The Presidential
Green Chemistry Challenge
Awards Program:
Summary of 2007 Award
Entries and Recipients
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The Presidential  Green Chemistry
Challenge Awards Program:
Summary of 2007 Award Entries
and Recipients


Introduction	1
Awards 	3
   Academic Award 	3
   Small Business Award	4
   Greener Synthetic Pathways Award	5
   Greener Reaction Conditions Award	6
   Designing Greener Chemicals Award	7
Entries from Academia	9
Entries from Small Businesses 	21
Entries from Industry and Government	41
Index  	63


   The Presidential Green Chemistry Challenge Awards Program is a competitive incentive
to create environmentally preferable chemicals and chemical processes. Each year the United
States Environmental Protection Agency (U.S. EPA) celebrates innovative,  award-winning
technologies developed by high-quality nominees. The year 2007 marks the 12th year of the
   The national policy established by the 1990 Pollution Prevention Act is aimed at reduc-
ing pollution at its source whenever feasible.  By applying scientific solutions to  real-world
environmental problems, the Green Chemistry Challenge has significantly reduced  the haz-
ards associated with designing, manufacturing, and using chemicals.
   Through a voluntary U.S. EPA Design for the Environment partnership with the chem-
ical  industry and professional scientific community, this  annual award program  seeks to
discover, highlight, and honor green chemistry.
   An independent panel of technical experts convened by the American Chemical Society
judged the  entries for the 2007 awards. The  judges used  criteria that included health  and
environmental benefits, scientific innovation,  and industrial applicability. Five of the more
than 90 entries were nationally recognized on June 26, 2007, at an awards ceremony in
Washington, D.C. This compilation summarizes the entries submitted for the 2007 awards.
These technologies are meant to succeed in the marketplace as well: each illustrates the tech-
nical feasibility, marketability, and profitability of green chemistry.
   For  further  information about the  Presidential  Green Chemistry Challenge and  U.S.
EPA's Green Chemistry Program, go to
NOTE: The summaries provided in this document were obtained from the entries received for the 2007 Presidential Green
Chemistry Challenge Awards. U.S.  EPA edited the descriptions for space, stylistic consistency and clarity but they were not
written or officially endorsed by the Agency The summaries are intended only to highlight a fraction of the information con-
tained in the nominated projects. These summaries were not used in the judging process. Judging  was conducted on all
information contained in the entries received. Claims made in these summaries have not been verified by U.S. EPA.


Academic Award
Hydrogen-Mediated Carbon—Carbon Bond Formation
   Innovation and Benefits
   A fundamental aspect of chemistry involves creating chemical bonds between carbon
   atoms. Chemical processes commonly used to make such bonds usually also generate
   significant amounts of waste. Professor Krische developed a broad new class of chem-
   ical reactions that make bonds  between carbon atoms using hydrogen and metal
   catalysts. This new class of reactions can be used to convert simple chemicals into
   complex substances, such as pharmaceuticals, pesticides, and other important chem-
   icals, with minimal waste.
   Reductions mediated by hydrogen, termed "hydrogenations", rank among the most wide-
ly used catalytic  methods  employed  industrially. They are generally  used  to  form
carbon—hydrogen (C—H) bonds. Professor Michael J. Krische  and his coworkers at  the
University of Texas at Austin have developed a new class of hydrogenation reactions that form
carbon—carbon (C—C) bonds. In these metal-catalyzed reactions, two or more organic mole-
cules combine with hydrogen gas to create a single, more complex product. Because all atoms
present in the starting  building-block molecules appear  in the final product,  Professor
Krische's reactions do not generate any byproducts or wastes. Hence, Professor Krische's C—C
bond-forming hydrogenations eliminate pollution at its source.
   Prior to Professor Krische's work, hydrogen-mediated C—C bond formations were lim-
ited  almost  exclusively to the use of carbon  monoxide in  reactions  such  as alkene
hydroformylation (1938)  and the  Fischer-Tropsch reaction  (1923). These  prototypical
hydrogen-mediated C—C bond formations are practiced industrially on an enormous scale.
Yet, despite the importance of these reactions, no one had engaged in systematic research
to develop related C—C bond-forming hydrogenations. Only a small fraction of hydro-
genation's potential  as a method of C—C coupling had been realized, and  the field lay fallow
for nearly 70 years.
   Professor Krische's hydrogen-mediated couplings  circumvent  the  use of preformed
organometallic reagents, such as Grignard and Gilman reagents, in carbonyl and imine
addition reactions.  Such organometallic reagents are highly reactive, typically moisture-
sensitive, and sometimes pyrophoric, meaning that they combust when exposed to  air.
Professor Krische's coupling reactions take advantage of catalysts that avoid the hazards of
traditional organometallic reagents.  Further, using chiral hydrogenation catalysts,  Professor
Krische's couplings  generate C—C bonds in a highly enantioselective fashion.
   Catalytic hydrogenation has been known for over a century and has stood the test of
time because of its efficiency, atom economy, and cost-effectiveness. By exploiting hydro-
genation as  a method of C—C bond formation, Professor Krische has added a broad, new
dimension to one of chemistry's most fundamental catalytic processes. The C—C bond-
forming hydrogenations developed  by Professor Krische allow chemists  to create complex
organic molecules in a highly selective fashion, eliminating both hazardous starting mate-
rials and hazardous waste.  Commercial application of this technology may eliminate vast
quantities of hazardous chemicals. The resulting  increases  in plant and worker safety may
enable industry to perform chemical transformations that  were too dangerous using tradi-
tional reagents.
Professor Michael J.
Krische, Department
of Chemistry and
University of Texas at

NovaSterilis Inc.
Small  Business  Award
Environmentally Benign Medical Sterilization  Using
Supercritical Carbon Dioxide
                                  Innovation and Benefits
                                  Sterilizing biological tissue for transplant is critical to safety and success in medical
                                  treatment. Common existing sterilization techniques use ethylene oxide or gamma radi-
                                  ation, which are toxic or have safety problems. NovaSterilis invented a technology that
                                  uses carbon dioxide and a form of peroxide to sterilize a wide variety of delicate bio-
                                  logical materials such as graft  tissue, vaccines, and  biopolymers. Their Nova 2200™
                                  sterilizer requires neither hazardous ethylene oxide nor gamma radiation.
                                   None of the common methods for medical sterilization is well-suited to sterilizing deli-
                               cate biological  materials. The sterility  of these  materials is critical.  Distribution of
                               contaminated donor tissues by tissue banks has resulted in serious infections and illnesses in
                               transplant patients. The two  most widely used sterilants (ethylene oxide and gamma radia-
                               tion) also raise toxicity and  safety concerns. Ethylene oxide is  a mutagenic, carcinogenic,
                               volatile, flammable,  reactive gas. Residues of ethylene oxide remain in the sterilized material,
                               increasing the risk of toxic side effects. Gamma radiation is highly penetrating and is lethal
                               to all cells. Neither ethylene oxide nor gamma radiation can sterilize packaged biological
                               products without eroding their physical integrity.
                                  NovaSterilis, a privately  held biotechnology company  in Ithaca, NY,  has  successfully
                               developed and commercialized a  highly effective and environmentally benign technique
                               for sterilizing  delicate  biological  materials using supercritical  carbon  dioxide  (CC^).
                               NovaSterilis licensed a patent for bacterial inactivation in biodegradable polymers that was
                               issued  to Professor Robert  S.  Langer and his  team at the Massachusetts Institute of
                               Technology. NovaSterilis then enhanced, expanded, and optimized the technology to kill
                               bacterial endospores. Their supercritical CCh technology uses low temperature and cycles
                               of moderate pressure  along with a peroxide (peracetic acid)  and  small amounts of water.
                               Their Nova 2200™ sterilizer consistently achieves rapid (less than 1 hour) and total inac-
                               tivation of a wide range of microbes, including  bacterial endospores. The mechanism of
                               bacterial inactivation  is not well-understood, but does not appear to involve bacterial cell
                               lysis or wholesale degradation of bacterial proteins.
                                  The new technology is compatible with sensitive biological materials and is effective for
                               a wide range of important biomedical materials including: (a) musculoskeletal allograft tis-
                               sue  (e.g.,  human  bone,  tendons,  dermis,  and heart  valves)  for  transplantation;
                               (b) biodegradable polymers and related materials used in medical devices, instruments, and
                               drugs;  (c) drug delivery systems; and (d)  whole-cell vaccines that retain high antigenicity.
                               Besides being a green chemical technology, supercritical CC>2 sterilization achieves  "termi-
                               nal" sterilization, that is, sterilization of the final packaged product. Terminal sterilization
                               provides greater assurance  of sterility than traditional methods of aseptic  processing.
                               Sterilization of double-bagged tissue  allows tissue banks  to ship terminally sterilized mus-
                               culoskeletal tissues in packages that can be opened in operating  rooms by surgical teams
                               immediately prior to use. NovaSterilis's patented technology addresses the market need in
                               tissue banks as well as other needs in the biomedical, biologies, medical device, pharma-
                               ceutical, and vaccine industries. By the end of 2006, NovaSterilis had sold several units to
                               tissue banks.

Greener Synthetic Pathways Award
Development and Commercial Application of
Environmentally Friendly Adhesives for Wood
  Innovation and Benefits
  Adhesives used in manufacturing plywood and other wood composites often contain
  formaldehyde, which is toxic.  Professor Kaichang Li of Oregon State University,
  Columbia Forest Products, and Hercules Incorporated developed an alternate adhesive
  made from  soy flour. Their environmentally friendly adhesive is  stronger than and
  cost-competitive with conventional adhesives. During 2006, Columbia used the new,
  soy-based adhesive to replace more than 47 million pounds of conventional formalde-
  hyde-based adhesives.
   Since the 1940s, the wood composites industry has been using synthetic adhesive resins
to bind wood pieces into composites, such as plywood, particleboard, and fiberboard. The
industry  has  been the predominate user of formaldehyde-based  adhesives  such as
phenol—formaldehyde and  urea—formaldehyde  (UF) resins. Formaldehyde is a probable
human carcinogen. The manufacture  and  use of wood composite panels bonded with
formaldehyde-based resins release formaldehyde into the air, creating hazards for both work-
ers and consumers.
   Inspired by the superior properties  of the protein that mussels use to adhere to rocks,
Professor  Li and his group at Oregon  State University invented environmentally friendly
wood adhesives based on abundant, renewable soy flour. Professor Li modified some of the
amino  acids in  soy  protein  to resemble those  of mussels' adhesive protein. Hercules
Incorporated provided a critical curing agent and the expertise to apply it to commercial pro-
duction of plywood.
   Oregon State University, Columbia Forest Products (CFP),  and Hercules  have jointly
commercialized soy-based adhesives to produce cost-competitive plywood and particleboard
for interior uses. The soy-based adhesives do not contain formaldehyde or use formaldehyde
as a raw material. They are  environmentally friendly, cost-competitive with the UF resin in
plywood,  and superior to the UF resin in strength and water resistance. All CFP plywood
plants now use soy-based adhesives, replacing more than 47 million pounds of the toxic UF
resin in 2006 and reducing  the emission of hazardous air pollutants (HAPs) from each CFP
plant by 50 to 90 percent.  This new CFP plywood is sold under the PureBond™  name.
During 2007, CFP will replace  UF at its particleboard plant. The company is also seeking
arrangements with other manufacturers to further the adoption of this technology.
    With this technology, those who make  and use furniture, kitchen cabinetry, and
other wood composite materials have a high-performing formaldehyde-free alternative.
As a result, indoor air quality in homes and offices could improve significantly. This
technology represents the first cost-competitive, environmentally friendly adhesive that
can replace the toxic UF resin. The technology can greatly enhance the global competi-
tiveness of U.S. wood composite companies. In addition, by creating a new market for
soy flour,  currently in over-supply, this technology provides economic  benefits for soy-
bean farmers.
Professor Kaichang
Li,  Department of
Wood Science and
Oregon State
Columbia Forest

                              Greener Reaction  Conditions Award
Direct Synthesis of Hydrogen Peroxide by Selective
Nanocatalyst Technology
                               Innovation and Benefits
                               Hydrogen peroxide is an environmentally friendly alternative to chlorine and chlorine-
                               containing  bleaches and oxidants.  It  is expensive,  however, and its  current
                               manufacturing process  involves  the  use of  hazardous  chemicals.  Headwaters
                               Technology Innovation  (HTI) developed an advanced  metal  catalyst that makes
                               hydrogen peroxide directly from hydrogen and oxygen, eliminates the use of hazardous
                               chemicals, and produces water as the only byproduct. HTI has demonstrated their new
                               technology and is partnering with Degussa AG to build plants to produce hydrogen
                                Hydrogen peroxide (H^C^) is a clean, versatile, environmentally friendly oxidant that
                              can substitute for environmentally harmful chlorinated oxidants in many manufacturing
                              operations. However, the existing manufacturing process for H2O2 is complex, expensive,
                              and energy-intensive. This process requires an anthraquinone working solution containing
                              several toxic chemicals. The solution is reduced by hydrogen in the presence of a catalyst,
                              forming anthrahydroquinone, which then reacts with oxygen to release H2O2. The H2O2
                              is removed from the solution with an energy-intensive stripping column and then concen-
                              trated by vacuum distillation. The bulk of the working solution is recycled, but the process
                              generates a waste stream of undesirable quinone-derived byproducts that requires environ-
                              mentally acceptable disposal.
                                Headwaters Technology Innovation (HTI) has produced a robust catalyst technology
                              that enables the synthesis of H2Ch directly from hydrogen and oxygen. This breakthrough
                              technology, called NxCat™,  is a palladium-platinum catalyst that eliminates all the haz-
                              ardous reaction conditions and chemicals of the existing process, along with its undesirable
                              byproducts. It produces H2O2 more efficiently, cutting both energy use and costs. It uses
                              innocuous, renewable feedstocks and generates no toxic waste.
                                NxCat™ catalysts work because of their precisely controlled surface morphology. HTI
                              has engineered a set of molecular templates and substrates that maintain control of the cat-
                              alyst's crystal structure, particle size, composition, dispersion, and stability. This  catalyst
                              has a uniform 4-nanometer feature size that safely enables a high rate of production with
                              a hydrogen gas concentration below 4 percent in air (i.e., below the flammability  limit of
                              hydrogen). It also maximizes the selectivity for H2O2 up to 100 percent.
                                The NxCat™ technology enables a simple, commercially viable H2O2 manufacturing
                              process. In partnership with Degussa AG (a major ^C^ manufacturer), HTI successful-
                              ly demonstrated the NxCat™ technology and, in 2006, completed construction of a
                              demonstration plant. This demonstration plant will allow the partners to collect the data
                              necessary to design a full-scale plant and  begin commercial production in 2009- The
                              NxCat™ process has the potential to cut the cost of ^C^ significantly, generating a
                              more competitively priced supply of H2O2 and increasing its market acceptance as an
                              industrial oxidant.  Except for its historically higher price, ^C^ is an excellent substitute
                              for the more frequently used—and far more deleterious—chlorinated oxidants. The
                              NxCat™ technology has the benefit of producing an effective, environmentally prefer-
                              able oxidant (H^C^) without  the waste or high cost associated with the traditional

Designing Greener  Chemicals Award
BiOH™ Polyols
  Innovation and Benefits
  Foam cushioning used in furniture or bedding is made from polyurethane, a man-
  made material. One of the two chemical building blocks used to make polyurethane is
  a  "polyol".  Polyols  are conventionally  manufactured  from  petroleum  products.
  CargiU's BiOH™ polyols are manufactured from renewable, biological sources such as
  vegetable oils. Foams  made with BiOH™ polyols are comparable to foams made from
  conventional polyols. As a result, each million pounds of BiOH™ polyols saves near-
  ly 700,000 pounds of crude oil. In addition,  CargiU's process reduces total energy use
  by 23 percent and carbon dioxide emissions by 36 percent.
   Polyols are key ingredients in flexible polyurethane foams, which are used in furniture and
bedding. Historically, polyurethane has been made from petrochemical polyols. The idea of
replacing these polyols with biobased polyols is not new, but the poor performance, color,
quality, consistency, and odor of previous biobased polyols restricted them to limited mar-
kets. Previous biobased polyols also suffer from poor chemical reactivity, resulting in foam
with inferior properties.
   Cargill has  successfully developed biobased polyols for several polyurethane applica-
tions, including flexible foams, which are the most technically challenging. Cargill  makes
BiOH™ polyols by converting the carbon—carbon double bonds in unsaturated vegetable
oils to epoxide derivatives and then further converting these derivatives to polyols using
mild temperature and ambient pressure. BiOH™ polyols provide excellent reactivity and
high levels of incorporation leading to high-performing polyurethane foams. These foams
set  a  new standard  for consistent quality with low odor  and  color.  Foams containing
BiOH™ polyols retain their white color longer without ultraviolet  stabilizers. They also
are  superior to foams containing only petroleum-based polyols in standard tests. In large
slabstock foams, such as those used in furniture and  bedding, BiOH 5000 polyol provides
a wide processing window, improved comfort factor, and reduced variations in density and
load-bearing capacity. In molded foams such as automotive seating and headrests, BiOH
2100 polyol can enhance load-bearing or hardness properties relative to conventional
   Use of BiOH™ polyols  reduces the environmental  footprint relative  to today's con-
ventional polyols for polyurethane production.  BiOH™ polyols "harvest" carbon  that
plants remove from the air during photosynthesis. All of the carbon in BiOH™ polyols is
recently fixed.  In conventional polyols, the carbon  is petroleum-based. Replacing  petro-
leum-based polyols with BiOH™ polyols cuts total energy use by 23 percent including a
61-percent reduction in nonrenewable energy use,  leading to a 36-percent reduction in
carbon dioxide emissions. For each million pounds of BiOH™ polyol used in place of
petroleum-based polyols, about 700,000 pounds (2,200 barrels) of crude oil are  saved,
thereby reducing the dependence  on petroleum. BiOH™ polyols diversify the  industry's
supply options and help mitigate the effects of uncertainty and volatility of petroleum sup-
ply and pricing. Cargill is the first company to commercialize biobased polyols on a large
scale in the  flexible  foam market. Formulators can now use biobased  polyols in flexible
foam without compromising product performance.  That the top North American polyol
users choose BiOH™ polyols is validation of CargiU's accomplishment.


Entries  from  Academia

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. A common alternative is the Anelli process, which
replaces the metal oxides with NaOCl and TEMPO  (2,2,6,6-tetramethylpiperidinyloxy).
The Anelli reaction is carried out in a two-phase (CH2Ci2—H^O) system using TEMPO as
a catalyst  and NaOCl as the oxidant. A co-catalyst, KBr, increases the reaction rate.
   Dr. Augustine's oxidation procedure is an extension of the Anelli process. His new pro-
cedure  replaces KBr with the more benign Na2B4Oy (borax)  and does not require any
organic solvents. In the absence of organic solvents, the reactant alcohol comprises about
38 percent of the total reaction volume compared  with only about 2.5 percent in the clas-
sic reaction using dichloromethane. This has positive cost, environmental,  and process
safety implications. A further advantage to the solvent-free reaction is the isolation of the
product aldehyde by phase separation from the aqueous solution, which saves even more
energy because there is no solvent to remove. Dr.  Augustine's process can oxidize a num-
ber of primary alcohols, producing the corresponding aldehydes in very good to excellent
yields. His process also oxidizes secondary alcohols to ketones in very good to excellent
   The Center  for Applied Catalysis has been collaborating  with  the  NutraSweet
Corporation to scale up this reaction. NutraSweet is currently using Dr. Augustine's process
to manufacture an aldehyde, 3,3-dimethylbutanal, on a commercial scale. This aldehyde is
a feedstock for Neotame, which is an FDA-approved  N-alkyl derivative of aspartame.

