost for Ikon refrigerants will be repaid within 3 years in most applications. At 20% market penetration by 2010, $0.08 per kWhr and 15% lower energy use, estimated energy cost savings by 2010 are $400 million per year. The human health and environmental benefits of the Ikon refrigerants will be significant. Their use will result in improvements in human health, improvements in air and water quality, and reductions in skin cancer and ecological and crop damage from UV radiation.

High Performance Macromolecular Antioxidants for Materials: A Green Chemistry Approach: Industrial antioxidants are an increasingly important and fast-growing market. The antioxidant market generates annual sales of approximately $2.1 billion, based mainly on low-molecular weight products with limited thermal stability, relatively low material protection, and higher material diffusion rates.

Polnox Corporation is in the process of introducing seven high-performance macromolecular antioxidants that it synthesizes from FDA-approved phenol antioxidants in a one-step process using biocatalysts and biomimetic catalysts. Polnox invented a new biotechnology-based methodology for synthesizing its macromolecular antioxidants. The starting materials for the Polnox macromolecular antioxidants include butylated hydroxyanisole, tert-butylhydroquinone, and propyl gallate. The Polnox antioxidants have shown superior oxidative resistance (1- to 30 fold) and higher thermal stability compared with current low-molecular-weight antioxidants. The antioxidants demonstrate superior performance in a wide range of materials and applications including but not limited to plastics and elastomers, lubricants, fuels, oil, cooking oil, food and food packaging, and beverage and other industries. They are cost-effective, safe to use, and have a superior price-to-performance ratio. Acute oral toxicity (LD50) tests for these materials are at the same level as other FDA-approved antioxidants already used in food.

Dr. Cholli and his team at the University of Massachusetts Lowell originally discovered the technology. In January 2004, Dr. Cholli formed Polnox Corporation to commercialize his antioxidants. Polnox has filed for 40 patents and has also demonstrated production feasibility by scale-up to the multi-kilogram (mini-pilot plant) scale batches for two of its seven core antioxidants. Polnox completed beta site tests in 2006 and is planning to commercializeone or more of its antioxidants during 2007.

High Performance Soy-Based Metalworking Fluid: Metalworking fluids used in operations requiring high lubricity are typically formulated with petroleum oil and chlorinated paraffins, which are neither environmentally friendly nor readily biodegradable. In fact, EPA has placed chlorinated paraffins under regulatory scrutiny because they exhibit aquatic toxicity and certain chain lengths are considered to be carcinogens. Current annual sales of chlorinated paraffins for metalworking fluids are approximately 75 million pounds.

Desilube Technology has developed an environmentally friendly metalworking fluid that contains the methyl ester of soybean oil plus the organic amine salt of a phosphoric acid and a fatty acid. This fluid does not contain any chlorinated or sulfurized compounds and is not prepared with petroleum oil. It has been used successfully in commercial applications that require high lubricity. Desilube’s soybean oil based metalworking fluid outperforms conventional petroleum oil formulated with 35 percent chlorinated paraffin in two heavy-duty machining operations: deep drawing and fine blanking. The performance of Desilube’s metalworking fluid is due to synergism between the methyl ester of soybean oil and the amine salt of phosphoric acid with a fatty acid. This synergism also applies to water-dilutable metalworking fluid designed for metal removal applications.

Most, if not all, metalworking fluids currently used in these and other heavy-duty applications contain chlorinated paraffins. Desilube’s soy-based metalworking fluid has the potential to help replace chlorinated paraffins. In addition, the soybean oil base stock also has the potential to replace petroleum oil, reduce the dependency of the United States on crude oil, and take advantage of the large domestic supply of soybean oil provided in good part by farmers supporting the United Soybean Board.

The most recent patents for these soy-based technologies were published in 2010 and assigned to the United Soybean Board. Commercial sales of the environmentally friendly metalworking fluid over the past two years have averaged $45,000 per year.

High-Efficiency Olefin to Polyolefin Process with Toxic Solvent Elimination: ZIVATECH has developed novel catalytic processes to dehydrogenate aliphatic (paraffin) hydrocarbons into olefins and, subsequently, to polymerize them into polyolefins. These processes use catalytic dehydrogenation reactors in conjunction with polymerization reactors and coordination-type metal catalysts, such as titanium trichloride. This technology replaces the conventional cracking and refining of paraffins, which require more energy. In developing these processes, ZIVATECH considered materials and energy conservation coupled with environmentally benign modifications (e.g., eliminating toxic or hazardous solvents, catalysts, and other media). Process improvements include increased polymer and olefin product yields, recycling of both reactants and intermediate products within the process, reduction of toxic solvent generation, reduction of process steps, and reduction of capital and operational costs (including materials and energy costs). In 2005, this technology received a U.S. patent. ZIVATECH is currently in the process of licensing and scaling up this technology.

