The Presidential
Green Chemistry Challenge
Awards Program:
Summary of 2007 Award
Entries and Recipients
An electronic version of this document is available at:
http://www.epa.gov/greenchemistry
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Environmental Protection Prevention and October 2007
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The Presidential Green Chemistry
Challenge Awards Program:
Summary of 2007 Award Entries
and Recipients
Contents
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
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Introduction
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
program.
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 www.epa.gov/greenchemistry
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.
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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
Biochemistry,
University of Texas at
Austin
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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.
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Greener Synthetic Pathways Award
Development and Commercial Application of
Environmentally Friendly Adhesives for Wood
Composites
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
Engineering,
Oregon State
University;
Columbia Forest
Products;
Hercules
Incorporated
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Greener Reaction Conditions Award
Headwaters
Technology
Innovation
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
peroxide.
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
process.
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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
polyols.
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.
Cargill,
Incorporated
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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
yields.
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
Corporation
Dr. Ashok L. Cholli,
Center for
Advanced
Materials,
University of
Massachusetts
Lowell
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Professor
Purnendu K.
Dasgupta,
Department of
Chemistry and
Biochemistry, The
University of Texas
at Arlington
Professor Arlin E.
Gyberg, Augsburg
College
Professor James E.
Hutchison,
Department of
Chemistry and
Director, Materials
Science Institute,
University of
Oregon
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
spectrometry.
Technology for affordable analysis of arsenic in the field is particularly needed in small
water systems in the United States and in developing countries. The most common field
analysis method is based on the over-100-year-old Gutzeit reaction chemistry. It uses toxic
lead acetate, mercuric bromide (HgBr2), and large amounts of sample to measure As levels
near the 10 ppb limit. It also creates costly disposal problems.
Professor Dasgupta invented an affordable field analyzer (costing less than $2,500 for
parts) that is unique, USGS-validated, small, robust, and fully automated. It uses an order-
of-magnitude less sample, requires no toxic chemicals, and can measure As down to
0.05 ppm, rivaling atomic spectrometers that cost much more. The technology is based on
the gas-phase chemiluminescence of arsine (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
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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
products.
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
Engineering,
University of
Washington
Professor Gennaro
J. Maffia,
Department of
Chemical
Engineering,
Widener University
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Professor Krzysztof
Matyjaszewski,
Department of
Chemistry,
Carnegie Mellon
University
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.
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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
University
Professor Satomi
Niwayama,
Department of
Chemistry and
Biochemistry,
Texas Tech
University
13
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Professor Michael
C. Pirrung,
Department of
Chemistry,
University of
California,
Riverside
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.
14
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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
Resources,
Mississippi State
University
Professor Vadim A.
Soloshonok and Dr.
Hisanori Ueki,
Department of
Chemistry and
Biochemistry, The
University of
Oklahoma
15
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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
Subramaniam,
Center for
Environmentally
Beneficial
Catalysis,
Department of
Chemical and
Petroleum
Engineering,
University of
Kansas
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
Mining
Engineering,
University of
Kentucky
Georgia-Pacific Mining Reagents that Improve Recovery,
Reduce Wastes, and Conserve Water and Other Natural
Resources
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.
16
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Novel, One-Step, Chromate-Free Coatings Containing
Anticorrosion Pigments to Replace Chromate
Pretreatment and Pigments
Paints and organic coatings are often used to protect metals and alloys from corrosion.
The paint industry uses approximately 600,000 metric tons of chromates annually for
chromate conversion coatings and as pigments. The "self-healing" property of chromates
makes them difficult to replace. Hexavalent chromate, Cr(VI), has been identified as toxic
and carcinogenic, however; it is subject to regulation by various government bodies.
Chromate exposures cause a gamut of health problems including ulcers, irritation of the
nasal mucosa, holes in the nasal septum, skin ulcers, allergic reactions, and nasal and lung
cancer.
Paints are formulated with high-molecular-weight polymers for good anticorrosion
properties. These polymers require solvents that are volatile organic compounds (VOCs).
During curing and drying of the paint, these VOCs evaporate, posing an occupational 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
Materials
Engineering,
University of
Cincinnati
Professor Thomas
Wildeman,
Department of
Chemistry and
Geochemistry,
Colorado School of
Mines
17
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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
University
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.
18
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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
Biomolecular
Engineering;
Wilfred A. van der
Donk, Department
of Chemistry;
William W. Metcalf,
Department of
Microbiology,
University of
Illinois
19
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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
Advanced
BioCatalytics
Corporation
Advanced
BioCatalytics
Corporation
21
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Amerikal Products
Corporation
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.