High-Performance Macromolecular Antioxidants for
Materials: A  Green  Chemistry Approach
   NOTE: This project is the result of a partnership between Polnox Corporation and Dr.
Ashok L. Cholli of the University of Massachusetts Lowell. The project was judged in both
the small business and academic categories. The abstract appears in the small business sec-
tion on page 34.
Dr. Robert L.
Augustine, Center
for Applied
Catalysis, Seton
Hall University;
The NutraSweet
Dr. Ashok L. Cholli,
Center for
University of

Purnendu K.
Department of
Chemistry and
Biochemistry, The
University of Texas
at Arlington
Professor Arlin E.
Gyberg, Augsburg
Professor James E.
Department of
Chemistry and
Director, Materials
Science Institute,
University of
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 approx-
imately 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
   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 (AsH^) 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) sepa-
rately. Professor Dasgupta filed patent applications in 2005 and 2006 for this technology.

A New, Heterogeneous, Fixed-Bed Catalyst for
Continuous-Flow Biodiesel Production from Waste Fats
and Oils
   NOTE: This project is  the result of a partnership between SarTec Corporation and
Professor Arlin E. Gyberg of Augsburg College. The project was judged in both the small
business and academic categories. The abstract appears in the small business section on 35-

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 func-
tionality 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.

Development of Environmentally Benign Nonfouling
Materials and Coatings for Marine Applications
   Biofouling on ship hulls and other marine surfaces has become a global environmental
and economic issue. The best antifouling coating is tributyltin- (TBT-) based paint, but it
is being phased out because of environmental concern over its effects on nontarget marine
organisms. Tin-free biocides such as copper particles or cuprous oxide are substituting for
TBT in the current market, but these biocides are also harmful to the marine environment,
and their application is very limited. Nontoxic,  fouling-release coatings based on silicone
also have very limited applications; they are only effective on vessels moving at high speeds
(over  14 knots). However, fouling occurs most  readily on static structures or ships mov-
ing slowly in  seawater close to  land.
   Professor Jiang's vision is to develop nonfouling coatings to which marine microorgan-
isms cannot attach, as  the next generation of marine coatings. With support  from the
Office of Naval Research (ONR, U.S. Navy), Professor Jiang has demonstrated for the first
time that coatings based on zwitterionic  sulfobetaine (SB) and carboxybetaine (CB) are
super-low-fouling. SB- and CB-based materials are biomimetic, nontoxic, very stable, eas-
ily handled,  and  low-cost. Professor Jiang has recently  developed the  first nontoxic,
super-low-fouling, zwitterionic-based marine  coatings. These coatings  have outstanding
performance  against marine microorganisms in  laboratory tests and effectively defer the
settlement of microorganisms in field tests. Professor Jiang is currently integrating self-pol-
ishing via hydrolysis into his existing coatings in order to create the first environmentally
benign, durable, effective, nonfouling paint products. He has filed  three patents for his
technology and is launching a startup company to commercialize it. In addition to marine
coatings, these materials are very promising for biomedical  applications and consumer

Application of Collagen Nano fibrils 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 set-
tling,  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
Professor Shaoyi
Jiang, Department
of Chemical
University of
Professor Gennaro
J. Maffia,
Department of
Widener University

Professor Krzysztof
Department of
Carnegie Mellon
kaolin. They have also shown promise in other environmental applications such aiding fil-
tration, separation of pollutants from aqueous streams, selective fractionation of molecules,
and oil droplet stabilization. Additional applications include cell culture, tissue engineer-
ing, 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 agen-
cies are investigating the technology.

Diminishing Copper Catalyst  Content in Atom Transfer
Radical Polymerization (ATRP) in the Presence of
Environmentally Friendly Reducing Agents
   Atom transfer radical polymerization (ATRP) is a transition-metal-mediated, controlled
polymerization process for radically polymerizable monomers that was discovered at Carnegie
Mellon University (CMU) in 1995- Since 2002, ATRP has been licensed to 7 of the 15 cor-
porations presently funding the research  at CMU (PPG, Dionex, Ciba, Kaneka, Mitsubishi,
WEP, and Encapson). Licensees have begun commercial production of high-performance,
less toxic, safer materials, including sealants, dispersants, coatings, adhesives, lubricants, addi-
tives, and materials for electronic, biomedical, health, and beauty applications in the United
States, Europe, and Japan.
   Since the conception of ATRP, Professor Matyjaszewski has been working to make it a
more environmentally benign process. During  the last 3 years, he and his team at CMU
developed new catalytic systems that allow a dramatic decrease in the concentration of
transition metal, while preserving good  control  over polymerization and polymer architec-
ture. The latest improvements are called activators generated by electron transfer (AGET,
2004), activators regenerated by electron  transfer (ARGET, 2005),  and initiators for con-
tinuous activator  regeneration (ICAR, 2006). These  methods allow the preparation,
storage, and use of the most active ATRP catalysts in their oxidatively stable state as well
as their direct use under standard industrial polymerization conditions. The recently dis-
covered ARGET ATRP allows a reduction in  the amount of copper catalyst from  over
1,000  ppm to less than 10 ppm in the  presence of environmentally friendly reducing
agents such as FDA-approved tin(II) octanoate,  sugars, and  ascorbic acid (Vitamin  C).
AGET and ARGET ATRP provide routes to pure block copolymers. The new processes
allow oxidatively stable catalyst precursors to be used in aqueous, homogeneous, dispersed
(miniemulsion, inverse miniemulsion, microemulsion, emulsion, and suspension), and sol-
ventless bulk  polymerizations. Professor Matyjaszewski's work is opening new routes for
production of many advanced polymeric materials in  a  more environmentally benign,
green way.

Regioregular Polythiophenes as a Platform for Organic
Photovoltaic Technology
   Global sustainability relies on renewable energy;  solar energy promises the greatest
long-term solution. At $5 per watt, however, traditional silicon-based solar cells (photo-
voltaics) are too expensive to have serious impact. Further, the production of silicon solar
cells requires toxic and explosive gases, corrosive liquids, and suspected carcinogens.
   Professor  Richard D.  McCullough's  fundamental discoveries  have  substantially
enhanced the potential of plastic solar cells to mitigate global warming. Earlier, Professor
McCullough  synthesized nearly 100 percent regioregular polythiophenes (rr-PTs)  with
unprecedented conductivities and created an energy-efficient, comparatively inexpensive
synthesis of pure rr-PTs.  He can now synthesize rr-PTs  in  a process  that dramatically
reduces hazardous chemicals, consumes significantly less energy, is cheaper, and is scalable
to industrially relevant levels (e.g., 100-kilogram batches).
   The solubility of poly(3-hexylthiophene) enhanced by side-chain modifications enables
it to be solution-processed and InkJet-printed onto various substrates, thus lowering pro-
duction  costs  for organic  solar cells. Professor  McCullough's synthesis  of poly-
(3-hexylthiophene)  is now the dominant technology for producing the most  efficient
polymer photovoltaics to date, with power conversion efficiencies of up  to 5 percent.
   In 2002, Professor McCullough cofounded Plextronics, a company committed to deliv-
ering  revolutionary  renewable  energy products.  These  products  include  organic
photovoltaics and organic light-emitting diode (OLED)  displays based on Plexcore™,
Professor McCullough's polythiophene technology. One of the products, Plexcore PV, is a
p-type semiconductor with tunable energy and bandgap that will improve the efficiency of
organic (or polymer) solar cells. It can be printed onto substrates,  thus enabling large area,
low-cost solar cell production that will drive the cost toward the commercially viable $1
per watt. Plexcore™  can be adapted to various applications, so  Plextronics is well-posi-
tioned to develop markets such as OLEDs, displays, solid-state white lighting, and solar
cells for integrated  building photovoltaics. Plextronics began kilogram-scale, commercial
production of poly(3-hexylthiophene) in 2003 and established a solar cell production facil-
ity in 2005-
Highly Efficient and Practical Monohydrolysis of
Symmetric D testers
   The development of environmentally friendly, cost-effective organic reactions is of cen-
tral importance in academia and  industry. Water is among the most environmentally
friendly solvents because it generates no hazards  during chemical conversion processes.
Therefore, water-mediated  organic reactions represent green chemistry. Water is also the
least expensive solvent.
   Desymmetrization of symmetric compounds is  one of the most cost-effective synthetic
reactions because symmetric compounds are typically commercially available at low cost or
are produced easily from inexpensive precursors on  a large scale. Desymmetrization of sym-
metric organic compounds  mediated by water would be of tremendous synthetic value and
would make a significant contribution to creating greener reaction processes.
   Monohydrolysis of symmetric diesters produces half-esters, which are highly versatile
building blocks in organic synthesis and have considerable commercial value. Because the
two ester groups in the symmetric diesters are equivalent, however, it can be challenging to
Professor Richard
D. McCullough,
Dean, Mellon
College of Science,
Carnegie Mellon
Professor Satomi
Department of
Chemistry and
Texas Tech

Professor Michael
C. Pirrung,
Department of
University of
distinguish the ester groups chemically. The most common method for effective monohy-
drolysis uses enzymes, which provide no basis for predicting the yield or enantioselectivity
Classical saponification usually affords only complex mixtures of dicarboxylic acids,  the
starting diesters, and a small amount of the half-esters, which are difficult to separate. As
a result, saponification yields a large amount of undesirable, dirty waste.
   Professor Niwayama discovered and has been developing a highly efficient and practi-
cal  monohydrolysis  of symmetric diesters.  Her  reaction  is  the  first  such selective,
nonenzymatic monohydrolysis of a series of symmetric diesters. In this reaction, aqueous
sodium hydroxide (NaOH) is added to a water—tetrahydrofuran (THF) suspension of a
symmetric diester at 0 °C. The reaction rapidly produces pure half-esters in high- to near-
quantitative yields without dirty waste. It uses only relatively simple apparatus, allowing
large-scale  production of half-esters and potential  industrial applications. Professor
Niwayama anticipates that this reaction will contribute to environmentally friendly green
chemistry in industry and academia.

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 prod-
ucts, 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 com-
monly used multicomponent  reactions and (2) their problematic preparation.
   The second  component is Professor Pirrung's development of a much more environ-
mentally friendly route to prepare isonitriles that also eliminates their stench. Traditional
routes to isonitriles involve dehydration of formamides with phosgene. Phosgene is a high-
ly 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 effi-
cient. 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, com-
binatorial libraries, and active pharmaceutical ingredients.

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 lum-
ber, but  these preservatives  have  environmental  concerns. A few U.S. localities have
restricted copper-treated wood, and increasing limitations are  expected. Future preserva-
tives 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 sig-
nificantly 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.

Biomimetic Reductive Processes
   Biomimetic reductive processes via organic base-catalyzed 1,3-proton transfer are con-
ceptually 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 environ-
mentally 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 syntheti-
cally 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 indus-
trially important reductive processes. These include (1) reductive amination of carbonyl
Professors Tor P.
Schultz and Darrel
D. Nicholas,
College of Forest
Mississippi State
Professor Vadim A.
Soloshonok and Dr.
Hisanori Ueki,
Department of
Chemistry and
Biochemistry, The
University of

                              compounds (aldehydes,  ketones); (2) consecutive 1,3-proton-shift-dehydrohalogenation
                              reactions that provide a general approach for the preparation of 2-aza-l,3-dienes (versatile
                              intermediates in the syntheses of nitrogen heterocyclic compounds); (3) hydrodehalogena-
                              tion of a-halogenated carbonyl compounds; (4) reduction of carboxylic acids to aldehydes;
                              (5) reductive amination of carboxylic acids to amines;  (6) enantioselective, organocata-
                              lytic, 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 tech-
                              nology for the large-scale synthesis of several amines containing trifiuoromethyl groups.
Professor Bala
Center for
Department of
Chemical and
University of
A Greener Hydroformylation Process
   Industrial processes for the catalytic hydroformylation of higher olefms (> Cj) are ham-
pered by limited syngas availability in the liquid phase and require rather harsh conditions
(5—30 MPa, 150—300 °C) to activate and stabilize the catalyst. Further, recovering the cat-
alyst requires much acid, alkali, and solvent, generating significant waste.
   Used as reaction media,  CCVexpanded liquids help overcome these drawbacks. For
example, partly replacing excess  1-octene (substrate) with dense CCh to create a CCV
expanded liquid (CXL) phase  in the  homogeneous hydroformylation of 1-octene with a
rhodium-based catalyst complex significantly increases both the hydroformylation rate and
the selectivity toward the linear aldehyde. The increased rate and selectivity correlate with
experimental results showing improved availability of the  gaseous  reactants in the CXL
phase. The observed time of flight (TOP; —300 h"1), n/i ratio (>10), and aldehyde selectiv-
ity (—90%) at  the optimum CCh content are either comparable to or better than values
reported with other media and catalysts. The operating pressure (3-8  MPa) and tempera-
ture (60 °C) for the CXL process  are significantly milder than those  reported for industrial
hydroformylation  processes. Following the reaction, excess CCh  easily precipitates the
rhodium catalyst complex from the reaction mixture.
   The CXL process is estimated to require approximately 50 percent of the capital cost
and 80 percent of the production cost of the benchmark Exxon process. The cost savings
from  the lower operating pressures and temperatures in the CXL process are substantially
more  than the  costs of the recompression and recycling of CC^. The environmental E-fac-
tor (kg of waste generated per kg of desired product) for the  CXL process is two- to
three-fold less than that of the  Exxon  process. In addition, the overall  toxicity index of the
CXL  process is approximately  40-fold lower than that  of the Exxon process. In principle,
the CXL process could tune selectivity in carbonylations, hydrogenations, and asymmetric
hydroformylations to produce  specialty chemicals and pharmaceuticals.
Professor Daniel
Tao, The
Department of
University of
 Georgia-Pacific Mining Reagents that Improve Recovery,
Reduce Wastes, and Conserve Water and Other Natural
   NOTE: This project is the result of a partnership between Georgia-Pacific Chemicals,
LLC and Professor Daniel Tao of the University of Kentucky. The project was judged in
both the academic and greener reaction conditions (Focus Area 2) categories. The abstract
appears in the Industry and Government section on page 50.

Novel, One-Step,  Chromate-Free Coatings Containing
Anticorrosion Pigments to Replace Chromate
Pretreatment and Pigments
   Paints and organic coatings are often used to protect metals and alloys from corrosion.
The paint industry uses  approximately 600,000 metric tons of chromates annually for
chromate conversion coatings and as pigments. The "self-healing" property of chromates
makes them difficult to replace. Hexavalent chromate, Cr(VI), has been identified as toxic
and  carcinogenic, however; it is  subject  to regulation by various  government bodies.
Chromate exposures cause a gamut of health problems including ulcers, irritation of the
nasal mucosa, holes in the nasal septum, skin ulcers, allergic reactions, and nasal and lung
   Paints are formulated with high-molecular-weight polymers for good anticorrosion
properties. These polymers  require solvents that are volatile organic compounds  (VOCs).
During curing and drying of the paint, these VOCs evaporate, posing an occupational safe-
ty hazard.
   Professor van Ooij invented a one-step, low-VOC, anticorrosion primer system for use
on metals, particularly aerospace aluminum alloys. The system can be applied directly to
the metal, eliminating the chromate conversion coating. The novel primer is produced by
mixing organofunctional bis-silanes with waterborne  resins like acrylates (e.g., Maincote
AE58 acrylic resin from Rohm & Haas), polyurethanes, or epoxies (like Daubond D9010
from Daubert Industries, Inc.). To  mimic the  self-healing properties of chromate pigments,
Professor van Ooij developed a synergistic silane-polymer structure incorporating com-
mercial pigments such as zinc phosphate. The  pigments leach out of the paint layer very
slowly and only when corrosion starts to develop. This novel primer eliminates chromates
entirely, yet performs equally well. Further, it cures at elevated temperature or at room tem-
perature, leading to tremendous cost savings.
   Professor van Ooij is commercializing his primer system through a small business that
he founded, ECOSIL Technologies LLC. Many  companies including DuPont, PPG,
Sherwin Williams,  Hentzen Paints,  and BASF have  received samples and are about to
launch more intensive cooperation with ECOSIL.

Passive  Treatment of Metal-Contaminated Water
   A serious environmental consequence of the mining legacy in the United States is large
flows of water laden with metals, usually known as acid mine drainage. These waters have
concentrations of hazardous contaminants such  as arsenic, cadmium, and lead  that are
harmful to human health and aquatic ecosystems. The typical treatment for these waters is
to add industrial chemicals to precipitate the  metals and then send the water through clar-
ifying,  settling, and  filtering tanks. Such  a  labor- and  material-intensive process is
expensive; it is also impossible to use at the remote sites of many of the abandoned mines
within western United States.
   Passive treatment is a process for removing contaminant metals from water using nat-
ural  materials  such  as wood chips, hay, manure, and limestone  instead of industrial
chemicals. The breakdown of these materials is catalyzed by natural bacterial consortia to
produce sulfide, carbonate,  and hydroxide ions that precipitate the contaminating metals.
These precipitates are filtered from the water using natural, constructed, wetland structures
that  blend into the landscape, replacing capital-intensive settling and filtering structures.
In summary, passive treatment not only looks green, but is chemically green.
Professor Wim J.
van Ooij,
Department of
Chemical  and
University of
Professor Thomas
Department of
Chemistry and
Colorado School of

                                 Passive treatment was first successful at the Westfork Lead Mine in Missouri. Full-scale
                              systems have been  built  for private  clients at the Cannon Gold Mine in Wenatchee,
                              Washington, the Haile Gold Mine in South Carolina, the Delamar Gold Mine in Oregon,
                              and the MSF Nickel Mine in Brazil. The systems at all of these sites eliminated active pre-
                              cipitating chemicals,  eliminated  energy and  material-intensive  separation steps,  and
                              removed metal contaminants such as  lead, cadmium, and arsenic, as well as zinc, copper,
                              and mineral acidity from the water. Following these successes at private sites, the U.S. EPA
                              recently adopted this technology at two places in the Ten Mile Creek Superfund Site near
                              Helena, Montana.
Professor Xumu
Zhang, Department
of Chemistry, The
Pennsylvania State
Practical Asymmetric  Catalytic Hydrogenation
   Over 50 percent of the world's pharmaceuticals are single enantiomers; sales of chiral
drugs were $159 billion in 2002. A growing challenge is to develop cost-effective, green
chemical catalytic processes to  make chiral molecules. Asymmetric chemocatalysis is one of
the most competitive replacements for classic chiral resolutions,  which generally require
large volumes of solvents, chiral resolving agents, and even waste treatment of unwanted
enantiomers.  The  cleanest and most  cost-effective  reductant  available is  hydrogen.
Asymmetric hydrogenation accounts for over 70 percent  of the current methods for com-
mercial asymmetric  chemocatalysis. Fundamental,  innovative  chemical methods  are
needed to develop  these green chemical processes. Breakthroughs in this area will have
broad applicability  in industry.
   Professor Zhang and his group have developed novel transition-metal-reduction cata-
lysts for the practical synthesis of chiral alcohols, amines, acids, amino alcohols, diols, and
a- and p-amino acids. They have investigated the fundamental factors controlling enan-
tioselectivity and invented a  toolbox  of practical chiral  ligands  for the asymmetric
hydrogenation of ketones, alkenes, imines, and aromatic compounds. They have observed
high activity (up to  50,000 turnovers) and enantioselectivity (up to 99 percent  enan-
tiomeric excess) for the hydrogenation of some substrates. They have demonstrated the
synthetic utility of asymmetric hydrogenation in the green chemical processes  with chal-
lenging asymmetric transformations  for important biologically active compounds such as
Lipitor®, Cymbalta®, and carbopenem.
   Professor Zhang's technology has numerous patents. He is commercializing  it through
Chiral Quest, Inc., which is providing his chiral technology to pharmaceutical and fine
chemical companies including Phoenix, Pfizer, Merck, and Eli Lilly. Phoenix Chemicals
Ltd. is currently manufacturing the Lipitor®  side-chain using Chiral Quest's technology.