Highly Water-Dispersed Oilfield Corrosion Inhibitors Eliminate over One Million Pounds of Nonrenewable Solvents Annually: Corrosion-induced leaks in hydrocarbon-producing equipment threaten safety, health, and the environment. Only recently, however, has anyone focused on safer corrosion inhibitors with reduced environmental impacts. Extensive product development by Baker Hughes has led to an innovative line of corrosion management chemicals that is free of hydrocarbon solvents, but contains active inhibitors that historically could only be formulated with these flammable solvents. The new, highly water-dispersed products exhibit better dispersibility and water partitioning in use than traditional products and, therefore, deliver the active inhibitors to metal surfaces more efficiently. The net result is significantly reduced field-level chemical use rates that do not compromise corrosion inhibitor performance.

This innovative technology entails much more than simply making water-soluble formulations. What truly distinguishes the new technology is its use of the inhibitors themselves as dispersing agents, both eliminating the need for hydrocarbon solvents and limiting or eliminating the need for additional additives or surfactants. The chemistry is based on formulated fatty acid amide–imidazoline technology. Careful adjustments of pH, hydrophilic-lipophilic balance, and levels of active ingredients produce stable dispersions of the inhibitors with no or only minimal added surfactants. As a result, oilfield operators can reap the benefits of the powerful chemicals commonly found in hydrocarbon-based, corrosion-inhibiting products in safer, water-based formulas that have less impact on the environment. The water-based products contain no naphthalene; they have higher flash-points than traditional, solvent-based products, so they are safer to store and handle.

Since 2006, Baker Hughes has commercialized five of these products. Based on 2009 sales, the net direct environmental impact of this technology is the elimination of at least 1 million pounds of hydrocarbon solvents annually. With continuing development and as oilfield deployment of this technology grows, the direct and indirect positive impacts of the technology are expected to increase several-fold in the very near term.

High-Performance Polyols from CO2 at Low Cost: The vast majority of polyols currently used in coatings, foams, adhesives, elastomers, and thermoplastic polyurethanes are derived exclusively from petrochemicals. Novomer has developed a proprietary technology platform that transforms waste carbon dioxide (CO2) into very precise, high-performance polyols at lower cost than polyols from either petroleum or natural oils. Novomer’s polyol technology platform combines several innovations. Novomer has developed a breakthrough cobalt-based CO2–epoxide catalyst that is over 500-fold more active and far more precise than past zinc-based catalysts. I

n 2011, Novomer modified its catalyst system with resin bed technology to recover and recycle the catalyst without losing activity or selectivity. Novomer was also the first to develop low-molecular-weight CO2-based polyols using chain-transfer agents. The manufacturing process for Novomer’s CO2-based polyols is a proven, low-cost, synthetic technology based on chemistry. It can be completed in existing chemical industry infrastructure under mild reaction conditions with conversions of over 90 percent in short timeframes. Using CO2 cuts raw material costs nearly in half, yielding a significant cost advantage. The environmental and human health benefits of Novomer’s CO2-based polyol technology platform are considerable. Because these polyols contain 40–50 percent CO2 by weight, they can potentially sequester 10 billion pounds of CO2 per year in targeted polyol markets.

More important, they enable the chemical industry to eliminate 10 billion pounds per year of petroleum-based raw materials, a source reduction that impacts the entire petrochemical value chain. In addition, because Novomer polycarbonate polyols contain no bisphenol A (BPA), they can potentially eliminate the use of BPA-containing resins in food-contact coatings. Novomer is commercializing its polyols in several markets. Jointly with the Dutch company, DSM, Novomer will introduce its first large-scale commercial polyol product for coil coating applications in 2012. In partnership with industry-leading polyol producers, formulators, and end users, Novomer is developing additional polyol products for footwear foams, rigid insulating foams, and polyurethane adhesives.

