The Presidential
Green Chemistry Challenge
Awards Program
Summary of 2005 Award
Entries and Recipients
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vvEPA
United States Office of Pollution EPA744-R-05-002
Environmental Protection Prevention and June 2005
Agency Toxics (7406M) www.epa.gov/greenchemistry
Recycled/Recyclable—Printed with Vegetable Oil Based Inks on 100% Postconsumer, Process Chlorine Free Recycled Paper
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Contents
Summary of 2005 Award Entries and Recipients. ...................... 1
Awards. [[[ 3
Academic Award 3
Small Business Award ......................................... 4
Alternative Synthetic Pathways Awards 5
Alternative Solvents/Reaction Conditions Award 7
Designing Safer Chemicals Award 8
Entries From Academia .......................................... 9
Entries From Small Businesses. ................................... 17
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Summary of 2005 Award Entries and Recipients
The Presidential Green Chemistry Challenge Awards Program is a competitive incentive
to create environmentally preferable chemicals and chemical processes. This year EPA cele-
brates an important milestone: 10 years of innovative, award-winning technologies developed
by high-quality nominees.
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 hazards
associated with the design, manufacture, and use of chemicals.
Through a voluntary EPA Design for the Environment partnership with the chemical
industry and professional scientific community, this annual award program seeks to discov-
er, highlight, and honor green chemistry.
Entries tor the 2005 awards were judged by an independent panel of technical experts
convened by the American Chemical Society. The judges used criteria that included health
and environmental benefits, scientific innovation, and industrial applicability. Six of the more
than 90 projects were nationally recognized on June 20, 2005, at an awards ceremony in
Washington, D.C. All the entries submitted to the 2005 competition are summarized in this
compilation. These technologies are meant to succeed in the marketplace as well: each illus-
trates the technical feasibility, marketability, and profitability of green chemistry.
For further information about the Presidential Green Chemistry Challenge and EPA's
Green Chemistry Program, go to www.epa.gov/greenchemistry.
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A Platform Strategy Using Ionic Liquids to Dissolve and
Process Cellulose for Advanced New Materials
Major chemical companies are currently making tremendous strides towards using renew-
able resources in biorefmeries. In a typical biorefinery, the complexity of natural polymers,
such as cellulose, is first broken down into simple building blocks (e.g., ethanol, lactic acid),
then built up into complex polymers. If one could use the biocomplexity of natural polymers
to form new materials directly, however, one could eliminate many destructive and con-
structive synthetic steps. Professor Rogers and his group have successfully demonstrated a
platform strategy to efficiently exploit the biocomplexity afforded by one of Nature's renew-
able polymers, cellulose, potentially reducing society's dependence on nonrenewable
petroleum-based feedstocks for synthetic polymers. No one had exploited the full potential
of cellulose previously, due in part to the shift towards petroleum-based polymers since the
1940s, difficulty in modifying the cellulose polymer properties, and the limited number of
common solvents for cellulose.
Professor Rogers's technology combines two major principles of green chemistry: devel-
oping environmentally preferable solvents and using biorenewable feedstocks to form
advanced materials. Professor Rogers has found that cellulose from virtually any source
(fibrous, amorphous, pulp, cotton, bacterial, filter paper, etc.) can be dissolved readily and
rapidly, without derivatization, in a low-melting ionic liquid (IL), l-butyl-3-methyliiiiida-
zolium chloride ([C4inim]Cl) by gentle heating (especially with microwaves). IL-dissolved
cellulose can easily be reconstituted in water in controlled architectures (fibers, membranes,
beads, floes, etc.) using conventional extrusion spinning or forming techniques. By Incorpo-
rating functional additives into the solution before reconstitution, Professor Rogers can
prepare blended or composite materials. The incorporated functional additives can be either
dissolved (e.g., dyes, complexants, other polymers) or dispersed (e.g., nanoparticles, clays,
enzymes) in the IL before or after dissolution of the cellulose. With this simple, noncovalent
approach, Professor Rogers can readily prepare encapsulated cellulose composites of tunable
architecture, functionality, and rheology. The IL can be recycled by a novel salting-out step
or by common cation exchange, both of which save energy compared to recycling by distil-
lation. Professor Rogers's current work is aimed at improved, more efficient, and economical
syntheses of [C-jiiiinJCl, studies of the IL toxicology, engineering process development, and
commercialization.