A Novel Phosphite Dehydrogenase Based NAD(P)H
Regeneration  Technology for Industrial Biocatalysis
   Enzyme-catalyzed  reactions that require stoichiometric amounts of reduced nicotin-
amide 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 speci-
ficity 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 phos-
phite 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 dras-
tically 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 specifici-
ty (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 thermo-
dynamic 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 read-
ily by calcium precipitation if necessary.
   The three professors used a membrane bio reactor to demonstrate the advantages of this
mutant PTDH over FDH for cofactor regeneration in the industrially important synthe-
sis of L-feTt-leucine and xylitol. Their PTDH system has broad applicability in industrial
synthesis of unnatural amino acids, polyols, chiral alcohols, and products  labeled with deu-
terium or tritium.  Recently,  BASF (Germany) and BioCatalytics (Pasadena, CA) licensed
their novel PTDH-based technology.
Professors Huimin
Zhao, Department
of Chemical and
Wilfred A. van der
Donk,  Department
of Chemistry;
William W. Metcalf,
Department of
University of


Entries  from  Small  Businesses
Changing the Nature of Surfactants: Low-Molecular-
Weight Proteins as Surfactant Synergists
   In many chemical processes, surfactants and solvents enhance chemical reactions by
reducing the surface energies of the reactions. The large markets that use surface-active
agents include cleaners, agriculture, coatings, oil, fabric processing, and  adhesives. The
majority of raw materials used to produce surfactants and solvents are petroleum-based.
Botanicals and other renewable, greener alternatives are available, but are confined to niche
markets  as their cost and performance have not met the needs of broader markets.
   Advanced  BioCatalytics developed Molecular Kinetics™, a technology based on a
patented, low-molecular-weight protein system. That system, C.O.D.E.™, significantly
reduces  interfacial tension. Currently, Advanced BioCatalytics  derives the C.O.D.E.™
proteins from the supernatant of a unique yeast fermentation process. The protein prod-
ucts are  made in a food processing facility in a strategic partnership between Kikkoman
Foods and Advanced BioCatalytics. C.O.D.E.™ can replace solvents in general-purpose
cleaners, most of which are hazardous. It enhances surfactants, reducing their volumes sig-
nificantly in cleaners and in numerous other chemical processes. For example, in a fabric
processing test, C.O.D.E.™-based wetting agents  reduced the amount of surfactant
required by over 90 percent.
   Demand for greener products is being fueled by the expanding public awareness of
environmentally responsible chemicals  and  tightening  regulatory  requirements.
C.O.D.E.™ proteins meet FDA guidelines for food contact, are safe for the user, and
improve the environment in many ways. They could potentially replace millions of pounds
of toxic chemicals,  reducing  air, water,  and environmental pollutants. The features of
C.O.D.E.™ provide chemical formulators with incentives that allow them  to produce dis-
tinct, higher-margin products in commodity markets. Since 2004, Advanced BioCatalytics
has commercialized four industrial and institutional products using C.O.D.E.™ proteins
and is working with several companies to  commercialize additional new products in 2007-

Uncoupling Biochemical Processes for Enhanced
Biological Efficiency
   Advanced BioCatalytics developed and patented naturally produced chemicals using a
protein-based system called C.O.D.E.™.  This  led to  a  platform technology it calls
Molecular Kinetics™, which uncouples oxidative phosphorylation in microbial metabo-
lism such that the breakdown of organic compounds by microbes accelerates dramatically.
The C.O.D.E.™ uncoupling factor signals microbes to view biofilms as nutrients  and to
digest them. C.O.D.E.™ products meet FDA guidelines for food contact, are approved
by the National Science Foundation (NSF) for potable water use, are safe for the  user, and
improve the environment in many ways. In 2002, the company commercialized this tech-
nology as Accell®.
   In industrial and municipal wastewater treatment facilities, Accell® can consistently
reduce sludge production and its associated costs by 30 percent or more. In addition, the
treatment plants operate more efficiently, with improved  effluent quality, better sludge set-
tling, increased plant throughput capacity, and the opportunity to reduce aeration costs by
over 30  percent in some cases. Aeration  is the greatest  user of energy in  these  facilities.
Using Accell® in its  wastewater treatment plant saved one industrial customer $5 million

Amerikal Products
APTech Group, Inc.
in capital equipment costs, reduced its operating costs, and saved over $200,000 per year
in environmental surcharges.
   The formation of bio films in cooling systems contaminates heat exchange surfaces and
fouls reverse osmosis filtration membranes drastically, corroding and degrading substrates
and reducing energy efficiency. C.O.D.E.™ can reduce the toxic biocides typically used to
control biofilm and biofouling by over 90 percent.
   In seawater desalinization, the cost of energy to pump water through the membranes is
the greatest operating expense. The process typically requires frequent cleaning cycles that
can degrade the expensive membranes. C.O.D.E.™ treatment can save over 20 percent of
energy use by reducing both operating pressures and cleaning cycles while increasing both
throughput and salt rejection.

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  °E 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 pro-
duction  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 consump-
tion 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.

A Greener Chemical Treatment for Cooling Tower Water
   Chemical  treatment of water in cooling towers is necessary to minimize microbiologi-
cal growth and to eliminate corrosion and scaling. Liquid cooling tower products contain
about 25 percent solids in  water. Many of the active ingredients are insoluble in  solutions
at neutral pH, so manufacturers must add sodium hydroxide (NaOH), a highly caustic
chemical, to increase the pH and stabilize the solution. NaOH typically accounts  for about
half of the solids in solution.

   APTech Group developed a product in which only the active ingredients  are mixed,
heated, filled into jars, and then cooled into a solid product. The solid product contains
sodium tolyltriazole, sodium salts of (1-hydroxyethylene) diphosphonic acid, sodium salts
of 2-phosphonobutane-l,2,4-tricarboxylic acid, the partial  sodium salt of acrylic acid ter-
polymer,  VersaFlex™  One   polymer  (Alco  Chemical),   the   sodium  salt  of
hydroxyphosphonoacetic acid, and sodium  chloride.  It does not  contain NaOH. The
product is reconstituted with water into a very dilute solution (approximately 0.5 percent
or less) onsite before use. This technology not only eliminates the discharge of NaOH into
wastewater streams, but also eliminates  the potential for spills of hazardous, highly con-
centrated chemicals that would have to be cleaned up by  local personnel and could kill
aquatic life if released into surface waters. It  also eliminates the problems associated with
disposal of the empty drums that had held the liquid chemicals. Solid chemicals can result
in savings for the user. The use of solid chemicals can eliminate the transport of 309 mil-
lion pounds of water and 38 million pounds of NaOH over  U.S. highways annually, saving
fuel and reducing the potential for spills.

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 firefight-
ing 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  com-
ponents, 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 food-
grade  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 dis-
tillate 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 dur-
ing the 2006 fire season with spectacular results.
International, Inc.

Century Industrial
Coatings  Inc.
Nulo™ Technology: HAP-Free,  Low-VOC,
Water-Based, Air-Dry Coatings
   The Nulo™ technology is a water-based coating developed to replace solvent-based
paints  in steel joist dip painting operations. The most transfer-efficient method to paint
open-weave steel joists is by dipping the joists into vats filled with paint. Traditionally, the
joist industry used solvent-based alkyd paints containing 3-5 pounds or more of volatile
organic compounds (VOCs) per gallon. Conventional water-based paints have not been
successful in dipping operations because of their high cost, poor film properties, and prob-
lems with their  stability. Time and pH fluctuations cause these paints to thicken and can
turn them into  an unusable gelatinous mass in the dip tank.
   Century Industrial Coatings developed Nulo™ as a new water-based paint that satis-
fies  the  joist industry's  needs for  reduced VOC emissions,  stability  in dip  tanks,
comparable cost, and product performance equal to that of solvent-based paints. Nulo™
paints contain no hazardous air pollutants (HAPs), have VOC levels of only 0.47 pounds
per gallon, and have the appearance of solvent-based paints. The viscosity of Nulo™ paints
is controlled with water, not volatile organic solvents. The benefits of using the Nulo™
paints to replace solvent-based paints include reduction of VOC emissions by 86 percent,
elimination of HAP emissions, elimination of fiammability and combustion problems, and
reduced impact  on human health and the environment.
   Nulo™ dip  primers have been in continuous commercial use since July 2003- Nulo™
primers have already replaced approximately 1  million gallons of solvent-based primers,
eliminating about 2.89 million pounds of VOC releases to the atmosphere. Replacing sol-
vent-based primers  with Nulo™ primers in joist plants would eliminate an  estimated
12.1 million pounds of VOC emissions each year. Century is in the process of expanding
its technology to other painting processes and industry sectors.
Changing World
Technologies, Inc.
Waste to Renewable Diesel
   Changing World Technologies, Inc. (CWT) has successfully developed and patented an
energy-efficient process that converts  organic  waste into diesel  oil.  Their Thermal
Conversion Process (TCP) is capable  of breaking down waste material using water, heat,
and pressure. The process can use a broad range  of wastes including animal carcasses  and
byproducts; fats, greases, and oils; and municipal and industrial wastes including plastics,
metals, and recycled automobiles. It does not require exotic chemicals or catalysts, and it
includes screening and grinding of waste; depolymerization at 290 °F and 80 psi; hydrol-
ysis at extreme temperature and pressure  (480 °F and 600 psi); and separation of the oil,
water, and solid products. Because the process relies on waste, which is typically generated
near areas of high energy demand, the company will be able to supply its renewable diesel
locally without having to use costly and constrained energy infrastructure.
   TCP is being demonstrated in a commercial environment. In December 1999, CWT
opened a pilot plant at the Philadelphia Naval Business Center with the support of the  Gas
Technology Institute. CWT began construction of its Carthage, MI facility in 2002, pro-
duced its first gallon of renewable diesel in 2004, and commissioned the plant in February
2005  as a joint venture with ConAgra Foods, Inc.  The company is currently selling its
renewable diesel for use in industrial boilers. The efficacy, efficiency, and other key quali-
ties of TCP have been reviewed and validated by a number of independent authoritative
organizations such as the Brookhaven National Laboratory, the Massachusetts Institute of

Technology, the U.S. Department of Energy, and the Vehicle Recycling Partnership. CWT
believes it is the first company to successfully demonstrate the ability to commercialize the
process of converting waste to oil in an energy-efficient manner.

Practical Asymmetric Catalytic Hydrogenation
   NOTE:  This project is the result of a partnership between Chiral Quest, Inc. and its
founder,  Professor Xumu Zhang of The  Pennsylvania State University. The project was
judged in both the academic and small business categories. The abstract appears in the aca-
demic section on 18.
Greening Atorvastatin Manufacture: Replacing a
Wasteful,  Cryogenic Borohydride Reduction with a
Green-by-Design, More Economical,  Biocatalytic
Reduction Enabled by Directed Evolution
   Atorvastatin calcium is the active pharmaceutical ingredient in Pfizer's cholesterol-low-
ering  drug  Lipitor®. The key  advanced chiral  intermediate in the  manufacture of
atorvastatin is £-butyl (4^?,6^?)-6-cyanomethyl-2,2-dimethyl-l,3-dioxane-4-acetate (ATS-8
orTBIN). It is the first isolated intermediate comprising both of atorvastatin's chiral cen-
ters. Pfizer's  traditional ATS-8 process uses a sodium borohydride (NaBH4) reduction of
the corresponding (5^)-hydroxy-3-ketoester (ATS-6 or HK) under cryogenic conditions to
give, after quenching, the (3^,5-/?)-dihydroxyester (ATS-7 or diol). The ATS-6 is first con-
verted  in situ  to a diastereodirecting  boron chelate by treatment  with hazardous
diethylmethoxyborane that is reacted with NaBH4 at below 85 °C to further  promote
diastereoselectivity. After the reaction, the borane reagent is regenerated and recovered by
repeated methanol quenches and vacuum distillations. Nonetheless, several percent of the
undesired (35) diastereomer is formed. Subsequently, the ATS-7 diol, an oil, is protected
as its acetonide, ATS-8, whose diastereopurity is upgraded by crystallization, with con-
comitant product  loss.
   The nominated technology represents a greener, more economical process for  reducing
ATS-6  to stereopure ATS-7. It  uses  a ketoreductase  biocatalyst  specifically evolved to
reduce ATS-6 with perfect diastereoselectivity under greener reaction conditions  (300 g/L
in water at ambient temperature and pressure)  in conjunction  with a previously evolved,
process-tolerant,  glucose dehydrogenase  biocatalyst that  returns the oxidized  cofactor
(NADP+) to its reduced state (NADPH).  The Codexis technology eliminates 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 ATS-7 with greater stereo-
purity.  Even  without  crystallization,  both ATS-7 diol from  this reaction  and ATS-8
produced from it  are more diastereopure than the atorvastatin  in Lipitor®. Codexis's bio-
catalytic  process is now in commercial  use to supply high-quality ATS-8  to generic
atorvastatin manufacturers on a multi-ton scale at shutdown prices.
Chiral Quest, Inc.
Codexis, Inc.

Cutting Edge
Formulations, Inc.
Corrosion-Resistance without Chromium:  On-Demand
Release of Environmentally Safe, Non-Chromium
Corrosion Inhibitors from Electroactive Polymer
   Currently, the prevalent primers and pretreatments  used to inhibit corrosion of alu-
minum  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 devel-
oping 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 envi-
ronment 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 synthe-
sized  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-l,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 asso-
ciated environmental and  safety risks. Crosslink has  identified a  business partner to
commercialize its technology during 2007-

Nature's Avenger™ Organic Herbicide: A Highly
Effective, Nontoxic,  Organic Alternative to Synthetic
and Natural Herbicides
   Nature's Avenger™ Organic Herbicide (NAO) is a safe, highly biodegradable, effective,
nonselective, post-emergent herbicide that has been approved by the U.S. EPA for organ-
ic agriculture production. NAO's active ingredient, ^-limonene, is the primary component
of citrus oil and is found naturally in more than 300 herbs, edible plants, and fruits. Citrus
oil is a strong degreasing agent that is commonly used in soaps, detergents, commercial
cleaners, deodorizers, shampoos, and mouthwashes. It is also used as a flavoring agent. This
natural degreaser strips away the waxy cuticle from weeds, subsequently dehydrating and
killing them.
   Earlier work demonstrated that «Mimonene by itself is a relatively weak herbicide. Work
by Cutting Edge showed that increasing the pH enhances the herbicidal efficacy signifi-
cantly. A mixture of proprietary inert ingredients also contributes  to activity such that
NAO is comparable in activity to Roundup® and paraquat, both of which are synthetic,
nonorganic herbicides.

   In the absence of an effective organic herbicide, organic growers tend to control weeds
primarily with mechanical tillage and hand labor, at a cost of approximately $1,000 per
acre. The availability of an easy-to-use, effective, cost-effective organic herbicide to control
weeds could revolutionize how organic growers manage their weeds. Using mechanical
tillage along with NAO in areas that cannot be mechanically tilled would bring the organ-
ic grower cost of NAO into a range of $45—80 per acre, which is  within the range of what
traditional, nonorganic growers pay for weed  control. In consumer and professional mar-
kets, the availability of a safer, more efficacious, organic herbicide gives the homeowner
and professional users an important alternative.

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 LiquidN™ 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 dura-
bility equal to or better  than that of conventional waterborne, solvent-based, or powder
coatings. The  LiquidN™ coatings can  be precision-sprayed at ambient temperatures,
enabling them to integrate easily into existing finishing processes.  Requiring only a few sec-
onds 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 bur-
   In addition to presenting Ecology Coatings with clear economic and environmental
advantages  over conventional industrial coatings, LiquidN™ coatings have unique char-
acteristics 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-suit-
ed for consumer electronics and other sensitive products. Unlike  existing coatings that are
generally limited to one  or two applications, LiquidN™ coatings are suitable for plastics,
metals, composites, paper, biodegradable  materials, and more.  Ecology Coatings's innova-
tive 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.

Liquid Seal and Nonhazardous Cleaner Eliminate
Odor,  Health, and Maintenance  Problems Stifling the
Acceptance and Implementation of Waterless Urinals
   The  Kohler Company approached Environmentally Sensitive Solutions, Inc. (ESS) to
develop the chemistry for a new waterless urinal  in a joint project. Waterless urinals have
existed for  years, but their high maintenance  requirements and lack of effective odor and
exposure controls have limited their large-scale adoption. ESS was to develop a superior
liquid seal and nonhazardous cleaner that would be an environmentally friendly combina-
tion, both  more effective than  current waterless urinal designs and safer than traditional,
caustic urinal cleaners.
Ecology Coatings
Solutions, Inc.

EverTech LLC
Exelus, Inc.
   The ESS unique liquid seal eliminates the odor that is problematic in traditional water-
less  urinals. The patent-pending liquid  seal  is  a  formulated  vegetable-oil-based,
biodegradable product that floats on the urine in the trap. This liquid seal is formulated to
prevent sewer gases and urine odors from emanating from the waterless urinal while allow-
ing urine through. Even when subjected to turbulence, the liquid seal repairs itself quickly,
preventing hazardous gases and undesirable odors from escaping. The liquid seal chemistry
also eliminates the need for the hazardous urinal pucks used as supplemental odor control
in an estimated 90 percent of flush urinals. These ^>-dichlorobenzene-based pucks have
been proven harmful to human health and the environment.
   The ESS waterless urinal cleaner is neutral, noncorrosive, and surfactant-based; it elim-
inates the hazards of traditional cleaners. For daily cleaning, the ESS  cleaner is compatible
with the liquid seal and does not adversely affect the performance of the liquid seal.
   The keys to waterless urinal acceptance and implementation are the complete odor con-
trol and low maintenance that only these green chemistries can provide. Each waterless
urinal has the potential to save up to 40,000 gallons of water per year. Kohler has imple-
mented the ESS liquid  seal and cleaner in the global launch of its Steward™ collection of
waterless urinals.