High-Solids Hybrid Sucrose Ester Polymer Technology: In 2007, the U.S. paint market included approximately 500 million gallons of solventborne paints and coatings. In general, these were solvent-rich, oil-based products containing over 350 grams per liter of volatile organic compounds (VOCs). Upcoming regulations in the United States, however, are tightening the limits for VOCs in coatings, especially architectural and industrial coatings. As one example, EPA’s VOC targets for 2010 are less than 100 grams per liter for non-flat architectural coatings. These and other regulations have necessitated a search for alternate, VOC-compliant products that feel and apply by brush, roller, and spray like high-VOC coatings.

Sherwin-Williams developed its innovative, high-solids, hybrid sucrose ester polymer technology to address this urgent need. Sherwin-Williams’s novel, high-solids, oxidative crosslinking hybrid sucrose ester technology uses a modified sucrose ester technology from the Procter and Gamble Company (P&G). At the request of Sherwin-Williams, P&G converted its Sucrose Ester 7.75 (Sefose® 7.75, which has no reactive groups) into a reactive Sucrose Ester 6.0 (Sefose® 6.0) with two reactive hydroxyls available for further modification.

Sherwin-Williams then acrylated Sucrose Ester 6.0 with methacrylic anhydride in a solventless process to obtain a 100-percent-solids acrylated sucrose ester polymer. This ester polymer was formulated, scaled-up, and commercialized into pigmented, oil-based coatings with excellent performance and application features for architectural and industrial maintenance applications. A single coat of the higher-solids product gives the opacification desired by customers. Subsequently, Sherwin-Williams replaced methacrylic anhydride with glycidyl methacrylate for industrial applications; this second-generation technology was acrylated and urethanated without generating waste byproducts via ring-opening of the epoxide.

This technology is enabling Sherwin-Williams to market the only compliant, oil-based, pigmented coating in the United States with VOCs less than half of the current oil-based coatings. In 2006 and 2007, Sherwin-Williams filed a patent application and commercialized three products using this technology.

Hydrofluoroethers (HFEs)—The Right Balance of Properties: Research on hydrofluoroethers (HFEs) started in 1994, and the first commercial compound came to the marketplace in 1996. The design of the hydrofluoroethers provides a balance of properties that make them excellent substitutes for ozone-depleting compounds. 3M formed a technical team in the early 1990s to find a substitute for ozone-depleting substances (ODSs, i.e., CFCs and HCFCs). In addition to addressing the issue of ozone depletion, the team also set criteria for candidate molecules on the basis of flammability, toxicity, photochemical reactivity (potential for smog formation), and global warming potential.

The 3M team investigated the performance, health, and environmental attributes of more than 100 compounds before the invention of HFEs. HFEs did not require the team to compromise on any of its desired qualities for an ODS replacement. HFEs do not deplete the ozone layer, do not contribute to photochemical smog, are very low in toxicity, are nonflammable, and have very low global warming potentials. The first commercial product for the HFE program was HFE-7100. HFE-7100 (C4F9OCH3) was brought to the market in 1996 and was followed by HFE-7200 (C4F9OCH2CH3) in 1997. Both of these compounds are approved for use under EPA’s Significant New Alternatives Policy Program (SNAP) for solvent cleaning, aerosol, and heat transfer applications. E

PA also declared these materials as VOC exempt on August 25, 1997. The acute and subchronic toxicity of HFE-7100 has been thoroughly investigated. An evaluation of these data by the American Industrial Hygiene Association Workplace Environment Exposure Limit Committee yielded an exposure guideline of 750 ppm. The exceptional low toxicity of HFEs make them unique in a marketplace that has traditionally had to compromise on the toxicity of available alternatives.

Hydrogen Sulfide Elimination: Mallinckrodt Baker has developed a method that eliminates hydrogen sulfide from the substances not precipitated by H2S test. The existing method uses hazardous hydrogen sulfide, takes about 5 hours to perform, and is precise only for combined alkali results. The new method is safer (does not use hazardous reagents), takes only 30 minutes to perform, and is accurate for individual element determinations.

Imation No Process Plates: Although the principles of lithography were first applied to printing in 1796, aluminum plates precoated with photoactive polymers did not enter volume production until the 1950s. Availability of these presensitized plates fueled rapid growth in the lithographic printing industry due to superior print performance and economy. When a conventional presensitized plate is exposed to ultraviolet radiation through a contact masking film, formation of ink receptive image areas is initiated. These plates then require wet development to activate the printing surface, most often using a mechanical processor that also rinses the plates.