Professor Rogers and his group are currently doing market research and business plan-
ning leading to the commercialization of targeted materials, either through joint
development agreements with existing chemical companies or through the creation of small
businesses. Green chemistry principles will guide the development work and product selec-
tion. For example, targeting polypropylene- and polyethylene-derived thermoplastic
materials for the automotive industry could result in materials with lower cost, greater flexi-
bility, lower weight, lower abrasion, lower toxicity, and improved biodegradability, as well as
significant reductions in the use of petroleum-derived plastics.
Professor Rogers's work combines a fundamental knowledge of ILs as solvents with a novel
technology for dissolving and reconstituting cellulose and similar polymers. Using green
chemistry principles to guide process development and commercialization, he envisions that
his platform strategy can lead to a variety of commercially viable advanced materials that will
obviate or reduce the use of synthetic polymers.
D.
The
University of
Alabama
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Inc.
Producing Natures Plastics Using Biotechnology
Metabolix is commercializing polyhydroxyalkanoates (PHAs), a broadly useful family of
natural, environmentally friendly, high-performing, biobased plastics, PHAs are based on a
biocatalytic process that uses renewable feedstocks, such as cornstarch, cane sugar, cellulose
hydrolysate, and vegetable oils. PHAs can provide a sustainable alternative to petrochemical
plastics in a wide variety of applications.
Metabolix uses biotechnology to introduce entire enzyme-catalyzed reaction pathways
into microbes, which then produce PHAs, in effect creating living biocatalysts. The perfor-
mance of these engineered microbes has been fully validated in commercial equipment,
demonstrating reliable production of a wide range of PHA copolymers at high yield and
reproducibility. A highly efficient commercial process to recover PHAs has also been devel-
oped and demonstrated. The routine expression of exogenous, chromosomally integrated
genes coding for the enzymes used in a non-native metabolic pathway is a tour deforce in the
application of biotechnology. These accomplishments have led Metabolix to form an alliance
with Archer Daniels Midland Company, announced in November 2004, to produce PHAs
commercially, starting with a 50,000 ton per year plant to be sited in the U.S. Midwest.
These new natural PHA plastics arc highly versatile, have a broad range of physical prop-
erties, and are practical alternatives to synthetic petrochemical plastics. PHAs range from
rigid to highly elastic, have very good barrier properties, and are resistant to hot water and
greases. Metabolix has developed PHA formulations suitable for processing on existing
equipment and demonstrated them in key end-use applications such as injection
molding, thermoforming, blown film, and extrusion melt casting including film, sheet, and
paper coating.
Metabolixs PHA natural plastics will bring a range of environmental benefits, including
reduced reliance on fossil carbon and reduced greenhouse gas emissions. PHAs are now made
from renewable raw materials, such as sugar and vegetable oils. In the future, they will be pro-
duced directly in plants. In addition, PHAs will reduce the burden of plastic waste on solid
waste systems, municipal waste treatment systems, and marine and wetlands ecosystems: they
will biodegrade to harmless products in a wide variety of both aerobic and anaerobic envi-
ronments, including soil, river and ocean water, septic systems, anaerobic digesters, and
compost.
Metabolixs PHA technology is the first commercialization of plastics based on renewable
resources that employs living biocatalysts in microbial fermentation to convert renewable raw
materials all the way to the finished copolymer product. PHAs are also the first family of plas-
tics that combine broadly useful properties with biodegradability in a wide range of
environments, including marine and wetlands ecosystems. Replacement of petrochemical
plastics with PHAs will also have significant economic benefits. Producing 25 million tons of
PHA natural plastics to replace about half of the petrochemical plastics currently used in the
U.S. would reduce oil imports by over 200 to 230 million barrels per year, improving the
U.S. trade balance by $6 to 9 billion a year, assuming oil at $30 to $40 per barrel.