22
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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.
Barricade
International, Inc.
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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
24
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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.
25
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Crosslink
Cutting Edge
Formulations, Inc.
Corrosion-Resistance without Chromium: On-Demand
Release of Environmentally Safe, Non-Chromium
Corrosion Inhibitors from Electroactive Polymer
Coatings
Currently, the prevalent primers and pretreatments used to inhibit corrosion of 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.
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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-
dens.
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
Environmentally
Sensitive
Solutions, Inc.
27
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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
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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
Technology
Styrene monomer is a large-volume commodity chemical with a current global demand
of about 25 million metric tons per year. The current technology is over 70 years old. It
relies on the dehydrogenation of ethylbenzene, which is a highly endothermic and 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
commercialization.
Exelus has invented a new zeolite catalyst technology and made other breakthroughs
that, for the first time, permit commercially viable reaction yields of 80 percent. The 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.
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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
infection.
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
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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,
Inc.
The LATA Group,
Inc.
31
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MYCELX
Technologies
Corporation
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.
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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
Elimination
Company, Inc.
Pantheon Chemical
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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.
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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
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Specialty Fertilizer
Products
Steward
Environmental
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
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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
Inc.
37
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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
firelogs.
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.
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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.
39
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Entries from Industry and
Government
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
Division
Laboratory
Albemarle
Catalysts Company
BV; ABB Lummus
Global Inc.
41
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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
Acid
Arkema Inc. has manufactured thioglycolic acid (TGA or mercaptoacetic acid) at its
plant in Axis, AL for over 20 years. TGA is used as an industrial intermediate, a 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,
42
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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
consumption.
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
Technologies
43
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Aspen Technology,
Inc.
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.
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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
recycling.
Battelle Memorial
Institute
Beaulieu Group,
LLC
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Benchmark
Performance
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
Stimulation
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.
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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
Paper
Buzyme® from Buckman Laboratories is a novel enzymatic technology to modify the
wood fibers used to manufacture paper. Buzyme® consists of a group of new cellulytic or
hemicellulytic enzymes made by fermentation in bacteria or fungi. For each grade of paper,
Buckman selects the enzyme that provides optimum results. This enzymatic treatment of
the wood fiber reduces the amount of mechanical refining required to reach desired fiber
properties. In various commercial applications in paper mills, this invention has given 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.
Bristol-Myers
Squibb Company
Buckman
Laboratories
International, Inc.
47
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Cytec Industries
Inc.
Cytec Industries
Inc.
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
Practices.
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
company.
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
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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
Company
Eli Lilly and
Company
49
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Emerson & Cuming
Georgia-Pacific
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
components.
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
50
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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.
Georgia-Pacific
Chemicals, LLC
51
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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.
52
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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 &
Company
Momentive
Performance
Materials Inc.
53
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Momentive
Performance
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.
54
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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
55
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The NutraSweet
Corporation;
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.
56
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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
prices.
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
Commercialization
Procter & Gamble has recently commercialized a patented, breakthrough chemical
innovation in environmentally friendly cleaning technology to provide superior cleaning
and significant energy savings in low-temperature (60 °F) wash water. Over 7 million U.S.
households have used Tide Coldwater® since its introduction in North America in January
2005-
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
Protocol.
The Procter &
Gamble Company
57
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Rhein Chemie
Corporation
Severn Trent
Services
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
requirements.
Bayoxide® E33 media achieves a three-fold reduction in waste. First, Bayoxide® E33
media is manufactured from iron sulfate, a waste product of the steel industry. Second, ser-
vice wash water from routine backwashing of the Bayoxide® E33 media can be reclaimed
58
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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
2006.
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
Center
59
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U.S. Department of
Energy, Argonne
National
Laboratory
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.
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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
Explosives
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
National
Laboratory
U.S. Department of
Energy, Los Alamos
National
Laboratory
61
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U.S. Department of
Energy, Los Alamos
National
Laboratory
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.
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Index
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
63
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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
Crosslink
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
64
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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
65
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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
66
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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
67
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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
68
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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
69
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"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
Center
Enzyme-Based Technology for Decontaminating Toxic Organophosphorus
Compounds 59
U.S. Department of Energy, Argonne National
Laboratory
Resin Wafer Technology 60
Solventless Process for Making Tackifiers and Adhesives 61
U.S. Department of Energy, Los Alamos National
Laboratory
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
70
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