Many developers contain hazardous solvents. Developer solutions saturate with dissolved coating compounds, including toxins and heavy metals. Total U.S. printing plate consumption in the year 2000 is expected to reach 68 million square yards. Wet processing of this total volume will consume over one million gallons of aqueous developer, based upon typical depletion rates. Depleted solutions containing coating solids require disposal at hazardous waste sites in many regions of the United States. In addition, more than 1.2 billion gallons of rinse water would become part of the waste stream.

Recognizing the environmental costs of the total waste stream, Imation launched an intensive Research and Development effort to commercialize plates requiring no wet chemical processing of any kind. Today, this no process technology provides a superior printing plate, without wet processing, under the trademark name "ImationTM No Process Plates." Demand for the technology is growing rapidly across the printing industry. ImationTM No Process Plates employ photoactive polymers that form printing surfaces without wet chemical processing. When the plate is exposed to ultraviolet radiation through a masking film, formation of ink receptive areas is initiated, but activation takes place on press under action of the ink/water emulsion during the normal plate roll up process.

This technology is applicable across the printing industry, from general commercial lithographic printing to forms, packaging, and newsprint operations. Environmental benefits available to the industry are truly significant and valuable because pollution is prevented through source reduction. When ImationTM No Process Plates are used along with Imation’s DryViewTM imagesetting films, even greater waste reductions are possible. If 68 million square yards of DryViewTM film were used to image plates, an additional 2.4 million gallons of film developer, 4.1 million gallons of fixer, and 675 million gallons of rinse waste could be eliminated from the waste stream.

IMPACT Technology: A Greener Polyether Polyol Process: The Bayer MaterialScience (BMS) IMPACT technology for polyether polyol (PET) production couples a breakthrough catalyst invention with an equally innovative process design. The IMPACT process includes modifying the double metal cyanide (DMC) catalyst to increase its reactivity more than 10-fold and exploiting an unusual kinetic property: the modified DMC selectively adds alkylene oxides to the lower-molecular-weight molecules in a mixture of molecular weights. Combining these two inventions gives a continuous process that requires less equipment. The new process generates less waste, eliminates process steps, and is inherently safer.

A gate-to-gate life cycle assessment (LCA) of the continuous process in comparison with conventional technology shows reductions of 76–80 percent in energy consumption, carbon dioxide (CO2) generation, acidification, eutrophication potential, and smog. Moreover, the BMS Channelview, TX plant eliminates over 34 kilotons of wastewater annually at typical run rates and reduces over 32 kilotons of CO2 equivalents at full capacity. Recently, total production in the United States using the continuous process reached a billion pounds, and BMS completed licensing its technology to major competitors.

These milestones have established IMPACT as the industry standard in environmental savings and productivity. Worldwide, plants will be converted or constructed for IMPACT technology, increasing the positive effects on the environment. Polyethers for use in polyurethanes have a multi-billionpound worldwide market with applications spanning nearly every market segment including insulation, coatings, elastomers, and flexible foams such as bedding, furniture, and automotive seating. BMS has a 23-percent market share with a global capacity of over 1,100 kilotons. Around 50 percent of BMS’s PET production can be manufactured using the IMPACT technology. BMS has converted about half of this volume to the new processes. BMS has used this technology to double PET production at the Channelview plant within four years to 200 kilotons and has lowered its variable production costs by 40 percent.

Implementation and Verification of Aqueous Alkaline Cleaners: Lockheed Martin Tactical Aircraft Systems (LMTAS) was the first aerospace company to implement innovative aqueous cleaning technology for cleaning tubing and honeycomb core. Tubing is used in the aerospace industry for transferring pressurized oxygen within an aerospace vehicle. Honeycomb core is used in the aerospace industry for producing bonded structural parts. Both applications require that the parts meet stringent cleanliness requirements. These requirements were previously met by using cold cleaning or vapor degreasing with chlorinated solvents.

These solvents included 1,1,1-trichloethane [sic] (TCA) and trichloroethylene (TCE). These chlorinated solvents are toxic, and TCA is an ozone depleting compound. The use of chlorinated solvents posed a threat to the environment because the solvents were commonly released into the air during cleaning operations and because the likelihood of a spill during their use was significant. These solvents were successfully replaced with aqueous cleaning technology. As of November 1993, 100 percent of tubing manufactured at LMTAS (including oxygen tubing) is being cleaned in an aqueous cleaning system. As of May 1994, 100 percent of all honeycomb core used at LMTAS is also being cleaned in an aqueous cleaning system.