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NovaLipid1™: Low Trans Fats and Oils Produced by
Enzymatic Interesterification of Vegetable Oils
Using Lipozyme®
Two major challenges facing the food and ingredient industry are providing health-con-
scious products to the public and developing environmentally responsible production
technology. Archer Daniels Midland Company (ADM) and Novo/ynes are commercializing
enzymatic interesterihcation, a technology that not only has a tremendous positive impact on
public health by reducing trans tatty acids in American diet, but also offers great environ-
mental benefits by eliminating the waste streams generated by the chemical interesterification
process,
Triglyccrides consist of one glycerol plus three fatty acids. Triglycerides that contain most-
ly unsaturated fatty acids are liquid at room temperature. Manufacturers partially
hydrogenate these fatty acids to make them solids at room temperature. Trans fatty acids form
during the hydrogenation process; they are found at high concentrations in a wide variety of
processed foods. Unfortunately, consumption of trans fatty acids is also a strong risk factor
for heart disease. To reduce trans fats in the American diet as much as possible, the FDA is
now requiring labeling of trans fats on all nutritional fact panels by January 1, 2006. In
response, the U.S. food and ingredient industry has been investigating methods to reduce
trans fats in food.
Of the available strategies, interesterification is the most effective way to decrease the trans
fat content in foods without sacrificing the functionality of partially hydrogcnatcd vegetable
oils. During interesterification, triglycerides containing saturated fatty acids exchange one or
two of their fatty acids with triglycerides containing unsaturated fatty acids, resulting in
triglycerides that do not contain any trans tatty acids. Enzymatic interesterification processes
have many benefits over chemical methods, but the high cost of the enzymatic process and
poor enzyme stability had prevented its adoption in the bulk fat industry.
Extensive research and development work by both Novozymes and ADM has led to the
commercialization of an enzymatic interesterification process. Novozymes developed a cost-
effective immobilized enzyme, and ADM developed a process to stabilize the immobilized
enzyme enough for successful commercial production. The interesterified oil provides food
companies with broad options for zero and reduced trans fat food products. Since the first
commercial production in 2002, ADM has produced more than 15 million pounds of inter-
esterified oils. ADM is currently expanding the enzyme process at two of its U.S. production
facilities.
Enzymatic interesterification positively affects both environmental and human health.
Environmental benefits include eliminating the use of several harsh chemicals, eliminating
byproducts and waste streams (solid and water) and improving the use of edible oil resources.
As one example, margarines and shortenings currently consume 10 billion pounds of hydro-
genated soybean oil each year. Compared to partial hydrogenation, the ADM/Novozymes
process has the potential to save 400 million pounds of soy bean oil, eliminate 20 million
pounds of sodium methoxidc, 116 million pounds of soaps, 50 million pounds of bleaching
clay, and 60 million gallons of water each year. The enzymatic process also contributes to
improved public health by replacing partially hydrogenated oils with interesterified oils that
contain no trans fatty acids and have increased polyunsaturated tatty acids.
Archer
Company
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& Co., Inc.
A Redesigned, Efficient Synthesis of Aprepitant, the
Active Ingredient in Emend®: A New Therapy for
Chemotherapy-Induced Ernests
Emend® is a new therapy for chemotherapy-induced nausea and vomiting, the most com-
mon side effects associated with chemotherapeutic treatment of cancer. Emend* has been
clinically shown to reduce nausea and vomiting when used during and shortly after
chemotherapy. Aprepitant is the active pharmaceutical ingredient in Emend®.
Aprepitant, which has two heterocyclic rings and three stereogenic centers, is a challeng-
ing synthetic target. Merck's first-generation commercial synthesis required six synthetic steps
and was based on the discovery synthesis. The raw material and environmental costs of this
route, however, along with operational safety issues compelled Merck to discover, develop,
and implement a completely new route to aprepitant.
Merck's new route to aprepitant demonstrates several important green chemistry princi-
ples. This innovative and convergent synthesis assembles the complex target in three highly
atom-economical steps using four fragments of comparable size and complexity. The first-
generation synthesis required stoichiometric amounts of an expensive, complex chiral acid as
a reagent to set the absolute stereochemistry of aprepitant. In contrast, the new synthesis
incorporates a chiral alcohol as a feedstock; this alcohol is itself synthesized in a catalytic
asymmetric reaction. Merck uses the stereochemistry of this alcohol feedstock in a practical
crystallization-induced asymmetric transformation to set the remaining stereogenic centers of
the molecule during two subsequent transformations. The new process nearly doubles the
yield of the first-generation synthesis. Much of the chemistry developed for the new route is
novel and has wider applications. In particular, the use of a stereogenic center that is an inte-
gral part of the final target molecule to set newstereocenters with high selectivity is applicable
to the large-scale synthesis of other chiral molecules, especially drug substances.