Everdex-Enhanced Alowood
   Deforestation of old-growth forests and rainforests is of growing concern given the far-
ranging debates today on climate change. Consumers, however, still want the look of exotic
hardwoods in products  such as flooring and furniture. Alowood offers an environmentally
friendly alternative: the opportunity  to  get an exotic look and performance  using fast-
growing plantation softwoods as the base  wood  impregnated with an innovative green
chemistry, the Everdex formulation.
   Everdex is a polymeric formulation made from urea, glyoxal, and starch in water; it does
not contain any formaldehyde. Softwoods, particularly sustainably grown, plantation soft-
woods, are immersed in dilute solutions of Everdex and subjected to a vacuum and pressure
treatment to impregnate them with Everdex. Next, the impregnated wood is heated, caus-
ing 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 nat-
ural hardwood.
   EverTech is currently selling Everdex-enhanced Alowood to the building industry seg-
ment as an alternative to natural hardwood. This innovative product is making a significant
positive environmental impact in that every piece of Alowood sold replaces a piece of hard-
wood lumber or exotic wood that can remain a part of the ecosystem. Alowood made from
plantation wood grown in about 30 years is preferable to exotic hardwoods that  often take
hundreds of years to grow.

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
£-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 regener-
ated. 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 alkyla-
tion. 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 struc-
ture 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  ofStyrene Monomer
   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  ther-
modynamically limited reaction.  Styrene  production consumes about  10  times more
energy than does the production of most other industrial  chemicals and is  a major con-
tributor 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
   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 tech-
nology  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 CC>2 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 pro-
duce all of the heat of reaction and most of the distillation  energy for the process without
generating any CCh.  Exelus has demonstrated its technology at the bench scale and expects
to begin pilot plant tests in mid-2007-
Exelus, Inc.

Fungi  Perfect!, LLC
GreenBlue (Green
Blue Institute)
Mycopesticides and Mycoattmctants
   Certain mold fungi, called entomopathogenic fungi, kill insects and use their carcasses
as platforms for disseminating spores. With limited  success, the pesticide industry has
attempted to deploy entomopathogenic fungal spores to kill pests such as termites and
ants. The spores of entomopathogenic fungi repel many of these  insects, however, and
insects have natural defenses against them. Soldier insects guarding the nest keep spore-
contaminated foragers from entering in order to protect  the queen and the colony from
   Fungi Perfect! has developed methods to deploy the presporulating mycelia of the ento-
mopathogenic fungi Metarhizium  and Beauveria as  natural agents to  attract and kill
termites and ants. The novelty of this technology is the discovery by Fungi Perfect! that
ants, termites, and flies are attracted to entomopathogenic fungi in  their  mycelial state,
prior to sporulation. Fungi Perfect!  isolated fungi from naturally infected insects and then
cultured the fungi selectively to create strains that delay spore production for several weeks.
The presporulating mycelia emit powerful attractants, trail-following elicitors, and feeding
stimulants, which draw select pests  to a chosen site, from where they spread the infectious
fungi  throughout the targeted nest  and ultimately to the queen. In choice tests, termites
prefer the presporulating mycelium  of Metarhizium anisopliae to wood as food. The infect-
ed colony, upon sporulation, repels  subsequent insect invasions.
   This mycotechnology is economical and scaleable; it uses current cell culture methods.
It has been awarded two patents, with more pending. Tests at Texas A & M University and
the U.S. Department of Agriculture show this technology works against  Formosan ter-
mites, eastern subterranean termites, and fire ants. Subsequent tests show positive results
in controlling carpenter ants and fungus gnats. This discovery may well replace toxic pes-
ticides and lead to novel  methods  for controlling insect pests worldwide,  protecting the
environment, people, and other organisms.

CleanGredients^™-: Systems-Based Information
Technology for Green  Chemistry
   CleanGredients™ is an online  database of environmental fate,  toxicology,  and other
data on cleaning product ingredients. CleanGredients™ 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.
   CleanGredients™ facilitates  the ongoing development and implementation of green
chemistry in the  cleaning products industry. It has the  potential  to expand into other
industry sectors. CleanGredients™ 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 non-
profit sector. The committees established the overall format and identified the specific
attributes for the CleanGredients™ database. Interested participants, now numbering
around 600, serve as peer reviewers.
   CleanGredients™ 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 ingre-
dients for environmentally preferable product formulations. CleanGredients™ lists only

chemicals that have been characterized adequately and meet key human and environmen-
tal characteristics. Formulators can search the database by general ingredient information
and physical properties to identify suitable candidate ingredients for particular applica-
tions. The  first CleanGredients™ 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.

The Use of Green Unikleen in Oil Spill Clean-Up, Both
on Land and in Water
   IPAX's flagship product, Green Unikleen, will improve oil spill clean-up, both on land
and at sea. Green Unikleen is a biodegradable, nontoxic, concentrated cleaner and degreas-
er that can be used with any manual or mechanical cleaning equipment. It is water-soluble
and has  no volatile organic compounds (VOCs). Its formula includes sodium silicate,
Biosoft S-100, Neodole 23-5 (Shell Oil; includes a mixture  of Cu-\3 alcohol ethoxylates),
a tetrasodium  salt, and Surco SXS (40—42 percent sodium xylene sulfonate and  up to
2 percent sodium sulfate in water).
   Green Unikleen has been used extensively for washing  automotive parts; it replaces
VOC solvents  and reduces hazardous waste. IPAX has research results demonstrating that
Green Unikleen is an improvement over current technologies to clean up oil spills on land.
Green Unikleen is able both to return oil-saturated soil back to a state that will support
plant growth and to allow recovery of the oil for its original use. Together with added bio-
supplementation,  Green  Unikleen can  reduce  residual petroleum  in  treated soil  to
0.1 percent, the maximum concentration allowed  for agriculture.
   For oil spills at sea,  Green Unikleen has been  shown to  be  a very effective dispersing
agent as well as a fire-preventive  and  -extinguishing additive. Green Unikleen breaks oil
spills into small droplets, forming a thin  emulsion that disperses in the water column. In
dispersed form, the oil is subject to natural degradation by marine microorganisms.  Green
Unikleen can be effective in dispersing most liquid oils and liquid water-in-oil emulsions
with viscosities below about 2,000  centistokes.  In a fire-extinguishing  demonstration,
Green Unikleen and water (1:10) required less than 2 minutes to extinguish a fire of ben-
zene, diesel fuel, and crude oil that had been allowed to heat up to  over 2,000 degrees
before treatment.  Green Unikleen is available commercially, and IPAX has applied for a
patent for its technology.

New Green Technology for Eliminating Hydrogen
Sulfide in Aqueous  Systems, Especially Petroleum
Industry Systems
   The  occurrence of hydrogen sulfide (H^S) in  aqueous systems is a major concern of
many industries. This concern is especially acute in the international oil and gas industry.
IrbS  constitutes a serious health, environmental,  and economic problem in virtually all
major oil and gas production operations. Massive global reservoirs and water systems are
now heavily contaminated with corrosive, poisonous IrbS and harmful iron sulfide precip-
itates that plug pipelines, impeding oil and gas production.
   The source of IrbS is the reduction of soluble sulfate (SC>4) in the water by indigenous,
aerobic, sulfate-reducing bacteria  (SRB). To combat H^S formation, the industry has used
IPAX Cleanogel,
The LATA Group,

biocides such as glutaraldehyde, acrolein, formaldehyde, quaternary amines, and chlorine
extensively. However, SRB are becoming resistant to them, necessitating the use of increas-
ingly toxic and dangerous biocides.
   LATA's biocompetitive exclusion (BCX) technology is designed to attack SRB. The
BCX process is initiated and sustained by patented, environmentally friendly formulas
named Max-Well 2000 that contain a combination of inorganic nitrate and nitrite. These
formulas target and directly manipulate the indigenous microflora of hydrocarbon-bearing
reservoirs and  a wide variety of surface injection and produced water systems. Low con-
centrations  of Max-Well 2000  act  as alternate  electron acceptors for indigenous,
nitrate-reducing bacteria  (NRB) so that they subsequently flourish and out-compete SRB
for essential  growth nutrients. The nitrite component is toxic to SRB and also reacts chem-
ically with existing H^S to form soluble, nonhazardous SC>4. The end result of the growth
of beneficial NRB populations is the production of nonhazardous nitrogen gas, elimina-
tion of existing H^S in the system, and continuous blocking of new H^S and  iron sulfide
production.  One successful field project with a major oil company is leading to treatment
expansions in the United  States and elsewhere. Another ongoing field trial with a major oil
company is destroying and controlling H^S in an oil and gas reservoir.

Novel Device for Removing Mercury from  Produced
Water and Vapor Streams
   Significant  amounts of mercury can be present in the vapor and produced water gen-
erated  by offshore drilling operations.  Mercury in produced water associates itself with
various impurities in the  water in the form of organometallic, colloidal, ionic, and metal-
lic species and as dissolved solids and  gases. The  broad range of organic and  inorganic
constituents in these streams makes treatment difficult. Treatments such as sulfide-impreg-
nated carbon-  or carbamate-based media that rely on a single stage to remove  all mercury
have been field-tested with poor results including organic fouling of the treatment media.
   The novel MYCELX  device uses a  three-stage approach.  Each upstream stage removes
components that would otherwise tend to foul the subsequent stage. Stage 1  uses solubility
and weak interactions. Stage  1 filtration media  are  impregnated with a curable viscoelastic
rheology modifier, MYCELX HRM™, which is the reaction product of drying and semi-
drying  oils with isobutyl methacrylate. These media exhibit  high affinity for  colloidal
mercury and insoluble organic compounds, binding them into a cohesive mass. Stage 2 uses
Lewis acid-base reactions.  In stage 2, a mixture of natural zeolite, MYCELX-impregnated car-
bon, and granular activated carbon exhibits high affinity for ionic  and organically bound
mercury and for soluble organic compounds, causing them to precipitate. The final stage uses
redox potential. This stage incorporates a matrix of braided copper  wire electroplated with
precious metals into an anisotropic electroless reduction module that isolates and extracts ele-
mental mercury.
   Tests of the three-stage unit with mercury-laden (63-6 ppm) produced water from the
field were successful at bringing the mercury levels below 0.5 ppb without a decrease in per-
formance  efficiency because of fouling. This device eliminates worker exposure to  toxic
compounds such as dimethyl mercury. It also eliminates mercury discharges into the oceans
and atmosphere. MYCELX did pilot performance tests and applied for a patent for this  tech-
nology in 2006.

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 p-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 ideal-
ly 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 (YNaRl and
AtNaR2) for automated nitrate analysis using continuous flow analysis and  discrete ana-
lyzers. 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.

PreKote® Surface Pretreatment: Replacing Hexavalent
Chromium  with an Environmentally Safe Solution
   Hexavalent chromium (Cr(VI)) is the industry standard for corrosion protection on
aluminum substrates prior to painting, but it is also toxic and hazardous. Discontinuing its
use is a U.S. EPA pollution prevention priority through the 1993 Executive Order 12856.
Cr(VI) is also on the European End of Life Vehicles (ELV) Directive of nonallowable mate-
rials. Most recently,  in May  2006, the Occupational Safety and  Health Administration
(OSHA) reduced the permissible exposure limit (PEL) for Cr(VI) by 52 percent in the
aerospace industry.
   In 1994, Pantheon Chemical began an extensive research program to find an environ-
mentally safe replacement for chromium pretreatments, also called chromium conversion
coatings. Pantheon designed  PreKote® on the molecular level  from environmentally safe
chemicals to clean and promote paint adhesion to substrates to be coated. PreKote® has a
neutral formula that is not  based on  metals. It eliminates the need for an acid precoating
treatment. Its corrosion inhibitors are not persistent, and its surfactants are biodegradable
and environmentally friendly. Unlike other pretreatments, PreKote® is suitable for use on
ferrous and nonferrous metals, anodized and phosphated surfaces, many plastics, and com-
posite materials.
The Nitrate
Company, Inc.
Pantheon Chemical

Penn Specialty
Chemicals,  Inc.
Polnox Corporation
   After years of extensive laboratory and field testing using highly advanced techniques of
surface analysis and molecular modeling, Pantheon introduced PreKote® to the U.S. mar-
ket as an  efficient, green substitute for chromium pretreatments. In 2003, the United
States Air  Force (USAF) approved and implemented the use of PreKote® as a replacement
for chromium pretreatments of aluminum substrates. Subsequently, leaders in the com-
mercial  aerospace market conducted extensive testing and implemented PreKote® for its
safety, performance, and economic  benefits.  PreKote® technology provides superior per-
formance  while it improves environmental and worker safety by eliminating heavy metal
waste streams and replacing toxic acids and solvents. It also decreases operational costs sig-
nificantly  by simplifying pretreatment procedures.

2-Methyltetmhydrofuran: A  Green  and Cost-Effective
Alternative to Alky I Ethers and Chlorinated Solvents
   2-Methyltetrahydrofuran (MeTHF)  is a green, cost-saving alternative to oil-derived sol-
vents such as  tetrahydrofuran  (THF), dichloromethane,  and diethyl ether. MeTHF  is
derived  from furfural, which is produced from naturally occurring pentoses in agricultur-
al waste like  corncobs or bagasse (sugar cane).  Penn Specialty Chemicals developed a
cutting-edge liquid-phase hydrogenation process to synthesize MeTHF in two steps from
furfural via 2-methylfuran. Penn  Specialty Chemicals also optimized this technology to
allow the large-scale commercialization  of MeTHF.
   MeTHF has a solid science and innovation foundation, provides important human
health and environmental benefits, and has a track record of broad applicability. The mar-
keting  of MeTHF is based on a strong internal R&D  program. The  science behind
MeTHF has been validated by scientific publications, a prestigious international innova-
tion nomination, and its commercial success  in the market.
   MeTHF is  a very versatile reaction solvent and is much more stable than THF under
acidic and basic conditions. Because it is more stable, it is suitable for carrying out a wide
combination of reactions successively in one  pot without solvent degradation. MeTHF is
also superior to mixtures of THF and toluene as an extraction solvent. These properties of
MeTHF reduce overall solvent use.
   MeTHF has important human health and environmental benefits. MeTHF is manu-
factured from green feedstocks. As a unique substitute for diethyl ether, MeTHF reduces
the potential for fire and explosion. MeTHF also reduces the contamination of process
effluent waters because, unlike THF, MeTHF is not water-soluble. Moreover, MeTHF can
easily be recycled at reduced energy  consumption, even in small-scale production.
   In 2006, Penn Specialty Chemicals opened a dedicated plant in Memphis, TN to man-
ufacture MeTHF. As a  result, MeTHF now has a multimillion-dollar emerging market
with a significant impact across industries, applications, and products.

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 pro-
tection, and higher material diffusion rates.

   Polnox Corporation is in the process of introducing seven high-performance macro-
molecular 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 hydroxy-
anisole, fer^-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 perfor-
mance 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-per-
formance ratio. Acute oral  toxicity (LDjo) 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 fea-
sibility  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 com-
mercialize one or more of its antioxidants during 2007-

A New, Heterogeneous, Fixed-Bed Catalyst for
Continuous-Flow  Biodiesel Production from Waste Fats
and Oils
   Fossil fuels have detrimental effects on the environment: they  release sequestered car-
bon compounds and other pollutants into the atmosphere. Biobased fuels such as biodiesel
are more environmentally  friendly because  their use recycles carbon through renewable
biomass, and they burn cleaner than  fossil fuels.  Current manufacturing processes for
biodiesel require high-quality, high-purity virgin oils, mostly soy  oil. The price of high-
quality  oil accounts for over 80 percent of the price of biodiesel. As a result, the biodiesel
industry is not commercially viable at present without government support.
   Working with Professor Arlin E. Gyberg at Augsburg College,  SarTec has developed a
technology to produce biodiesel in a fixed-bed, flow-through reactor that could change
how the industry produces  this renewable fuel. The key to this new reactor is a highly effi-
cient, heterogeneous catalyst that  efficiently and economically converts inexpensive plant
oils and animal fats to biodiesel. The catalyst contains modified porous microspheres based
on zirconia (zirconium dioxide).
   In addition to the environmental advantages of biofuel over fossil fuels, SarTec's process
offers several advantages over the current biodiesel production method: (1) the production
process  uses less energy overall; (2) the process uses cheap feedstocks such as waste grease
and animal tallow as well as a variety of plant oils; (3) the zirconia-based catalyst is con-
tained in a fixed-bed reactor, eliminating the current need to add  catalyst to the reaction
mixture continuously, which, in turn, reduces the amount of waste produced; and (4) the
new technology eliminates unwanted side reactions that produce soaps from free  fatty
acids, thereby reducing the amount of hazardous waste. During 2006, SarTec applied for
a patent for this technology, and it also produced biodiesel with a lab-scale reactor using a
variety of feedstocks including waste frying  grease.  The company  is currently working to
scale up its technology for large-scale biodiesel production.
SarTec Corporation

Specialty Fertilizer
Solutions, LLC
Biodegradable,  Water-Soluble, Anionic Polymers
Prepared in an Environmentally Benign Process
Enhance Nutrition Efficiency, Reduce Waste,  and
Reduce Runoff of Phosphorus
   Historically, phosphorous fertilization of crops has created a problem. Once phospho-
rous is applied to the soil, reactions with various cations including calcium, magnesium,
aluminum, and iron fix 75—95 percent of the phosphorus, reducing its efficiency as a nutri-
ent. As a result, farmers  must use excess phosphorus to achieve high crop yields. Poor
phosphorous efficiency has led to a buildup of residual phosphorous in soils, which has
environmental consequences.
   To overcome this problem, Specialty Fertilizer Products has designed a family of dicar-
boxylic copolymers that increase the efficiency of phosphorous fertilizers. The technology
includes manufacturing several related, low-molecular-weight,  itaconic—maleic copolymers
and adding specific polymers to phosphorous fertilizers, which both enhances agricultural
efficiency and reduces the environmental impact of fertilization.
   Specialty  Fertilizer uses a green process  to synthesize its  nontoxic, water-soluble,
biodegradable polymers. The main component in these polymers  (by weight) is itaconic
acid, a monomer that 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. The polymers biodegrade after use,
so the environmental footprint of this technology is negligible.
   The use of specific polymers derived from this process with  granular and fluid phos-
phorous fertilizers greatly increases phosphorous availability in  soils, resulting  in  greater
absorption of phosphorous into growing plants. Benefits include reduced phosphate accu-
mulation in soil and an average increase of 10—15 percent in crop biomass at minimal cost.
Also, improved phosphorous uptake reduces phosphorous runoff and, therefore, contami-
nation and eutrophication of waterways.
   This technology also enables more biomass-derived fuel to be made with less environ-
mental impact. By making phosphorus supply much more energy-efficient, far less fuel is
consumed to grow more useful  biomass and produce  more plant-derived  liquid fuels.
Specialty Fertilizer sells these polymers under the trade name AVAIL™.