Implementation of aqueous cleaning technology at LMTAS eliminated approximately 360 tons of air emissions per year and resulted in a cost savings of $490,000 per year. In addition to replacing chlorinated solvents with the innovative aqueous cleaning technology, LMTAS also explored the use of environmentally safe methods for quantifying surface contaminants on parts cleaned by various cleaning technologies. Traditionally, extraction with CFC-113 followed by gravimetric or FTIR analysis has been used for quantifying surface contaminants. The use of CFC-113 is undesirable due to its ozone depleting potential. LMTAS has demonstrated the usefulness of carbon dioxide coulometry for determining the amount of residue remaining on a surface after cleaning and has used this technique for comparing the cleaning effectiveness of various cleaning technologies.

Improved Resource Use in Carbon Nanotube Synthesis via Mechanistic Understanding: Carbon nanotube (CNT) production by catalytic chemical vapor deposition (CVD) currently exceeds 300 tons per year and is growing. The current CVD process has very low yields (3 percent or less) and high energy requirements. Emissions from ethene- and H2-fed CVD reactors contain over 45 distinct chemicals including: the potent greenhouse gas, methane; toxic and smog-forming compounds, such as benzene and 1,3-butadiene; and trace quantities of polycyclic aromatic hydrocarbons.

Eliminating thermal treatment of the feedstock gases may prevent the formation of unwanted byproducts, reduce energy demands, and improve overall control of the synthesis, but heating the feedstock gas is necessary to generate the critical, previously unidentified, CNT precursor molecules required for rapid CNT growth. Using in situ CNT height measurements and gas analysis, Professor Plata and her group identified the heat-generated compounds correlated with rapid CNT formation (e.g., propyne and but-1-en-3-yne). She then mixed each of these chemicals with typical feedstock gases (C2H4 and H2) without preheating and tested them with a heated metal catalyst. She found that several alkynes (e.g., ethyne, propyne, and but-1-en-3-yne) accelerate CNT formation.

This new mechanism for CNT formation features C–C bond formation between intact chemical precursors, similar to polymerizations. It challenges the accepted hypothesis that precursors must completely dissociate into C or C2 units before "precipitating" from the metal. Using these mechanistic insights, Professor Plata can form high-purity CNTs rapidly.

Her technology improves yields by 15-fold, reduces energy costs by 50 percent, and reduces the ethene and H2 starting materials by 20 and 40 percent, respectively. It also reduces unwanted byproducts by over 10-fold (translating to ton-sized reductions in toxic and smog-forming chemicals and greenhouse gases). The reduced starting materials and energy requirements also lower the cost of CNTs without sacrificing product quality. A commercial CNT manufacturer has licensed this patent-pending work.

In Vivo Synthesis of Lepidopteran Pheromone Precursors in Saccharomyces Cereviseae: An Economical Process for the Production of Effective, Nontoxic, Environmentally Safe Insect Control Products: Since the advent of DDT more than 50 years ago, broad spectrum neurotoxic insecticides have provided the principle means for the control of economically important insects in agriculture and public health programs. Whereas the use of synthetic insecticides initially resulted in spectacular increases in crop yields and the suppression of some important human and animal disease vectors, the development of insecticide resistance in insect pest populations and the environmental damage caused by insecticides were quickly recognized as serious drawbacks to their use.

Today, the environmental and human health effects associated with the manufacture and use of insecticides for pest control are widely recognized, including their acute toxicity to nontarget organisms (including human applicators), their persistence in the biosphere, and major point-source pollution associated with their manufacture. Despite these effects, the scale of release of active ingredients in insecticide formulations into the global environment is enormous; in the United States alone it is more than 400 million kg/year.

Pheromones have been used on a worldwide basis for the control of insect pests for more than 15 years. Unlike conventional broad-spectrum insecticides, pheromones are nontoxic and highly specific for the species they are intended to control. Unfortunately, their effectiveness and selectivity depend upon high chemical and stereospecific purity, making them expensive to synthesize. The latter factor has limited their commercial success versus conventional insecticides. The major market for pheromone-based disruption products is in the United States and amounts to less than $50 million/year. In contrast, the worldwide insecticide market is greater than $6 billion/year.