Implementing the new route has drastically improved the environmental impact of
aprepitant production. Merck's new route eliminates all of the operational hazards associated
with the first-generation synthesis, including those of sodium cyanide, dimethyl titanocene,
and gaseous ammonia. The shorter synthesis and milder reaction conditions have also
reduced the energy requirements significantly. Most important, the new synthesis requires
only 20% of the raw materials and water used by the original one. By adopting this new
route, Merck has eliminated approximately 340,000 liters of waste per 1,000 kg of aprepi-
tant that it produces.
The alternative synthetic pathway for the synthesis of aprepitant as discovered and imple-
mented by Merck is an excellent example of minimizing environmental impact while greatly
reducing production costs by employing the principles of green chemistry. Merck imple-
mented the new synthesis during its first year of production of Emend®; as a result, Merck
will realize the benefits of this route for virtually the entire lifetime of this product. The choice
to implement the new route at the outset of production has led to a huge reduction in the
cost to produce aprepitant, demonstrating quite clearly that green chemistry solutions can be
aligned with cost-effective ones.
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A UV-Curable, One-Component, Low-VOCRefinish
Primer: Driving Eco-Efficiency Improvements
The market for automotive refinish coatings in North America exceeds $2 billion for both
collision repairs and commercial vehicle applications. Over 50,000 body shops in North
America use these products. For more than a decade, automotive refmishers and coating
manufacturers have dealt with increasing regulation of emissions of volatile organic com-
pounds (VOCs). At first, coating manufacturers were able to meet VOC maximums with
high-performance products such as two-component reactive urcthancs, which require sol-
vents as carriers for their high-molecular-weight resins. As thresholds for VOCs became
lower, however, manufacturers had to reformulate their reactive coatings, and the resulting
reformulations were slow to set a film. Waterborne coatings are also available, but their util-
ity has been limited by the time it takes the water to evaporate. Continuing market pressures
demanded faster film setting without compromising either quality or emissions.
Through intense research and development, BASF has invented a new urethane acrylate
oligomer primer system. The resin cross-links with monomer (added to reduce viscosity) into
a film when the acrylate double bonds are broken by radical propagation. The oligomers and
monomers react into the film's cross-linked structure, improving adhesion, water resistance,
solvent resistance, hardness, flexibility, and cure speed. The primer cures in minutes by visi-
ble or near-ultraviolet (UV) light from inexpensive UV-A lamps or even sunlight. BASF's
UV-cured primer eliminates the need for bake ovens that cure the current primers, greatly
reducing energy consumption. BASF's primer performs better than the current convention-
al urethane technologies: it cures ten times faster, requires fewer preparation steps, has a lower
application rate, is more durable, controls corrosion better, and has an unlimited shelf life.
BASF is currently offering its UV-cured primers in its R-M® line as Flash Fill™ VP126 and
in its Glasurit® line as 151-70.
BASF's primer contains only 1.7 pounds of VOCs per gallon, in contrast to 3.5 to 4.8
pounds of VOCs per gallon of conventional primers, a reduction of over 50%. The primer
meets even the stringent requirements of South Coast California, whereas its superior prop-
erties ensure its acceptance throughout the U.S. market. The one-component nature of the
product reduces hazardous waste and cleaning of equipment, which typically requires sol-
vents. Applications in repair facilities over the past year have shown that only one-third as
much primer is needed and that waste is reduced from 20% to nearly zero. The BASF acry-
late-based technology requires less complex, less costly personal protective equipment (PPE)
than the traditional isocyanate-based coatings; this, in turn, increases the probability that
small body shops will purchase and use the PPE, increasing worker safety.
This eco-efficient product is the first step in an automobile refmishing coating system for
which BASF plans to include the globally accepted waterborne basecoat from BASF (sold
under the Glasurit® brand as line 90). In the near future, this system can be finished with the
application of a one-component, UV-A-curable clearcoat. The system will deliver quality,
energy efficiency, economy, and speed for the small businessman operating a local body shop,
while respecting the health and safety of the workers in this establishment and the environ-
ment in which these products are manufactured and used. To fully support these claims,
BASF has conducted an eco-efficiency study with an independent evaluation.