Development and  Commercial Application of
SAMMS™, a Novel Adsorbent for Reducing Mercury
and Other Toxic Heavy Metals
   SAMMS™ (self-assembled monolayers on mesoporous silica) was developed and com-
mercialized to adsorb toxic metals such as mercury and to replace less-effective adsorbents
such as activated carbon and ion  exchange resins. SAMMS™ is a nanoporous  adsorbent
that forms strong chemical bonds with the target toxic material. It provides superior cost
economics and adsorption capacity; it also reduces the volume of hazardous waste. It is cur-
rently being deployed in the chemical industry.
   The original functionalization  of SAMMS™ used toluene as the solvent. The resulting
waste stream included water, methanol, toluene, and traces of mercaptan. It is impractical
to separate the components of this mixture; therefore, it was usually disposed  of as haz-
ardous waste. This process was improved by substituting a  green solvent,  supercritical

carbon dioxide (sc CC^),  which allows complete silane deposition. With this patented
process, SAMMS™ manufacturing is faster and more efficient. The sc CC>2 process also
results in a higher-quality, defect-free silane monolayer with no residual silane in solution.
When the reaction is complete, the only byproduct is the  alcohol from the hydrolysis of
the alkoxysilane. The CC>2 and the alcohol are readily separated and captured for recycling,
eliminating the waste stream of excess reagents and solvent in the traditional synthesis. The
SAMMS™ materials emerge from the reactor clean, dry, and ready for reuse. The com-
bined impact of a green manufacturing process for SAMMS™ and the superior adsorption
characteristics of SAMMS™ materials result in a long-term  reduction in  release of toxic
metals into the environment.
   The SAMMS™ technology and its commercialization represent collaboration between
researchers at  Pacific Northwest National Laboratory who did the original research and
Steward Environmental Solutions, which licensed the technology and scaled up the man-
ufacturing process. In 2006, Steward applied for two patents  covering its green synthesis.

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 Feed™ 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 hor-
mones, 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 damag-
ing 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 effective-
ness. 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 stud-
ies 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.
Stoller Enterprises

Super Trap Inc.
Torchem LLC
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 carbon-
ate).  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 leach-
ing 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. GEL-
COR® 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.

Manufactured Firelogs Based on Whole Timber
   Conventional manufactured  firelogs offer lower  emissions  than cordwood. They are
made of recycled materials such as sawdust bound together with petroleum wax from fos-
sil fuel, which is a solid fuel additive. In the last few years, however, sharp increases in crude
oil prices have greatly increased manufacturing costs  for  these conventional products.
   Torchem has developed a  natural alternative to  conventional manufactured  firelogs
using cleaner-burning,  inexpensive, bioderived materials. Torch firelogs are made  from
whole timber and  crude glycerol by a simple timber treatment process. The timber is cut-
off parts of plantation-grown trees that have only minimal commercial value as a feedstock
for the paper industry. Because the timber is whole, Torchem can use a liquid fuel additive,
glycerol. Crude glycerol is  a low-value byproduct of biodiesel production. Torch firelogs
offer an all-natural solution. They burn with  emissions  factors that are 50 percent lower
than conventional manufactured fire logs, and they contain no fossil fuel components. In
addition, they are available to consumers at a lower price than conventional manufactured
   Torchem LLC is a joint business venture  between Torch Innovations and Chemco Inc.,
established to market the new Torch firelog for use in domestic fireplaces, stoves, and out-
doors. After  successful product testing, Torchem commissioned emissions profiles for its
product in December 2006.

Olefins by High-Intensity Oxidation
   Ethylene is the highest-volume, highest-value commodity chemical. Over 120 million
tons are produced annually with a value of over $100 billion. The conventional path to
ethylene is the energy-intensive steam cracking of ethane. This approach consumes approx-
imately 500 trillion British  thermal units  per year (Btu/yr), the  equivalent of over
80 million barrels of oil. Steam cracking also suffers from poor selectivity for ethylene, but
is well-established and has favorable process economics.
   Velocys is at the  cutting edge of microchannel process technology, a platform with the
potential to provide substantial cost and energy savings. With the support of the U.S.
Department of Energy's Industrial Technologies Program, Velocys  has been collaborating
with Dow Chemical Company and Pacific Northwest National Laboratory. Velocys and its
partners have developed a breakthrough process for producing ethylene. The process uses
oxidative dehydrogenation in Velocys's proprietary microchannel process technology archi-
tecture, along  with carefully controlled  temperature  and a catalyst adapted to  the
microchannel  environment. This  approach improves feedstock use and saves substantial
energy. These benefits stem  from the novel  reaction path and  the unique  ability of
microchannel  devices to tailor reaction rates and temperatures. The process can provide
higher selectivities,  conversions, and throughputs  than the conventional steam cracking
process, which is equilibrium-limited. Dr. Terry  Mazanec, Senior Technical  Program
Manager at Velocys, leads a multidisciplinary team that has demonstrated that microchan-
nel oxidative dehydrogenation can achieve the economic targets set by Dow, the world's
leading producer of ethylene.
   The potential  benefits  of this novel, oxidative dehydrogenation route to ethylene are
substantial. By 2020, Velocys's process could save 150 trillion Btu per year, eliminate more
than eight million pounds per year of oxides of nitrogen  (NOx), and eliminate more than
10 million pounds per year of sulfur  oxides (SOx). Velocys has  scheduled construction of
its first commercial  demonstration facility during 2007-
Velocys Inc.


Entries from  Industry  and


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 prod-
uct 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 manufac-
turing 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 envi-
ronmental 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 aery-
late  polymers. They do  not  contain any  fluorochemicals, alkylphenol  ethoxylates,
poly(vinyl chloride), phthalates, or heavy metals intentionally added or present as impuri-
ties 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, solvent-
based 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 water-
based 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 formula-
tions to Post-it® Sticky  Picture Paper for printing digital pictures and to other specialty
applications in 2005-

Alky Clean®: The Safe Alkylation  Technology for
Producing Clean  Gasoline
   Refinery alkylate is a clean gasoline component produced from light olefms (C^) and
isobutane. It consists of relatively harmless isoparaffms with low vapor pressures and very
high octane numbers. Further,  it eliminates environmentally unfriendly components such
as aromatics (e.g., benzene), olefms, and sulfur and nitrogen compounds that are present
in competing gasoline components. Alkylate is the preferred gasoline component to meet
stricter environmental regulations.
   Traditional alkylate production, currently about 30 billion gallons per year worldwide,
requires hazardous processes catalyzed by liquid acids  (HF or H^SO^. HF is extremely
toxic: it can form aerosol  clouds that can be lethal even more  than  5 miles from their
source. Sulfuric acid technologies are  extremely corrosive.  Worldwide,  they generate
10—20 billion pounds per year  of spent acid, which must be transported and regenerated.
3M Office Supplies
Catalysts Company
BV; ABB Lummus
Global  Inc.

Arch Treatment
Technologies, Inc.
Arkema Inc.
For more than 40 years, academic and industrial researchers have searched for an econom-
ic, benign, solid acid catalyst technology to replace these liquid acid technologies.
   The AlkyClean® process is an economically attractive and environmentally safe alter-
native that is now commercially available.  AlkyClean® replaces the liquid acids with a
novel, true solid acid zeolite catalyst in an innovative process. The zeolite-based formula-
tion contains no halogens, has acid sites of optimum strength for alkylation, and exhibits
the necessary activity, stability, and capacity for catalyst regeneration required for a suc-
cessful process. Albemarle Catalysts of Houston, TX produced the zeolite catalyst, and
ABB  Lummus  Global  of Bloomfield, NJ designed and prepared a demonstration plant.
This 10-barrel-per-day plant in Finland has been producing high-quality alkylate for more
than 2 years using a refinery slipstream. During this time, the technology has been opti-
mized for commercialization. Product quality is on par with existing technologies. The new
process does not produce wastewater or sludge, and does not require any acid neutraliza-
tion facilities or post-treatment of any kind.

Wolman® AG Metal-Free Wood Preservative
   Wolman® AG is the first organic preservative for pressure-treating wood used in decks,
fences, and residential  projects. The  active ingredients  are  carbon-based and contain  no
metals. This is a long-envisioned breakthrough in wood preservation.
   Wolman® AG preservative offers broad-spectrum protection against wood decay and
termites yet does not contain copper, as do current alternatives. Just as an earlier transition
replaced chromium  and  arsenate  with  copper in  common wood preservatives, this
advancement offers  control  of termites  and  fungal  decay without  copper.  Instead,
Wolman® AG takes advantage of the  synergistic qualities of three organic biocides: propi-
conazole, tebuconazole, and  imidacloprid, which have long histories of residential and
agricultural use. They readily undergo bacterial degradation in soil and groundwater,
becoming nonhazardous materials. As a result, Wolman® AG is intended for  use on out-
of-ground wood, which  accounts  for nearly  80  percent of  all applications  for
pressure-treated wood.
   Proven efficacious in field  and lab tests, wood treated with Wolman® AG is recyclable
after use as decking. It  can be burned for energy in commercial incinerators in accordance
with  state  and local laws.  It is  safe for landfills because  any runoff is biodegradable.
Wolman® AG contains the three biocides blended with emulsifiers  to produce a concen-
trated aqueous  formulation. The formulation has a pH  of 7-5, close to that of water. It is
not regulated as a hazardous  material for land, water,  or air transport. In addition, the
amount of preservative needed is comparatively small, reducing total production and trans-
portation requirements. The mammalian acute toxicity for Wolman® AG is 4,000 mg/kg,
in contrast to that of copper-based alternatives, which have acute toxicities of 800 mg/kg
or less. The price of Wolman® AG is comparable to or less than that of copper-based alter-
natives. In 2006, the product  was first used at a customer's plant.

Green Chemistry in the Manufacture of Thioglycolic
   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 compo-
nent  of cosmetics, and a component of products to treat hides and leather.  Arkema's
traditional process included hydrogen sulfide (H^S) as a feedstock.  H^S is a poisonous,

flammable, colorless gas that is regulated as an air pollutant, a water pollutant, and a haz-
ardous waste. Because of its requirements for high-purity H^S feedstock, Arkema was
buying IrbS from a source in Canada and  transporting over 4 million pounds of pressur-
ized, liquid H2$ by railcar to Alabama each year.
   Arkema developed and implemented a beneficial process change that replaced the H^S
in its manufacturing process with sodium  hydrosulfide (NaSH). NaSH is safer for work-
ers, is subject to fewer air, water, and waste regulations, is comparable to IrbS 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  H2$  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.

Reducing the Environmental, Health,  and  Safety Impact
of Cooling Water Treatment Programs
   Typical conventional cooling water treatment programs require corrosion control, scale
inhibition, and microbiological control. Among common water-treatment chemicals are
potentially hazardous and toxic materials. Ashland Water Technologies developed a solu-
tion that significantly reduces the environmental,  health,  and safety impact of cooling
water treatment programs without sacrificing performance. The unique combination of
SONOXIDE ultrasonic  treatment for microbiological  control, ENVIROPLUS cooling
water treatment products for  corrosion and scale control, and the ULTRA-SERV solid
chemical inventory  management program delivers a  high-performance,  environmentally
responsible program and enhances safety by eliminating the need for liquid chemicals.
   ULTRA-SERV is a solid chemical feed system that reliably dissolves and delivers a solid,
concentrated form of ENVIROPLUS corrosion and scale control product to recirculating
cooling systems. The ENVIROPLUS series of cooling water treatment products includes
a patented, complex, synergistic blend of multifunctional components that provide excep-
tional multimetal corrosion  inhibition and scale control  in alkaline cooling water systems.
The blend includes  polymeric antiscalants (biodegradable carboxylic antiscalants), phos-
phonocarboxylates,  and other  organic  and inorganic components.  ENVIROPLUS
products reduce the environmental impact  of treated water discharge because they are
inherently biodegradable, contain no heavy metals, and contain very low phosphorous.
This profile enables plants to comply with  increasingly stringent discharge limitations and
allows cooling towers to operate at higher cycles of concentration, thereby reducing water
   SONOXIDE ultrasonic water treatment  for  microbiological control enhances health,
safety, and environmental benefits even further. SONOXIDE ultrasonic treatment pro-
vides total-system  microbiological control by  applying low-power,  high-frequency
ultrasound. SONOXIDE treatment controls total bacteria and biofilm  in recirculating
cooling systems, virtually eliminating the need for chemical microbiocides. SONOXIDE
is currently in use in over 500  cooling systems worldwide. Ashland introduced the newest
component, ULTRA-SERV, in 2006.
Ashland Water

Aspen Technology,
BASF Corporation
 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 sol-
 ubility 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 solubil-
 ity 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 selec-
 tion,  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 sol-
 vent 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.

A Non-HAP (Hazardous Air Pollutant)  Coating for
 Extruded Aluminum
   The market for coatings of extruded aluminum is dominated by spray-applied, solvent-
 containing 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 per-
cent 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.

Development and Commercialization ofBiobased Resins
and Toners
   Over 400 million pounds of electrostatic dry toners based on petroleum-derived resins are
consumed in the United States annually to make over 3 trillion copies in copiers and print-
ers. Only a small fraction of this paper is recycled, however, because conventional toners are
not designed for ready de-inking.
   With early-stage  funding from the  Ohio Soybean  Council  (OSC),  Battelle and
Advanced Image Resources (AIR) formed a team to develop and market biobased resins
and toners for office copiers and printers. A novel Battelle technology uses oil, protein, and
carbohydrate  from soybean and other crops as chemical feedstocks.  Battelle has developed
bioderived resins and toners from these feedstocks through innovative, cost-effective chem-
ical modifications and processing. Battelle and AIR, the licensee of the technology, have
coordinated to move from early-stage laboratory development to full-scale manufacturing
and commercialization. Their efforts have resulted in a cost-competitive, highly marketable
product that  is compatible with  current hardware and  will provide users with seamless,
environmentally friendly printing and copying.
   The new technology also offers advantages in recycling waste office paper without sac-
rificing print  quality. Improved de-inking of the fused ink from waste copy paper results
in higher-quality recovered materials and streamlines the recycling process. Preliminary
lifecycle analysis shows significant energy savings and reduced carbon dioxide emissions in
the full-value chain from resin manufacture using biobased feedstocks, to toner produc-
tion, and finally to recovery of secondary fibers from the office waste stream. At 25 percent
market penetration, this technology could save 9-25 trillion British  thermal units per year
(Btu/yr) and  eliminate over 360,000  tons of carbon dioxide emissions per year. Overall,
soy toner provides a  cost-effective, systems-oriented, environmentally benign  solution to
the growing problem of waste paper generated from copiers and printers. In 2006, AIR
successfully scaled up production of the resin and toners for use in HP LaserJet 4250 Laser
Printer cartridges.

Nexterra™ Carpet: Modified PET Carpet Backing
   Carpet tile backings have previously been made of polymers such as poly(vinyl chloride)
(PVC), polyurethane, or mixtures of various thermoplastics that are derived from petro-
chemicals.  The  manufacture or  disposal  of some of these  backing materials  raises
environmental concerns. Further, the energy required for the physical separation of the tile
backing and the face fiber (usually by grinding or air elutriation) adds to the cost of recy-
cling current tile backings.  Physical separation also leads to impure component streams for
Battelle Memorial
Beaulieu Group,

Group, Inc.
   Beaulieu has developed a modified polyethylene terephthalate (PET) backing system
that contains a much lower percentage of products derived from virgin petroleum, requires
significantly less energy to  produce,  and offers new solutions to carpet  tile  recycling.
Beaulieu had already been purchasing postconsumer PET bottles and converting them into
carpet fiber. Now, however, Beaulieu is also converting plastic PET bottles  into a pliable,
flexible  carpet  tile  backing system  using  a unique  transesterification process  (patent
allowed). This process lowers both the molecular weight and the melting point of the poly-
mer. Beaulieu's  modified PET polymer allows the company to use postconsumer ground
glass as a filler in their backing.
   Altogether, their backing system contains 85 percent postconsumer materials and only
15 percent virgin petrochemicals by weight. Traditional carpet tiles contain  approximately
50 percent virgin petrochemicals. The exclusive modified PET backing enables more cost-
effective and energy-efficient recycling.  The solubility of the polymer in  polar solvents
allows separation of the carpet tile backing from the face  fiber (usually nylon  6 or 6,6).
During  recycling, Beaulieu uses  a glycol monomer bath at 150—180  °C to  dissolve the
polymer, separating it and the glass from the insoluble face fiber.
   Beaulieu launched Nexterra™ carpet tiles in May 2005- The company estimates its
2005  product sales at $1—5 million, and  is expecting significant sales growth during 2006.

GreensKeeper® Polymer Slurries for Oil and Gas Well
   In December 2003, the major oil and  gas pumping service companies (Benchmark's cus-
tomers) 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 evaluat-
ed 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 suspen-
sion 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 slur-
ries, GreensKeeper® slurry products are  nonflammable, thus reducing fire  and explosion
risk during production, transport, storage, and use. Unlike diesel, they are  not DOT-reg-
ulated, 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.

Irbesartan (Avapro®)  Greenness Project
   Irbesartan, which is chemically synthesized, is an  angiotensin II receptor antagonist
used to treat hypertension and renal disease in type 2 diabetic patients. Although clinical
trials had demonstrated the medical benefits of Irbesartan, the original synthetic process
was difficult to manage from an environmental, health, and safety (EHS) perspective. The
primary concerns included a potential runaway bromination reaction, severe skin and eye
irritation from  an  intermediate product,  and negative environmental effects of several
organic solvents. Previously, Bristol-Myers Squibb (BMS) had mitigated some of the neg-
ative EHS impacts of the original synthesis, but the bromination in the first synthetic step
remained  a concern. This bromination  created a nonbiodegradable byproduct that
required incineration and, thereby, created a significant waste disposal problem.
   To address that problem and further minimize EHS impacts, BMS modified the bromi-
nation  and  crystallization processes it  uses  in  the  synthesis  and  modified  the
recrystallization process for the active pharmaceutical ingredient. These modifications have
increased yield,  saved energy, reduced the use of hazardous materials, reduced waste, and
improved  workplace health and safety.  Based  on  a projected  5-year  production  of
Irbesartan, BMS expects to  save over 680 metric tons  of solid chemicals, over 40 million
liters of solvents, and 4.4  million  liters  of water.  Other projected benefits include a
325-ton reduction in solid waste requiring incineration and a savings of 24,400 megawatts
of energy from recycling the two remaining process solvents.

Enzymes to Reduce Energy Use and Increase Recycling of
   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 ben-
efits 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, cor-
rugated 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 vir-
gin wood pulp each year.
   Buzyme® products make it possible to recycle more paper, produce  paper more effi-
ciently, and manufacture higher quality paper.  Enzymes produce several  benefits: enzyme
biotechnology comes from renewable resources, is safe to use, and is itself completely recy-
clable. 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 tech-
nology has been studied in  laboratories for some years, Buckman has recently found the
keys to make it  successful on a full-scale industrial basis.
Squibb Company
International,  Inc.