The goal of the work of Dr. Knipple at Cornell University is to develop a cheaper process for pheromone synthesis. Toward this goal, he has proposed to use genetic and molecular technology to clone and functionally express in vivo genes encoding desaturase enzymes present in the pheromone glands of adult female moths, which catalyze the formation of key unsaturated pheromone intermediates. Accomplishment of the technical objectives of this work will contribute materially and methodologically to development of an alternative biosynthetic process for commercial pheromone production. Achievement of the latter goal will significantly improve the economic competitiveness of existing pheromone products and could provide the basis for the expansion of this promising insect control technology into other markets.

Increased Utilization of Raw Materials in the Production of Vinyl Chloride Monomer: Commercial catalytic oxidation processes have been adapted for disposal of organic solvents, ground-water pollutants, synthetic co-products, incinerator flue exhaust, and automotive exhausts. In the large-scale catalytic oxidation of chlorinated hydrocarbons, fuel value is typically recovered as steam and chlorine is recovered as HCl and/or Cl2. Various approaches are disclosed in the patent and scientific literature. Studies of the deactivation of commercial catalysts over long-term exposure of streams of chlorinated and nonchlorinated hydrocarbons found that during long-term use the reaction temperature needed to be increased in order to maintain high conversion rates and reduce catalyst deactivation.

In commercial scale catalytic oxidation of chlorinated materials, the maximum operating temperatures are limited by the optimal temperature range for the chosen catalyst as well as the corrosion resistance inherent in the metals used for the equipment. For example, certain economical nickel alloy steels undergo catastrophic corrosion in the presence of HCl at or above 530 ºC. Increasing the operating temperature of the reaction approaching 530 ºC will lead to higher corrosion rates. It would therefore be desirable from an economic standpoint to maintain very high conversion of 99% or higher of feedstocks over long periods of time without risking increased rates of corrosion.

Geon developed CatoxidTM as a catalytic process for the recovery of chlorine and energy from chlorinated organic materials. Typically, such materials are co-products of the production of useful chemicals such as vinyl chloride monomer (VCM), or other chlorinated and nonchlorinated products. The recovery is accomplished by catalytically reacting the organochlorines and an oxygen containing gas such as air to produce hydrogen chloride (HCl), carbon dioxide (CO2), and water in a fluidized bed reactor. No additional fuel is required to sustain the exothermic reaction, and the chemical energy of the materials is recovered as steam.

The HCl produced is fed directly to an oxychlorination reactor and recovered as 1,2-dichloroethane (EDC). The EDC is subsequently converted to VCM and ultimately PVC. The CatoxidTM process thus reduces the amount of chlorine required to produce a specific amount of the desired product VCM, and also reduces the fuel requirements of the production facility. Unlike incineration, which is the only acceptable alternative, the CatoxidTM process has no vents to the atmosphere. In addition, since no aqueous hydrochloric acid is generated (as is usually the case for incinerators), there is no need to utilize caustic or limestone to neutralize the acid. The CatoxidTM process was developed for the EDC/VCM/PVC industry and is directly applicable to many technologies used to produce VCM.

Industry-University-Government Partnership for Converting Regional Wastes into Chemical Products: A unique partnership in Maryland is demonstrating innovative approaches to simultaneously solve environmental problems and facilitate economic development. This partnership includes two companies (a composting company and a specialty chemical company), a chemical engineering professor, and a technology development specialist from a state economic development office. The goal of this partnership is to convert food and agricultural wastes into chemical products - thereby reducing nutrient addition to the Chesapeake Bay while creating manufacturing industries based on the state’s renewable natural resources.

Beginning with wastes from Maryland’s crab-packing industry, the partners guided research and development, leveraged state and federal resources, and obtained private sector funding to establish a manufacturing operation. The culmination of this partnership is ChitinWorks America, a private company that is converting wastes from Maryland’s crab-packing industry into the specialty biopolymer, chitosan. This manufacturing operation meets the state’s need to cost-effectively manage nutrient-rich wastes, while sparing the state’s crab packing industry the financial burdens associated with landfilling. Additionally, the product of this manufacturing operation is an environmentally-friendly biopolymer for various specialty applications (e.g. oil drilling).

Inert Filler TB-1: The U.S. Army has a requirement for projectiles and mortars to be loaded with inert (non-explosive) filler for training exercises and demonstration purposes. The primary inert filler used for many years at the Iowa Army Ammunition Plant (IAAAP) was Inert Filler E (Type II Filler; Spec: MIL-I-60350). This inert filler required ergonomically inferior methods to drill a 5" fuze well for a typical inert build (M549). The previous methods required either (1) drilling a 5" deep by 2" wide fuze well with drill bits that quickly became gummed up with filler so that the drilling required to install a fuze could take several hours per round, or (2) inserting a 5"-long shaft funnel into the poured inert filler before the filler set up to limit the drilling required.