Corporation
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Archer
Company
Archer RC™: A Nonvolatile, Reactive Coalescent for
the Reduction ofVOCs in Latex Paints
Since the 1980s, waterborne latex coatings have found increasingly broad acceptance in
architectural and industrial applications. Traditional latex coatings are based on small-parti-
cle emulsions of a synthetic resin, such as acrylate- and styrene-based polymers. They require
substantial quantities of a coalescent to facilitate the formation of a coating film as water
evaporates after the coating is applied. The coalescent softens (plasticizes) the latex particles,
allowing them to flow together to form a continuous film with optimal performance prop-
erties. After film formation, traditional coalescents slowly diffuse out of the film into the
atmosphere. The glass transition temperature of the latex polymer increases as the coalescent
molecules evaporate, and the film hardens. Alcohol esters and ether alcohols, such as ethyl-
ene glycol monobutyl ether (EGBE) and Texanol® (2,2,4-trimethyl-l,3-pentanediol
monoisobutyrate), are commonly used as coalescents. They are also volatile organic com-
pounds (VOCs). Both environmental concerns and economics continue to drive the trend to
reduce the VOCs in coating formulations. Inventing new latex polymers that do not require
a coalescent is another option, but these polymers often produce soft films and are expensive
to synthesize, test, and commercialize. Without a coalescent, the latex coating may crack and
may not adhere to the substrate surface when dry at ambient temperatures.
Archer RC™ provides the same function as traditional coalescing agents, but eliminates
the unwanted VOC emissions. Instead of evaporating into the air, the unsaturated fatty acid
component of Archer RC™ oxidizes and even cross-links into the coating. Archer RC™ is pro-
duced by interesterifying vegetable oil fatty acid esters with propylene glycol to make the
propylene glycol monoesters of the fatty acids. Corn and sunflower oils are preferred feed-
stocks for Archer RC™ because they have a high level of unsaturated fatty acids and tend to
resist the yellowing associated with linolenic acid, found at higher levels in soybean and lin-
seed oils. Because Archer RC1M remains in the coating after film formation, it adds to the
overall solids of a latex paint, providing an economic advantage over volatile coalescents.
The largest commercial category for latex paint, the architectural market, was 618.4 mil-
lion gallons in the U.S. in 2001. Typically, coalescing solvents constitute 2 to 3% of the
finished paint by volume; this corresponds to an estimated 120 million pounds of coalescing
solvents in the U.S. and perhaps three times that amount globally. Currently, nearly all of
these solvents are lost into the atmosphere each year.
Archer Daniels Midland Company has developed and tested a number of paint formula-
tions using Archer RC™ in place of conventional coalescing solvents. In these tests, Archer
RC™ performed as well as commercial coalescents such as Texanol*. Archer RC™ often had
other advantages as well, such as lower odor, increased scrub resistance, and better opacity.
Paint companies and other raw material suppliers have demonstrated success formulating
paints with Archer RC™ and their existing commercial polymers. Archer RC™ has been in
commercial use since March 2004.
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The Application of Ultrasound (Sonication) to Catalyze
Reactions in Some Industrial Processes
Ultrasound has potential as a safe and clean method to catalyze reactions. It uses high-
frequency sound waves to change reaction paths and speed up reactions, thus reducing or
eliminating added chemicals. The methodology has so far not been scaled up tor industrial
application to any great extent. Dr. MacRitchie and his collaborators are working to apply
ultrasound to three areas that have the potential to lead to industrial processes. These are: (1)
the modification of wheat gluten to create value-added products; (2) the clarification of fruit
juices; and (3) the purification of potable water. Dr. MacRitchie is using ultrasound to pro-
duce value-added products from gluten by enhancing functional properties such as solubility,
gelling, foaming, and emulsifying. For example, ultrasound can increase the solubility of
gluten, making it suitable for use in fortified beverages. Previous methods have used concen-
trated acids or enzymes, but these are not environmentally friendly. Dr. MacRitchie and his
colleagues are collaborating closely with Midwest Grain Products in Atchison, Kansas, one of
the major manufacturers of gluten. Presently, manufacturers mainly use enzymes to clarify
fruit juices. Ultrasound offers the possibility of clarification without additional chemicals.