Cytec Industries
Cytec Industries
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 eco-
nomic aspects of products under development. Cytec  chemists and engineers use the
CIMS web-based  process management software from the earliest stages of product devel-
opment 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 employ-
ees about earlier NPD processes. Cytec developed the SH&E questions after consultation
with the American Institute of Chemical Engineers' Center for Sustainable Technology
   CIMS puts in place common best-practice processes and tools  that help drive com-
mercialization  by designing safe, energy-efficient,  and environmentally  sound products
and processes. A critical component of CIMS is the Stage-Gate® process, which drives sus-
tainable development. The Stage-Gate® process incorporates SH&E questions into the first
stages of the new product development process,  allowing researchers  to evaluate the sus-
tainability of a product early in the development process. Additional tools built into CIMS
include  Sustainable Futures models  developed  by the  U.S.  EPA and  Cytec's Solvent
Selection Guide that includes hazard information on  120 common solvents. Cytec incor-
porated the U.S. 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

Revolutionizing Energy-Curing Resins for Food
Packaging Applications
   Solvent-free, energy-curing technologies have recently emerged as mainstream  tech-
nologies  in printing  human  food  packages. These technologies  are  energy-efficient
processes that use  accelerated electrons or UV photons to polymerize acrylate resins into a
branched network of large polymers. In contrast to solvent- or water-based technologies,
these solvent-free technologies do not require prolonged energy-intensive heating and dry-
ing cycles or expensive solvent abatement systems.  Overall, radiation-curing systems save
an estimated 85 percent of the energy required for traditional systems. In addition, these
technologies can also improve production speed and print quality.
   Following the principles of green chemistry and  sustainability, Cytec Industries Inc. has
developed a new range of low-extractable, low-odor (LEO) acrylate resins for use in ener-
gy-curing packaging inks and  overprint varnishes. Renewable resources such as  tall  oil
derivatives and glycerol account for 15 percent of the starting materials in the LEO prod-
uct line. The  LEO resins are characterized  by enhanced size and complexity, lower
migration from the packaging matrix, and frugal synthetic processes  using nontoxic and
preapproved building blocks. When formulated in inks, varnishes, or adhesives, these new
acrylate resins are  able to meet the most stringent regulatory safety requirements. In addi-
tion, Cytec has also developed testing protocols streamlined for the study of migration of

acrylates at the part-per-billion level to confirm minimal potential human exposure. Cytec
launched the LEO project commercially in 2006. During that year, LEO resins eliminat-
ed 20 tons of waste, and Cytec anticipates even greater savings in the  future.

Optifilm Enhancer 400 — A Nonvolatile Coalescent for
Formulating High-Performance, Reduced-VOC
Architectural Coatings
   Attainment of mandated ambient ozone standards continues to present great difficul-
ties  in  urban  areas  of the United  States,  where both nitrogen  oxides  (NOx)  and
anthropogenic volatile organic compounds (VOCs) are present at high levels in ground-
level air pollution. State and local regulatory agencies have identified paints and coatings
and, more specifically, architectural coatings as significant sources of VOCs. Consequently,
these agencies have developed regulations limiting the amount of VOCs in architectural
coating formulations. Currently,  the strictest  limits exist in California's  South Coast Air
Quality Management District.
   Traditional waterborne latex architectural coatings for interior and  exterior applications
require additives referred to as coalescents  or coalescing aids. These additives allow the latex
particles in the coating resin to form a contiguous film after application and to provide the
protective properties  and appearance required of the coating. In the past, the typical  coa-
lescents have been VOCs, which have been implicated as contributors to  the formation of
ground-level ozone.
   In response to the need to  reduce VOCs in architectural coatings, Eastman Chemical
Company has developed Optifilm Enhancer 400, a nonvolatile alternative to traditional
coalescents. Optifilm  Enhancer 400 allows paint manufacturers more  flexibility to achieve
the performance  they require;  it also reduces or eliminates the contribution of the coales-
cent to ozone formation. When tested neat by ASTM D2369,  Optifilm  Enhancer 400 is
99-3 percent nonvolatile; it has excellent efficiency to coalesce latex paints while main-
taining a good balance of performance properties. Optifilm Enhancer 400  delivers  excellent
film integrity, touch-up properties, and scrub resistance, even in paints formulated to  very
low VOC contents. Paints using Optifilm 400 have also demonstrated good exterior dura-
bility after 3 years of exposure. Optifilm  Enhancer 400 has been in use  in commercially
available architectural coatings since 2004.

A Practical,  Green Chemical Approach for
Manufacturing an Investigational New Drug
Candidate at Eli Lilly and Company
   This nomination describes  an  innovative, environmentally friendly route for the com-
mercial  production of an active pharmaceutical ingredient (API) that  is an investigational
new drug candidate currently undergoing clinical trials. The improved route delivers the API
in exceptionally high  purity (over 99-9 percent), a significant accomplishment considering
the potential for positional isomers for all  five of its aromatic rings. The improved  synthesis
is based on a novel SNAT methodology and a regioselective cycloaddition.
    Eli Lilly and Company uses a metric  called "e-factor" internally that  is similar, but
not identical to, Sheldon's E factor. Lilly's e-factor is the total mass of all  raw materials,
including water, used to produce  each kilogram of API beginning from routinely avail-
able commercial starting materials. Despite the structural complexity  of Eli Lilly's new
Eastman Chemical
Eli Lilly and

Emerson & Cuming
Chemicals,  LLC
API, the new route has a net e-factor of 146 kilograms per kilogram API, an 84-percent
reduction relative to the original process R&D route. Eli Lilly demonstrated the selected
commercial route for the API on a pilot-plant scale during 2006 in Indianapolis, IN.
Previously, the company had also developed two other synthetic routes at pilot-plant
scale at their 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 testimonial to the importance of
incorporating the 12 green chemistry principles into the design and definition of syn-
thetic processes. Peak production volumes from tens to hundreds of metric tons are
typical for APIs used for the same indications as Eli Lilly's investigational API. An e-fac-
tor improvement of 778 kilograms per kilogram of API in the new synthesis at peak
production would provide savings in all materials of 17—170 million pounds per year. In
2006, Eli Lilly filed a patent application for its selected commercial route.

Tin- and Copper-Compatible  Conductive Adhesive for
Lead-Free Electronic Circuit Assembly
   Tin—lead eutectic  solder is currently the most common product used to attach elec-
tronic components on circuit boards. Lead, however, is a known toxin. Because lead can
leach into  the  environment,  the European  Commission in its Waste  Electrical and
Electronic Equipment Directive enacted legislation in July 2006 mandating recycling of
consumer electronics  containing lead. This has prompted electronic circuit assemblers to
seek an  alternative attachment product. Conductive adhesives have  also been  used for
years, but their use has been limited to attaching palladium—silver-, silver-, and  gold-ter-
minated components on both ceramic hybrid  boards  and flexible polyester circuits.
Previous conductive adhesives were not stable  on low-cost tin- and tin—lead-terminated
   Emerson & Cuming's novel, patented chemistry allows it to achieve stable contact resis-
tance and stable adhesion under damp-heat and high-temperature aging conditions with
tin, tin—lead, and copper finishes. Compatibility with these finishes was not possible in the
past. This compatibility was achieved by preventing galvanic corrosion on these less expen-
sive, non-noble metal finishes.  The  incorporation  of  a corrosion  inhibitor and  a
low-melting alloy into the adhesive formulation prevents oxidation on  these finishes under
extreme environmental conditions  and leads to  stable performance over  time. About
40  major  electronic  circuit assembly companies currently purchase these Emerson &
Cuming adhesives. These customers are from very demanding industry sectors including
the automotive, medical, military, consumer electronics, and telecommunications sectors.
Over the last  3 years, these adhesives have effectively eliminated the use of 12 metric tons
of tin—lead eutectic solder. By 2010, this conductive adhesive technology will be replacing
about 40 metric tons  of solder per year.

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 hydropho-
bicity 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 associat-
ed 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 bil-
lion 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 ener-
gy efficiency at the mine site.

Nitamin Steady Delivery® Fertilizers for Improved
Nitrogen Efficiency in  Crops
   Worldwide, farmers apply approximately 82 million metric tons of nitrogen fertilizer,
primarily urea, to cropland annually. Plants are often unable to take up all of the nitrogen
released into the  soil from urea hydrolysis and salt-based fertilizers such as ammonium
nitrate, so the excess nitrogen leaches through the soil and contaminates nearby waterways.
Agricultural nitrogen is a major contributor to the increasing nitrate levels in many water-
ways around the world. These  excess nitrates create hypoxic areas in which the levels of
dissolved oxygen are  too low to support life.
   Nitamin® fertilizers provide an economic solution to this problem by slowing the rate
at which nitrogen becomes  available to the plant. By reacting urea with ammonia and
formaldehyde under specific conditions to  form a  blend of small urea-formaldehyde poly-
mers and cyclic compounds, Georgia-Pacific can control the rate at which the nitrogen is
released to plants. The primary Nitamin®  fertilizer product releases nitrogen for approxi-
mately 90  days, corresponding well  to the requirements of many crops. This controlled
delivery allows the plant to use more of the applied nitrogen, resulting in reduced applica-
tion rates  and reduced leaching. Nitamin® fertilizer reduces the amount  of nitrogen used
by 25 percent (onions and tomatoes) to 55 percent (cabbage). In other studies with pota-
toes, onions, and tomatoes, Nitamin® fertilizer increased crop yields by  7—54 percent.
Based on U.S. figures alone,  even a 5 percent reduction in the amount of nitrogen applied
to crops could eliminate the application of 810 million pounds of nitrogen annually. This
improved  efficiency of nitrogen use coupled with affordability is the highlight of this tech-
nology. Georgia-Pacific first commercialized its technology in January 2004. During 2005,
universities and growers ran over 80 trials  with different crops  to verify the marketability
of Nitamin® fertilizer. During  spring 2006, Georgia-Pacific will commercialize a liquid
Nitamin® fertilizer for use on vegetables.
Chemicals, LLC

Merck & Co., Inc.
Merck & Co., Inc.
Kilogram-Scale Purification  of Pharmaceutical
Candidates and Intermediates  Using Preparative
Supercritical Fluid Chromatography
   Preparative chromatography is increasingly used in the pharmaceutical industry to puri-
fy kilogram quantities  of developmental compounds  for  preclinical  evaluation.
Historically, the  industry has carried out  these separations by high-performance  liquid
chromatography (HPLC) using large amounts of petrochemical-derived organic solvents.
Merck has recently demonstrated the possibility of performing these separations  at the
kilogram scale using subcritical or  supercritical fluid chromatography (SFC), in  which
pressurized carbon  dioxide (CCh) replaces the hydrocarbon solvents often used in HPLC.
   Using custom-designed preparative SFC equipment prepared in collaboration with sev-
eral  vendors,  Merck  has  recently  carried  out  the  first kilogram-scale   SFC
enantioseparations  of pharmaceutical intermediates in the pharmaceutical industry. Merck
has reported its results in a recent publication (Welsh, C.J. et al., LC-GC, 2005, 16—29).
In one example,  enantioseparation of 2.5 kilograms of an intermediate was projected to
require 36,000 liters of solvent by HPLC, but used only 900 liters by SFC. Although this
example is extreme, a 10-fold decrease in solvent consumption is typical. Equally impor-
tant, SFC also produces a corresponding decrease in solvent  evaporation,  leading  to
considerable savings in equipment, time, and energy. Further, preparative SFC is general-
ly more productive than HPLC, especially for chiral separations. The SFC advantage can
be extreme, as in the case where there was  no suitable HPLC purification  for a single
stereoisomer of a drug candidate intermediate, yet SFC (5 cm i.d.  column,  350 g/min,
830 L organic solvent) purified 1.7 kilograms easily in only 72 hours.  During 2005, Merck
demonstrated  preparative SFC using  a  15-ton  CC^  bulk  tank and  custom-built,
3-kilogram-per-minute CCh delivery system.
   Merck has  demonstrated that preparative SFC is not  only a more environmentally
friendly method  for purifying developmental drugs and intermediates, it is simply  better,
with greater productivity and cost-effectiveness, both of which are important considera-
tions for large-scale separations  to support pharmaceutical manufacturing.

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 reac-
tion 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 cat-
alytic hydrogenation of indole ene acids.

   The new synthesis is convergent and highly atom-efficient, involves minimal extrac-
tions, distillations, or aqueous washes, and makes minimal use of protecting groups. By
implementing its new manufacturing route, Merck reduced its overall aqueous and organ-
ic 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 posi-
tive impact of scientific innovation on reducing the environmental footprint of a chemical
process. It also embodies the  association between innovation in green chemistry and busi-
ness  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.

TmctionBack®: Alternative Green Adhesives for Textile
Composites in  Commercial Buildings
   Poor indoor air quality is an important environmental health risk associated with build-
ing interiors. Traditional modular carpet installation requires adhesives and sealants that
contain such volatile organic  compounds (VOCs) as  formaldehyde and 2-ethyl-l-hexanol.
Carpet installation may also require surface preparation including sanding and removal of
old adhesive, which degrades air quality further.
   Milliken's TractionBack® anti-skid, adhesive-free backing is a thin coating formulation
applied to the felt on the bottom of carpet tile. The formulation is an amorphous ethyl-
ene—propylene copolymer that is tackified with a hydrocarbon resin and tall-oil rosin, a
biobased component. The raw materials in the formulation have  almost no measurable
VOCs in the solid state. TractionBack® for modular carpet eliminates the need for onsite
adhesive applications and repairs traditionally required for new and replacement installa-
tions, thus eliminating related VOCs. Milliken estimates that TractionBack® eliminates the
use of 400 tons of sealants and adhesives as well as 16,000 five-gallon containers of adhe-
sive and sealant each year.
   TractionBack® eliminates  chemical pollutants such as adhesives, floor primers, sealants,
and other VOCs;  eliminates  biological pollutants such as mold and bacteria; and reduces
the particulate hazards of sanding and surface  preparation. Additional environmental ben-
efits  include  (1)   energy reduction during  production;  (2) waste reduction  during
installation; (3) waste reduction to landfill by extending product life because individual
tiles can be repositioned or replaced easily; (4) reduction of downtime for building spaces;
(5) incorporation  of biobased raw materials; and (6)  removal of polyvinyl chloride (PVC),
which  has environmental issues related to its production,  installation, and eventual dis-
posal. TractionBack® uses fewer resources in both manufacturing and installation, reducing
waste and eco-footprint. TractionBack® has been on the market since 2003- Milliken devel-
oped the current formulation for TractionBack® in 2005-

Commercialization ofNXTZ®:  An Ethanol-Free,
Low-VOC, High-Performance Silane for Silica  Tires
   Silica tires have experienced remarkable growth in the last decade because of their supe-
rior 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.
Milliken &
Materials Inc.

Materials  Inc.
   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, how-
ever, 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 (GARB) 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 mer-
captosilanes. NXT Z® silane contains both mercaptan and thiocarboxylate functionalities
linked by high-boiling diols in place of the ethanol-derived alkoxy groups used in tradi-
tional 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.

Novel Superspreading Siliconized Surfactants
   Silicone surfactants are a unique class of materials because of their high surface activity
and easy-to-tune properties.  The most common structures are poly(alkylene oxide)-substi-
tuted polydimethylsiloxanes, but  these surfactants suffer  from hydrolytic  instability in
alkaline or acidic environments.
   Momentive's novel  technology  combines the reduced surface tension  and low-use lev-
els  typical  of silicone-based  surfactants  with the  stability  in  acidic  and  alkaline
environments  that is more typical of hydrocarbon surfactants. Momentive's surfactants are
stable in aqueous solutions from pH 2 to pH 12 without decomposition. These surfactants
reduce the equilibrium surface  tension of aqueous solutions to 21.5 mN/m  at 0.1 weight
percent, exhibit low critical micelle concentrations, and provide superspreading properties.
   Momentive's pH-stable, siliconized surfactants provide benefits typically achieved only
with fluorinated surfactants. In  aqueous solutions, these materials approach the low surface
tensions required for many current fluorosurfactant applications, and the silicon-contain-
ing portions provide friction reduction similar to that of the perfluorinated backbones. The
acidic and basic stability of the new surfactants is similar to that of surfactants  based on
perfluorooctane  sulfonate (PFOS). Momentive's  materials can replace fluorosurfactants,
which have come under scrutiny for their environmental persistence and bioaccumulation.
   Silwet® Superspreader agricultural adjuvants represent another use of this technology.
By helping water spread over and penetrate low-energy surfaces, superspreading surfactants
help farmers conserve water while they control pests. Because they improve spray coverage,
superspreaders allow lower rates of pesticide use. Because this novel class of superspreading
adjuvants is pH-stable, the shelf life of pesticide formulations containing these surfactants
is longer, and  it is practical  to package them in smaller containers, making  their benefits
available to the entire pesticide marketplace. Momentive has filed several patent applica-
tions for its pH-stable siliconized surfactants.

3D  Trasar BioControl
   Microbes grow well in the warm, nutrient-rich waters of cooling systems. Unchecked,
microbes coat the heat exchanger surfaces, impeding heat transfer and increasing energy
costs. Biocides are added to control microbial activity. Although 99 percent of the micro-
bial population resides on inaccessible surfaces in a cooling system, the industry could only
monitor floating  microbes. The result was either excessive biocide dosing (to preserve a
margin for error)  with subsequent discharge of biocides into natural waterways or insuffi-
cient biocide dosing. Either case increased energy use and public health concerns.
   3D Trasar BioControl adds a fluorescent molecule, Resazurin, to the water in cooling
systems. Microbial enzymes react with Resazurin and change its fluorescence: BioReporter
(Resazurin) + microbial respiratory enzymes =  BioProduct (Resorufm). Continuous  mon-
itoring  of the fluorescence  of both  Resazurin and  Resorufm allows  instantaneous
measurement of the total microbial activity in the system. Oxidizing biocide is added to
the system only in response to increasing microbial activity. Oxidizing biocides also react
with Resorufm and Resazurin, but do so at a much slower rate than do microbial enzymes.
Fluorescent detection of the degradation of Resorufm by the oxidizing biocide is used to
determine the precise endpoint for biocide addition.
   With 3D Trasar  BioControl, biomonitoring and control are continuous and compre-
hensive. Biocide  is  applied only when microbial activity is detected and  before the
population enters the log growth  phase. As a  result, oxidizing biocide use is reduced by
30—90 percent. Even a 30-percent reduction in oxidizing biocide worldwide could save
16 million pounds of biocide. 3D Trasar BioControl allows the most efficient use of bio-
cide, ensures microbial control, reduces the formation of absorbable organic halide (AOX)
from halogen-based oxidizing biocides, and reduces toxic discharge. During 2006, Nalco
deployed over 1,400 new 3D BioControl units for a total of 3,000.