Removing the funnel required striking it with a rubber mallet to break it loose; frequently the suction created made the funnel difficult to pull out and more drilling was still required to finish the fuze well. IAAAP achieved its goal by replacing Inert Filler E with inert filler TB-1, which meets all filler requirements. Inert filler TB-1 is easy to machine and drill: it takes only 20 seconds to drill a 5" long by 2" wide fuze well. Inert Filler TB-1 contains no hazardous materials and costs 40-percent less than the former Inert Filler E. Funnel scrap from pouring the Inert Filler TB-1 into projectiles should be 100-percent recyclable without separation, which allows the scrap to be saved for later use and minimizes waste generation.

Excess Inert Filler TB-1 easily flakes off from projectiles and equipment, so cleanup is very easy. Cleaning previous inert fillers required solvent and paper wipes; the solvent-contaminated paper wipes were hazardous waste. The U.S. Army has approved the loading of 2,000 inert 760 ammunition rounds with Inert Filler TB-1.

InfiGreenTM Polyols : Polyurethane manufacturers are seeking to pursue sustainability by reducing their carbon footprint, improving their green image, and cutting costs. The growing market for the polyols used to make polyurethane is currently about 11 billion pounds, but has few green options. Biobased polyols (primarily soy-based polyols) reduce polyurethane’s carbon footprint, but have significant consequences including higher prices for food and agricultural land. In addition, polyurethane manufacturing generates significant amounts of scrap, and virtually all post-consumer polyurethane scrap goes into landfills. With InfiGreenTM polyols and recycling technology, InfiChem Polymers is providing sustainable, green, economical raw materials that are not biobased and do not divert land from food production. This technology transforms polyurethane foams into InfiGreenTM polyols with over 60 percent recycled content for reuse in polyurethanes.

The process liquefies scrap foam in a reaction with glycol, and then transposes it into various InfiGreenTM polyols by propoxylation or patent-pending chemical steps; it typically generates less than one percent waste. InfiChem Polymers demonstrated its process on a pilot scale with both flexible and rigid foam scrap. Substituting one pound of conventional petroleum-based polyols with InfiGreenTM polyols reduces the carbon footprint by approximately two pounds of carbon dioxide (CO2). Polyurethane manufacturers can benefit from closed-loop recycling of their polyurethane production scrap, which can significantly reduce their landfill costs and provide them with InfiGreenTM polyols at prices typically below those for conventional petroleum-based and biobased polyols.

InfiGreenTM polyols are currently used in automotive seat cushions and in the construction industry. InfiChem Polymers expects to reach its current capacity of one million pounds of InfiGreenTM polyols in late 2011; within 5 years, it expects sales of 50 million pounds in NAFTA countries. With projected worldwide production of 180 million pounds of InfiGreenTM polyols, the company will consume approximately 106 million pounds of polyurethane scrap or approximately 0.03 percent of all polyurethane produced.

Innovative Green Chemistry for Sustainable Manufacture of Caprolactam: Evergreen Nylon Recycling LLC (ENR) has developed an innovative green chemistry pathway for producing nylon 6 using sustainable, renewable feedstock. The process chemically renews nylon 6 by manufacturing caprolactam (the base monomer of nylon 6) from post-consumer nylon 6 carpet and other nylon 6 waste articles. This is the world"s first, large-scale, sustainable (closed-loop) nylon recycling process, and it eliminates the annual use of 700,000 barrels of crude oil, 83 million pounds of benzene, 120 million pounds of cumene, and 86 million pounds of phenol as the source feedstock for caprolactam.

Additionally, numerous direct environmental benefits are gained. Over 200 million pounds of nylon wastes (post-consumer & post-industrial) are diverted from landfills each year. There is zero use or generation or emissions of toxic materials in the Evergreen process. Air emissions are significantly lower as compared to traditional caprolactam manufacturing, and the feedstock for the process is indefinitely renewable because nylon 6 can be recycled by Evergreen over and over again without ever degrading product quality.

The technology has been implemented through a $100 million investment in the ENR plant in Augusta, GA. Start-up occurred in December and full-rate production is expected by mid-2001.

Innovative Process for Treatment of Hog Waste and Production of Saleable Produ