A New Corrosion Inhibitor Reduces the Environmental
Impact of Industrially Treated Water
   Industrial water treatment systems suffer from the dual challenges of mineral scale foul-
ing 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  treat-
ments 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 implemen-
tation 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 cool-
ing 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  tradi-
tional 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  phos-
Nalco Company
Nalco Company

The NutraSweet
Dr. Robert L.
Augustine, Center
for Applied
Catalysis, Seton
Hall University

Osmose, Inc.
PPG Industries, Inc.
phate levels compared with systems that use degradable polyphosphate. The cost and per-
formance 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.

Bromine-Free,  TEMPO-Based Catalyst System for the
Oxidation of Alcohols
   NOTE: This project is the result of a partnership between Dr. Robert L. Augustine of
the Center for Applied Catalysis at Seton Hall University and The NutraSweet Corporation.
The project was judged in both the greener synthetic pathways (Focus Area 1) and academ-
ic categories. The abstract appears in the academic section on page 9-

MicroPro™ Technology in Wood Preservation
   For over 75  years, water-borne preservatives have relied on solubilized ingredients to
penetrate the wood  being treated. Currently, approximately 85 percent of the pressure-
treated wood in the United States is treated with amine—copper preservatives. The two
most commonly used  amine—copper preservatives require a  solvent, monoethanolamine
(MEA), to solubilize the copper component. MEA is a corrosive compound and a known
kidney and liver toxin; it poses potential health and environmental hazards. It also facili-
tates the growth of mold on treated wood, reducing commercial acceptability.
   Osmose, Inc. of Buffalo, NY developed MicroPro™, which uses micronized copper to
penetrate wood, eliminating the use of any solvent. The copper particles in MicroPro™
are between 250 and 500  nm, allowing the preservative to penetrate the wood's cell struc-
ture uniformly.  The  particle size is small enough that the copper can be forced into the
cellular structure areas of wood by pressure treatment, but large enough that it cannot read-
ily move back out under normal pressure conditions. MicroPro™ has the potential to
eliminate the use of 200 million pounds of MEA annually, equal to about half of the cur-
rent  MEA production. MicroPro™-treated wood leaches substantially less copper in
service than does wood treated with current  amine—copper systems. This reduces the envi-
ronmental impact of copper from structures in aquatic and terrestrial environments  by
approximately 75 percent compared with the current systems.
   MicroPro™ can  be shipped at almost four-fold greater concentration than other cur-
rent preservatives. The higher concentration of ingredients in MicroPro™ reduces the fuel
energy required  to deliver preservative to wood-treating plants by almost 75 percent, which
reduces  costs and overall environmental impact. In 2005, the U.S.  EPA registered Smart
Sense™ MicroPro™ as a pesticide.  By November 2006, this product was being used by
18 wood-treatment plants in 9 states.

The Use ofChitosan in Paint Detackification
   Automatic spray painting of automobiles, appliances, and other large articles is done in
water-washed paint spray booths. The traditional, wet-paint spraying operations of automo-
tive original equipment manufacturers (OEMs) transfer only 50—80 percent of the paint onto
the vehicle; the remaining 20—50 percent is deposited in an air stream that is later purified in
a circulating water curtain. Paint denaturants, also called "detackifiers", are added to the water
curtain circulating in  down-draft, water-washed, paint spray booths to render the oversprayed
paint nonsticky. Paint detackifiers denature, coagulate, and flocculate the oversprayed paint
in the water curtain, allowing it to settle out as sludge and be separated  from  the water.
During 2005, the automotive industry used approximately 31 million pounds of detackifiers.

   The current melamine—formaldehyde-based detackifiers contain small amounts of resid-
ual free formaldehyde, a known carcinogen. Alternative acrylic acid based paint detackifiers
are derived from ethylene and propylene, which are produced during petroleum cracking
and,  therefore, require nonrenewable feedstocks and are subject to fluctuations in petroleum
   BC4200NP is a liquid,  chitosan-based, paint denaturant technology that provides an
alternative to both traditional melamine—formaldehyde and acrylic acid based denaturants.
Chitosan is poly(glucosamine), a polysaccharide structurally similar to cellulose. It is made by
deacetylating chitin from crab, lobster, and shrimp shells that are a waste product of food pro-
duction. Because chitosan is less acidic than traditional products, it requires 87 percent less
sodium hydroxide for pH control. It retards the growth of anaerobic organisms, so the cir-
culating water requires less biocide. It also produces paint sludges that are more amenable to
biodegradation than are traditional sludges. At optimal  chitosan concentrations, BC4200NP
is less costly or at least cost-neutral compared with traditional technologies. The Mitsubishi
Motors facility in Normal, IL has been using it for over a year and a half with excellent results.

Tide Coldwater®: Energy Conservation through
Residential Laundering Innovation and
   Procter  & Gamble has  recently commercialized  a patented, breakthrough chemical
innovation in environmentally friendly cleaning technology to provide superior cleaning
and significant energy savings in low-temperature (60  °F) wash water. Over 7 million U.S.
households have used Tide Coldwater® since its introduction in North America in January
   Tide Coldwater® uses surfactant systems designed  to be more hydrophobic than other
detergents. The liquid detergent  formula uses an optimized combination of alcohol ether
sulfate, linear alkyl  benzene sulfonate, and ethoxylated zwitterionic and alkyl amine sur-
factants.  In combination  with  a builder/chelant  to sequester metals,  soil suspension
systems, enzymes (protease  and amylase), and brightener systems, this proprietary surfac-
tant  system delivers superior cleaning performance in cold water. The powder detergent
formula is based on high-solubility alkyl sulfate, a proprietary branched surfactant. It also
contains sodium nonanoyl oxybenzene sulfonate, a proprietary bleach activator, along with
other additives in common  with  the liquid version.
   In blind consumer tests, Tide Coldwater® provides superior cleaning in cold water rel-
ative to detergents formulated for warm and hot water. Without sacrificing performance in
stain removal or whitening, consumers can save up  to $63 per year in home energy costs,
reducing greenhouse gas emissions from fossil-fueled power plants. Using a peer-reviewed
model  for residential energy use, Procter & Gamble  estimates that Tide Coldwater® will
reduce the  fraction of residential energy used to heat  water by up to 26—36 percent, with
an associated reduction in  carbon dioxide (CC^) emissions of up to 1,259 pounds per
household per year. The potential benefits of this innovation are significant: if everyone in
the United States switched to cold water for laundry, the potential energy savings would be
70—90  billion kilowatt-hours per year, representing  up to  3 percent of the nation's energy
consumption. These savings are the equivalent of 26—34 million tons of CCh per year, rep-
resenting over 8 percent of the CC^ reduction target for the United States set in the Kyoto
The Procter &
Gamble Company

Rhein Chemie
Severn Trent
Optimizing Renewable Resources in  the Production of
Polyurethane Systems and Plastics
   Biobased products can help protect and preserve the environment. In addition, they can
create a safer, healthier workplace, help cut air and water pollution, reduce the generation
of hazardous waste, decrease the use of potentially toxic substances, and improve recycling
opportunities.  Soy-based  polyols  can  substitute for  petroleum-based polyols  in
polyurethanes, but the available acid groups in soy polyols can cause hydrolytic degrada-
tion and variable reactivity, leading to polyurethanes with inferior properties.
   Rhein Chemie Corporation  created soy-based polyol  additives for the production of
low-density, insulated spray foams for the industrial, commercial, and residential insulation
markets. These particular soy-based systems use water as a blowing agent to replace chlo-
rofluorocarbons (CFCs)  and use flame retardants  to reduce smoke effects as required for
class 1 foams (the highest flame spread and smoke standard in the insulation industry). The
combination of these Rhein Chemie technologies enables their insulation system to reduce
depletion of the ozone layer effectively.
   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 P200 and Addocat 102) to form a "green" polymer. Stabaxol, a
carbodiimide, scavenges  the acid groups on the biopolyols and improves both the reactiv-
ity and the hydrolytic stability. Stabaxol also minimizes the deactivation of the catalysts by
reacting out the acids that lead to variable reactivity.
   Rhein Chemie pioneered the additive technology for soy-based polyol systems and toll
manufactured the first commercial polyurethane  systems for spray foams in the United
States for industrial, commercial, and residential insulation. Rhein Chemie's soy-based
polyol  additives  are effective, environmentally friendly alternatives to petroleum-based
products and have been in commercial use in the United States for the past 5 years.

Iron  Oxide for Arsenic Removal from Drinking Water
   The U.S. EPA's best  available technologies for removing arsenic from drinking water
include aluminum adsorption, ion exchange, reverse osmosis, and coagulation filtration.
Adsorption technology is among the simplest approaches for removing metals, such as
arsenic, from drinking water, but conventional adsorbents such as activated carbon or acti-
vated alumina have a limited capacity for arsenic.
   Severn Trent Services worked with LANXESS Corporation to develop the proprietary
Bayoxide® E33 media for efficient, effective adsorption of arsenic. Bayoxide® E33 consists
of iron oxide hydroxide in the a-FeOOH form; it  has a very high specific surface area and
a high adsorption capacity for arsenic.  Bayoxide® E33 is mechanically robust, is stable with
a uniform grain size, has a low leaching potential, has good water distribution across the
media  minimizing pressure buildup, and is immediately effective in a start-stop process.
Bayoxide® E33 can remove arsenic from groundwater to well below 4 micrograms per liter.
In an adsorption system, SORB 33®, the Bayoxide® E33 media life expectancy depends on
site-specific water quality and operating levels. The exhausted media is nonhazardous, pass-
ing the U.S. EPA's Toxicity  Characteristic Leaching  Procedure  (TCLP)  threshold
   Bayoxide® E33 media achieves a three-fold reduction in waste. First, Bayoxide® E33
media is manufactured from iron sulfate, a waste product of the steel industry. Second, ser-
vice wash water from routine backwashing of the Bayoxide® E33  media can be reclaimed

and returned to the plant inlet. Third, exhausted Bayoxide® E33 serves as a source of iron
oxide for steel  manufacturing processes, namely direct reduction iron (DRI) process and
sintering plants, eliminating the disposal of Bayoxide® E33 into landfills.
   The U.S. market for adsorptive arsenic removal media is estimated at over 6,000 met-
ric tons  per year, excluding residential applications. As of November 2006, Severn Trent
Services had sold Bayoxide® E33 to municipalities in 35 States in the United States.

Dequest PB — Carboxymethyl Inulin: A Versatile Scale
Inhibitor from the Roots of Chicory
   Fouling of surfaces by mineral salts is a major problem in water-bearing systems because
scaling reduces the efficiency of heat transfer and interferes with the operational perform-
ance of industrial processes.  Previous  scale inhibitors were  either products with  poor
biodegradability and moderate toxicity  but good  performance (e.g.,  polyacrylates) or
biodegradable products with limited applicability (e.g., polyaspartates).
   Carboxymethyl inulin (CMI) is based on inulin,  an oligosaccharide harvested from the
roots  of chicory. Developed by Solutia  and  Cosun (The Netherlands), CMI provides a
cost-effective, safe, and versatile alternative to  traditional antiscalants. It combines  good
biodegradability with very low toxicity. It also  has excellent scale inhibition performance
for various types of scales, particularly sulfate scales. CMI can be used in many applica-
tions, but is especially well-suited for  use  in environmentally  sensitive areas, such as
offshore oil production. For example, CMI is used as a barium sulfate scale inhibitor in the
Norwegian offshore oil drilling sector of the North Sea. CMI also  is  a suitable replacement
for poorly biodegradable scale inhibitors  in water and process water treatment, as well as
in pulp and paper and sugar refining applications. In addition, the attributes of CMI make
it a candidate  as a laundry aid to prevent redeposition  and  as a builder component in
household and industrial automatic dishwasher and laundry formulations. A CMI-based,
phosphate-free automatic dishwashing  tablet was launched on the European market in
   In 2006, Solutia generated the first commercial sales of CMI in the United States under
the trade name Dequest PB. At full market penetration, Dequest PB has the potential to
replace 125 million pounds of polyacrylates currently used in U.S. and Canadian house-
hold and institutional laundry detergent formulations to prevent redeposition. Solutia and
Cosun are currently developing a wider range of inulin-based products with different func-
tionalities  and  performance characteristics.

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
Solutia Inc.
U.S. Army, U.S.
Army Edgewood
Chemical Biological

U.S. Department of
Energy, Argonne
hazardous chemicals before they can contaminate wider areas. Because the enzymes are cat-
alytic,  only small  quantities  are  required, greatly reducing transportation and storage
requirements (by as much as 25- to 50-fold). The enzymes are also nontoxic, noncorrosive,
and environmentally safe.  Initially intended to  decontaminate equipment, facilities, and
large areas, these enzymes  could potentially be used in shower systems to decontaminate
personnel and casualties.
   The specific bacterial  enzymes are organophosphorus hydrolase  (originally called
parathion hydrolase)  and organophosphorus acid  anhydrolase  (an  X-Pro dipeptidase,
EC 3.4.13-9). These two enzymes are effective against V- and G-type nerve agents, respec-
tively.  Genencor  International,  the  premier manufacturer of industrial  and  specialty
enzymes in the United States, is using its state-of-the-art fermentation manufacturing tech-
nology to produce  the enzymes.  Genencor has begun commercial production and now has
industrial-scale quantities  of the enzymes  available under the  trade name DEFENZ™.
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, Ail-Clear™, in August 2005-

Resin Wafer Technology
   The U.S.  Department  of Energy  has identified separations technology as one of the
most significant cost barriers in process-intensive fields such as fossil energy consumption,
water management, and  CC^ sequestration. Electrodeionization (EDI) is  an electrical
process that separates low-concentration, charged species  from process  streams. In conven-
tional EDI, loose ion exchange resins are used to produce ultrapure water.
   Resin wafer technology replaces loose  resins and enables the extension  of EDI well
beyond its conventional applications.  Resin wafers are fabricated from  commercially avail-
able ion exchange resins and retain the chemical  activity of their components. They can be
molded into desired shapes using thermoplastics to provide structural integrity. The wafers
can also incorporate such materials as  biocatalysts,  immobilization resins, electron con-
ductivity nanoparticles, and fillers to control porosity.
   Resin wafers offer several advantages: (1) controlled porosity, which makes stream flow
more  efficient;  (2) enhanced  ion conductivity,  which reduces power consumption; and
(3) reduced leakage,  which both  increases product recovery and cuts waste stream loss.
Resin wafers also provide new functionalities not available with conventional EDI. These
include direct immobilization of biocatalysts, which allows integrated bioconversion and
separations; modification of wafer composition and format, which increases ion selectivity
and direct pH control; and in situ catalysis. Resin wafers allow new processes in biobased
chemical production, industrial water management, chemical production and purification,
and, potentially, hydrogen production and CC^ sequestration.
   Resin wafer technology also offers significant environmental benefits. It reduces the cost
of producing biobased chemicals,  making them  more competitive with petrochemicals. It
decreases fresh water use and the release of wastewater. It reduces energy and chemical use
during the production of organic  acids, esters, and other chemicals. Finally, it can poten-
tially enhance CCh sequestration from flue  gases and hydrogen production from water.
Resin wafer technology has been awarded 7 patents over  the past 5 years.

Solventless Process for Making Tackifiers and Adhesives
   Worldwide, over 2.5 million tons of pressure-sensitive adhesives (PSAs) are manufac-
tured annually for use in many industries, including pulp and paper, electronics, wireless
telecommunications, medical devices, cosmetic and personal hygiene, and others. PSAs are
made by combining tackifier dispersions with latex dispersions. Tackifier dispersions are
made either from low-temperature resins that melt at less than 100 °C or from resins that
melt at higher temperatures. High-temperature resins are dissolved in organic solvents then
heated to evaporate and recover excess solvent, resulting in some solvent emissions. Over
time, any residual solvents in the adhesive also evaporate into the environment. Low-tem-
perature resins are heated, melted, slowly added to hot water, and continuously stirred for
over 4 hours to form an emulsion containing up to 50 weight-percent water. The emulsion
is then transported to the site at which the adhesive is made. After the adhesive has been
coated onto a substrate, radiant heating removes the excess water.
   Argonne National Laboratory has developed a new process to make tackifier dispersions
for PSAs. The Argonne process pulverizes the resin to an average particle size of less than
5 micrometers and then directly forms the dispersion in water, in just a few minutes, with-
out dissolving the resin in solvents, melting it, or using excess water. The process does not
require solvents or heat to process either high- or low-temperature resins. It also eliminates
the need for transporting excess water. Argonne's process is cost-effective and energy-effi-
cient. It  reduces the cost of manufacturing water-based tackifier dispersions by over
35 percent  and uses less than 25 percent of the energy required by conventional processes.
As a result, it reduces greenhouse gas emissions.
   Argonne has  filed a patent application for this technology. Dyna-Tech Adhesives, Inc.
has manufactured 500 pounds of resin with an average size of 2.5 micrometers for testing.

Green Primaries: Environmentally Friendly, Sensitive
   Initiating devices use primary explosives (i.e., primaries) to detonate main charge explo-
sives. 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-TV2-
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,  manu-
facturing, 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, ini-
tiating sensitivities and explosive performance;  elimination of toxic waste; and release of
U.S. Department of
Energy, Argonne
U.S. Department of
Energy, Los Alamos

U.S. Department of
Energy, Los Alamos
only innocuous byproducts upon detonation. The benign detonation byproducts prevent
chronic lead exposure to civilians and military personnel. Green primaries are safely pre-
pared in, and desensitized by, water or ethanol, so toxic fumes and solvents are eliminated
during preparation. Green primaries eliminate the potential for accidental explosions, sav-
ing 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.

Ultrapure  Carbon  and Carbon—Nitride Nanomateriah
Derived from  Simple Pyrolyses of Nearly Chock-Full
Nitrogen Compounds
   Currently, carbon-based nanomaterials are manufactured primarily from residual oils or
hydrocarbon precursors at extremely high temperatures and  applied pressures. The toxic
fumes and hazardous waste generated by these high-temperature, high-pressure reactions
are detrimental to the environment and cause personal health risks.
   Dr. Huynh has developed solventless pyrolytic conditions to prepare ultrapure carbon
nanoparticles and diamond-hard carbon—nitride nano-architectures from novel high-nitro-
gen  compounds,  the so-called nearly chock-full  nitrogen  compounds. This  requires
simultaneous manipulation of melting points, heating patterns, and decomposition tem-
peratures. Dr.  Huynh's  solid-state pyrolyses  can  be tuned  controllably to produce
nanomaterials of the size, shape, morphology, density, dimension, and  nitrogen content
required for a wide variety of applications. Some of these applications include next-gener-
ation computer chips, kinetic-energy penetrators with enhanced lethality, better insulation
materials, tougher  and harder cutting tools, high-sensitivity sensors,  automobiles with
greater fuel efficiency, aerospace components with enhanced  performance characteristics,
and longer-lasting medical implants. Unlike hydrocarbon feedstocks that contain primar-
ily C—H and C=C  bonds, these high-nitrogen compounds contain  multiple C=N bonds
and N=N linkages  that make their thermal  decompositions downhill processes owing to
the extrusion of nitrogen  gas as the only byproduct. Multiple N=N linkages make these
high-nitrogen compounds nonvolatile and viscous, so they are easy to handle.
   With Dr. Huynh's innovation, ultrapure carbon and carbon—nitride nanomaterials can
be manufactured quantitatively with  absolutely no  hydrogen-incorporating byproducts.
The manufacture of these carbon-based nanomaterials from high-nitrogen compounds is
advantageous and cost-effective. This process abolishes specialized facilities and equipment,
eliminates personal  exposure  to high-temperature  and applied-pressure reaction condi-
tions, eradicates lengthy preparation and complicated purification, and drastically reduces
production costs associated with liability insurance  and  the  removal of toxic fumes and
hazardous waste. Essentially, Dr. Huynh has creatively applied high-nitrogen chemistry to
solve environmental and  nanotechnological problems. One patent  has  been granted for
this technology; another is pending.

Award winners are indicated with *.
3M Office Supplies Division Laboratory
Development of Water-Based Materials for Post-it® Super Sticky Notes	41
ABB Lummus Global Inc.; Albemarle Catalysts
Company BV
AlkyClean®: The Safe Alkylation Technology for Producing Clean Gasoline	41
Advanced BioCatalytics Corporation
Changing the Nature of Surfactants: Low-Molecular-Weight Proteins as
Surfactant Synergists	21
Uncoupling Biochemical Processes for Enhanced Biological Efficiency	21
Albemarle Catalysts Company BV; ABB Lummus
Global Inc.
AlkyClean®: The Safe Alkylation Technology for Producing Clean Gasoline	41
Amerikal  Products Corporation
Genesis® BRIGL Wash	22
APTech Group, Inc.
A Greener Chemical Treatment for Cooling Tower Water	22
Arch Treatment Technologies, Inc.
Wolman® AG Metal-Free Wood Preservative	42
Arkema Inc.
Green Chemistry in the Manufacture ofThioglycolic Acid 	42
Ashland Water Technologies
Reducing the Environmental, Health,  and Safety Impact of Cooling Water
Treatment Programs  	43
Aspen Technology, Inc.
Correlating and Predicting Drug Molecule Solubility with a Nonrandom,
Two-Liquid Segment Activity Coefficient Model 	44
Augsburg College, Arlin E.  Gyberg
A New, Heterogeneous, Fixed-Bed Catalyst for Continuous-Flow Biodiesel
Production from Waste Fats and Oils	10
Augustine,  Robert L., Center for Applied Catalysis, Seton Hall
University;  The NutraSweet Corporation
Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols 	9
Barricade International, Inc.
Environmentally and Toxicologically Safe Firefighting Gel	23
BASF  Corporation
A Non-HAP (Hazardous Air Pollutant) Coating for Extruded Aluminum 	44
Battelle Memorial Institute
Development and Commercialization  ofBiobased Resins and Toners	45
Beaulieu Group, LLC
Nexterra™ Carpet: Modified PET Carpet Backing 	45
Benchmark Performance  Group, Inc.
GreensKeeper® Polymer Slurries for Oil and Gas Well Stimulation 	46

     Bristol-Myers Squibb Company
     Irbesartan (Avapro®) Greenness Project	47
     Buckman Laboratories International, Inc.
     Enzymes to Reduce Energy Use and Increase Recycling of Paper	47
     *Cargill, Incorporated
     BiOH™Polyols	47
     Carnegie Mellon University, Department of Chemistry,
     Krzysztof Matyjaszewski
     Diminishing Copper Catalyst Content in Atom Transfer Radical
     Polymerization (ATRP) in the Presence of Environmentally Friendly
               •its 	12
    Carnegie Mellon University, Mellon College of Science,
    Richard D. McCullough
    Regioregular Polythiophenes as a Platform for Organic Photovoltaic Technology 	13
    Century Industrial Coatings Inc.
    Nulo™ Technology: HAP-Free, Low-VOC, Water-Based, Air-Dry Coatings 	24
    Changing World Technologies, Inc.
    Waste to Renewable Diesel	24
    Chiral Quest, Inc.
    Practical Asymmetric Catalytic Hydrogenation 	25
    Cholli, Ashok L., Center for Advanced Materials, University of
    Massachusetts Lowell
    High-Performance Macromolecular Antioxidants for Materials: A Green
    Chemistry Approach 	9
    Codexis, Inc.
    Greening Atorvastatin Manufacture: Replacing a Wasteful, Cryogenic
    Eorohydride Reduction with a Green-by-Design, More Economical,  Eiocatalytic Reduction
    Enabled by Directed Evolution	25
    Colorado School of Mines, Department of Chemistry
    and Geochemistry, Thomas Wildeman
    Passive  Treatment of Metal-Contaminated Water 	17
    "Columbia Forest Products;  Kaichang Li, Department of
    Wood Science and Engineering, Oregon State University;
    Hercules Incorporated
    Development and Commercial Application of Environmentally Friendly
    Adhesives for Wood Composites	5
    Corrosion-Resistance without Chromium: On-Demand Release of
    Environmentally Safe, Non-Chromium Corrosion Inhibitors from
    Electroactive Polymer Coatings 	26
    Cutting Edge Formulations, Inc.
    Nature's Avenger1^ Organic Herbicide: A Highly Effective, Nontoxic, Organic
    Alternative to Synthetic and Natural Herbicides 	26
    Cytec Industries Inc.
    Cytec Innovation Management System: Sustainable Development of
    New Products	48
    Revolutionizing Energy-Curing Resins for Food Packaging Applications	48

Dasgupta, Purnendu K., Department of Chemistry and
Biochemistry, University of Texas at Arlington
A Green Analyzer for Arsenic in Drinking Water 	10
Eastman Chemical Company
Optifilm Enhancer 400 — A Nonvolatile Coalescentfor Formulating
High-Performance, Reduced-VOCArchitectural Coatings	49
Ecology Coatings
Green Chemistry for Industrial Coatings	27
Eli Lilly and Company
A Practical, Green Chemical Approach for Manufacturing an Investigational
New Drug Candidate at Eli Lilly and Company	49
Emerson & Cuming
Tin- and Copper-Compatible Conductive Adhesive for Lead-Free Electronic
Circuit Assembly 	50
Environmentally Sensitive Solutions, Inc.
Liquid Seal and Nonhazardous Cleaner Eliminate Odor, Health, and
Maintenance Problems Stifling the Acceptance and Implementation of
Waterless Urinals	27
EverTech LLC
Everdex-Enhanced Alowood 	28
Exelus,  Inc.
ExSact — A "Green" Gasoline Technology  	28
ExSyM — The Next Generation of Styrene Monomer Technology 	29
Fungi Perfect!, LLC
Mycopesticides and Mycoattractants	30
Georgia-Pacific Chemicals, LLC
Georgia-Pacific Mining Reagents That Improve Recovery, Reduce Wastes, and
Conserve Water and Other Natural Resources	50
Nitamin® Steady Delivery® Fertilizers for Improved Nitrogen Efficiency
in Crops	51
GreenBlue (Green Blue Institute)
CleanGredients^M: Systems-Based Information Technology for Green Chemistry	30
Gyberg, Arlin E., Augsburg College
A New, Heterogeneous, Fixed-Bed Catalyst for Continuous-Flow Biodiesel
Production from Waste Fats and Oils	10
* Head waters Technology Innovation
Direct Synthesis of Hydrogen Peroxide by Selective Nanocatalyst Technology	6
"Hercules Incorporated; Columbia Forest Products;
Kaichang Li, Department of Wood Science and Engineering,
Oregon State University
Development and Commercial Application of Environmentally Friendly
Adhesives for Wood Composites	5
Hutchison,  James  E., Department of Chemistry and Materials
Science Institute,  University of Oregon
Greener Production of Functionalized Nanoparticles 	10

     IPAX Cleanogel, Inc.
     The Use of Green Unikleen in Oil Spill Clean-Up, Both on Land and in Water	31
     Jiang, Shaoyi, Department of Chemical  Engineering,
     University of Washington
     Development of Environmentally Benign Nonfouling Materials and
     Coatings for Marine Applications	//
     *Krische,  Michael J.,  Department of Chemistry and
     Biochemistry,  University of Texas at Austin
     Hydrogen-Mediated Carbon—Carbon Bond Formation	3
     The LATA  Group, Inc.
     New Green Technology for Eliminating Hydrogen Sulfide in Aqueous Systems,
     Especially Petroleum Industry Systems 	31
     *Li, Kaichang, Department of Wood Science and Engineering,
     Oregon State University; Columbia Forest Products;
     Hercules Incorporated
     Development and Commercial Application of Environmentally Friendly
     Adhesives for Wood Composites	5
     Maffia, Gennaro J., Department of Chemical Engineering,
     Widener University
     Application of Collagen Nanofibrils in Green Processing and Synthesis 	//
     Matyjaszewski,  Krzysztof, Department of Chemistry, Carnegie
     Mellon  University
     Diminishing Copper Catalyst Content in Atom Transfer Radical
     Polymerization (ATRP) in the Presence of Environmentally Friendly
               •its 	12
     McCullough, Richard D., Mellon College of Science,
     Carnegie Mellon University
     Regioregular Polythiophenes as a Platform for Organic Photovoltaic Technology 	13
     Merck & Co., Inc.
     Kilogram-Scale Purification of Pharmaceutical Candidates and Intermediates
     Using Preparative Supercritical Fluid Chromatography	52
     A New, Highly Efficient, Environmentally Responsible Synthesis of
     Laropiprant (MK-0524) 	52
     Metcalf, William W., Department of Microbiology, University
     of Illinois; Huimin Zhao, Department of Chemical and
     Biomolecular Engineering; Wilfred A. van der Donk,
     Department of Chemistry
     A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology
    for Industrial Biocatalysis	19
     Milliken & Company
     TractionBack®: Alternative Green Adhesives for Textile Composites in
     Commercial Buildings 	53
     Mississippi State University, College of Forest Resources,
     Tor P. Schultz and Darrel D.  Nicholas
     Enhancing the Efficacy of Totally Organic Wood Preservatives with Low-Cost,
     Benign Additives 	15

Momentive Performance Materials Inc.
Commercialization ofNXTZ®: An Ethanol-Free, Low-VOC,
High-Performance Silane for Silica Tires 	53
Novel Superspreading Siliconized Surfactants	54
MYCELX Technologies Corporation
Novel Device for Removing Mercury from Produced Water and Vapor Streams	32
Nalco Company
3D Trasar BioControl	55
A New Corrosion Inhibitor Reduces the Environmental Impact of Industrially
Treated Water	55
Nicholas, Darrel  D. and Tor P. Schultz, College of
Forest Resources, Mississippi State University
Enhancing the Efficacy of Totally Organic Wood Preservatives with Low-Cost,
Benign Additives 	15
The Nitrate Elimination Company, Inc.
Greener Chemistry for Nitrate Analysis: Enzymatic Reduction Method	33
Niwayama, Satomi, Department of Chemistry and
Biochemistry, Texas Tech University,
Highly Efficient and Practical Monohydrolysis of Symmetric Diesters	13
*NovaSterilis Inc.
Environmentally Benign Medical Sterilization Using Supercritical
Carbon Dioxide 	4
The NutraSweet Corporation; Robert L. Augustine, Center
for Applied Catalysis, Seton Hall University
Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols	56
"Oregon State University, Department of Wood  Science
and Engineering, Kaichang  Li; Columbia  Forest Products;
Hercules Incorporated
Development and Commercial Application of Environmentally Friendly
Adhesives for Wood Composites	5
Osmose, Inc.
MicroPro™ Technology in Wood Preservation	56
Pantheon Chemical
PreKote® Surface Pretreatment: Replacing Hexavalent Chromium with an
Environmentally Safe Solution 	33
Penn Specialty Chemicals, Inc.
2-Methyltetrahydrofuran: A Green and Cost-Effective Alternative to
Alkyl Ethers and Chlorinated Solvents 	34
The Pennsylvania State University, Department of
Chemistry, Xumu Zhang
Practical Asymmetric Catalytic Hydrogenation 	18
Pirrung, Michael C, Department of Chemistry, University of
California, Riverside
Environmentally Friendly Isonitrile-Based Syntheses 	14

    Polnox Corporation
    High-Performance Macromolecular Antioxidants for Materials: A Green
    Chemistry Approach 	34
    PPG Industries, Inc.
    The Use ofChitosan in Paint Detackification 	56
    The Procter & Gamble Company
    Tide Coldwater®: Energy Conservation through Residential Laundering
    Innovation and Commercialization	57
    Rhein Chemie Corporation
    Optimizing Renewable Resources in the Production of Polyurethane Systems
    and Plastics	58
    SarTec Corporation
    A New, Heterogeneous, Fixed-Bed Catalyst for Continuous-Flow Eiodiesel
    Production from Waste Fats and Oils	35
    Schultz, Tor P. and Darrel D. Nicholas, College of Forest
    Resources, Mississippi State University
    Enhancing the Efficacy of Totally Organic Wood Preservatives with Low-Cost,
    Benign Additives 	15
    Seton Hall University, Center for Applied Catalysis, Robert L.
    Augustine; The NutraSweet Corporation
    Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols 	9
    Severn Trent Services
    Iron Oxide for Arsenic Removal from Drinking Water	58
    Soloshonok, Vadim A. and Hisanori Ueki, Department of
    Chemistry and Biochemistry, University of Oklahoma
    Biomimetic Reductive Processes	15
    Solutia Inc.
    Dequest PB — Carboxymethyl Inulin: A Versatile Scale Inhibitor from the
    Roots of Chicory 	59
    Specialty Fertilizer Products
    Biodegradable, Water-Soluble, Anionic Polymers Prepared in an
    Environmentally Benign Process Enhance Nutrition Efficiency, Reduce
    Waste, and Reduce Runoff of Phosphorus 	36
    Steward Environmental Solutions, LLC
    Development and Commercial Application ofSAMMS™, a Novel Adsorbent
    for Reducing Mercury and Other Toxic Heavy Metals	36
    Stoller  Enterprises Inc.
    Alternative to Methyl Bromide to Overcome Nematode Damage to Crops and
    Concomitantly Enhance Yield, Crop Quality, and Abiotic and Biotic Tolerance 	37
    Subramaniam, Bala, Department of  Chemical and Petroleum
    Engineering, Center for Environmentally Beneficial
    Catalysis,  University of Kansas
    A Greener Hydroformylation Process	16
    Super Trap Inc.
    GEL-COR®: A New, Environmentally Compatible, Bullet-Trapping
    Medium for Small-Arms Firing Ranges 	38

Tao, Daniel, The Department of Mining Engineering,
University of Kentucky
Georgia-Pacific Mining Reagents that Improve Recovery, Reduce Wastes, and
Conserve Water and Other Natural Resources	16
Texas Tech University, Department of Chemistry and
Biochemistry, Satomi Niwayama
Highly Efficient and Practical Monohydrolysis of Symmetric Diesters	13
Torchem LLC
Manufactured Firelogs Based on Whole Timber	38
Ueki, Hisanori and Vadim A. Soloshonok,  Department of
Chemistry and Biochemistry, University of Oklahoma
Biomimetic Reductive Processes	15
University of California, Riverside, Department of
Chemistry, Michael C. Pirrung
Environmentally Friendly Isonitrile-Based Syntheses 	14
University of Cincinnati, Department of Chemical and
Materials Engineering, Wim J. van Ooij
Novel, One-step, Chromate-free Coatings Containing Anticorrosion
Pigments to Replace Chromate Pretreatment and Pigments 	17
University of Illinois, Department of Chemical and
Biomolecular Engineering, Huimin Zhao; Department
of Chemistry, Wilfred A. van der Donk; Department of
Microbiology, William W. Metcalf
A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology
for Industrial Bio'catalysis	19
University of Kansas, Department of Chemical and
Petroleum Engineering,  Center for Environmentally
Beneficial Catalysis, Bala Subramaniam
A Greener Hydroformylation Process	16
University of Kentucky, The Department of Mining
Engineering,  Daniel  Tao
Georgia-Pacific Mining Reagents that Improve Recovery, Reduce Wastes, and
Conserve Water and Other Natural Resources	16
University of Massachusetts Lowell, Center for
Advanced Materials, Ashok L. Cholli
High-Performance Macromolecular Antioxidants for Materials: A Green
Chemistry Approach 	9
University of Oklahoma, Department of Chemistry and
Biochemistry, Vadim A. Soloshonok and Hisanori Ueki
Biomimetic Reductive Processes	15
University of Oregon, Department of Chemistry and
Materials Science Institute, James E. Hutchison
Greener Production of Functionalized Nanoparticles 	10
University of Texas at Arlington, Department of
Chemistry and Biochemistry, Purnendu K. Dasgupta
A Green Analyzer for Arsenic in Drinking Water 	10

    "University of Texas at Austin, Department of
    Chemistry and Biochemistry, Michael J. Krische
    Hydrogen-Mediated Carbon—Carbon Bond Formation	3
    University of Washington, Department of Chemical
    Engineering, Shaoyi Jiang
    Development of Environmentally Benign Nonfouling Materials and
    Coatings for Marine Applications	//
    U.S. Army, U.S. Army Edgewood Chemical Biological
    Enzyme-Based Technology for Decontaminating Toxic Organophosphorus
    Compounds	59
    U.S. Department of Energy, Argonne National
    Resin Wafer Technology	60
    Solventless Process for Making Tackifiers and Adhesives	61
    U.S. Department of Energy, Los Alamos National
    Green Primaries: Environmentally Friendly, Sensitive Explosives	61
    Ultrapure Carbon and Carbon—Nitride Nanomaterials Derived from Simple
    Pyrolyses of Nearly Chock-Full Nitrogen Compounds	62
    van der Donk, Wilfred A., Department of Chemistry,
    University of Illinois; Huimin Zhao, Department of
    Chemical and Biomolecular Engineering; William W.
    Metcalf, Department of Microbiology
    A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology
    for Industrial Biocatalysis	19
    van Ooij, Wim J., Department of Chemical and Materials
    Engineering, University of Cincinnati
    Novel, One-step,  Chromate-jree Coatings Containing Anticorrosion
    Pigments to Replace Chromate Pretreatment and Pigments 	17
    Velocys  Inc.
    Olefins by High-Intensity Oxidation	39
    Widener University, Department of Chemical
    Engineering, Gennaro J. Maffia
    Application of Collagen Nanofibrils in Green Processing and Synthesis 	/ /
    Wildeman, Thomas, Department of Chemistry and
    Geochemistry, Colorado School of Mines
    Passive Treatment of Metal-Contaminated Water 	17
    Zhang, Xumu, Department of Chemistry, The Pennsylvania
    State University
    Practical Asymmetric Catalytic Hydrogenation 	18
    Zhao, Huimin, Department of Chemical and Biomolecular
    Engineering, University of Illinois; Wilfred A. van der Donk,
    Department of Chemistry; William W. Metcalf,  Department
    of Microbiology
    A Novel Phosphite Dehydrogenase Based NAD(P)H Regeneration Technology
    for Industrial Biocatalysis	19

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