Water contamination by microorganisms or by chemical pollutants such as pesticides is
another problem to which Dr. MacRitchie will apply ultrasonics to replace traditional
hazardous chemicals.
Biocatalytically Synthesized High-Performance Novel
Antioxidants for Materials
Industrial antioxidants are an increasingly important and fast-growing market. The
antioxidants market in the U.S. is currently $1.4 billion, comprised of several low-molecu-
lar-wcight antioxidants. Dr. Cholli and his group have developed high-performance
macromolecular antioxidants that are synthesized in a one-step process using biocatalysts and
bio mimetic catalysts. These antioxidants have shown superior oxidative resistance (1- to 30-
fold) and higher thermal stability compared to current low-molecular-weight antioxidants.
This novel class of antioxidant technology is now ready for commercialization through
Polnox Corporation. Dr. Cholli and his team at the University of Massachusetts Lowell orig-
inally developed Polnox's technology. Polnox's antioxidants have demonstrated superior
performance in a wide range of materials and applications including, but not limited to,
foods, oils and lubricants, fuels, plastics, and packaging. An acute oral toxicity (LDso) test for
these materials meets the requirements of other FDA-approved antioxidants. Scale-up to
multikilogram scale has been demonstrated.
Bioinspired Thymine-Based Photopolymers: A Green
Chemistry Platform for Innovation, Research,
Education, and Outreach
Thymine-based photopolymers mimic the UV-light-induced formation and splitting of
dimers in DNA. The styrene derivative vinylbenzyl thymine (VBT) offers unique polyfunc-
tionality for polymerization, derivatization, hydrogen bonding, and pi-stacking, as well as
Dr. Finlay MacRitchie,
Department of Grain
Science Industry,
Kansas State University
Dr. L. Cholli,
Center for Advanced
Materials, Uniwersity of
Massachusetts Lowell
Professor John C.
Warner, School of
and the
Enwironment and
Director, Green
Chemistry Program,
University of
Massachusetts Lowell
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Professor Krzysztof
Matyjaszewski,
Department of
Chemistry, Carnegie
Mellon University
Dr. Savvas Vasileiadis
photocrosslinking. The applications of thymine-based photopolymers are benign, atom-eco-
nomical, energy-efficient, water-soluble, and processable under ambient conditions. VBT
prototypes, combining these features, demonstrate the technical feasibility' of commercial
applications of benign, prepolymerized photoresists: as a nontoxic, reversible hair fixative; for
ambient, aqueous lithography of recyclable printed wiring boards; and for light-modulated
pharmaceutical formulations. These highlight safety at the point-of-use with "light as a
reagent", avoiding the danger of reactive monomers and emissions of volatile organic sol-
vents. Immobilization of antimicrobials with VBT can substitute for chlorinated
disinfectants, reduce the overuse and release of antibiotics, and preclude bacterial resistance.
Success with VBT for surface-patterning conjugated-polymer nanocomposites and the facil-
ity of VBT for specific host-guest chemistry to embed analytes in sensor coatings offer links
to the emerging fields of plastic electronics, functional inks, and smart textiles. VBT proto-
types have driven 12 collaborations and 30 student projects; they have served 25 courses and
60 outreach events. This technology has been awarded four patents; two more patents are
pending.
Development of Environmentally Benign Low-VOC
Manufacturing Processes for Functional Materials:
Towards Elimination of Transition Metals from Materials
Made by Atom Transfer Radical Polymerization (ATRP)
Atom Transfer Radical Polymerization (ATRP) is a controlled, transition-metal-mediated
process to polymerize appropriate monomers by radical mechanisms; it was discovered in Dr.
Matyjaszewski's laboratories in 1995. At present, many industrial research programs are
actively incorporating this process to prepare polymers for a broad spectrum of applications.
Commercial products including coatings and adhesives have been using this technology since
2002. The estimated market for well-defined functional polymers that could be made by the
ATRP technology exceeds $20 billion per year.
Since 1995, Dr. Matyjaszewski's group has led efforts to develop more active catalyst sys-
tems targeted at reducing the levels of metals in ATRP systems. His group has also led the
development of environmentally benign procedures for preparing many functional materials
using ATRP. Previously, the most active catalysts could not be used in these systems, howev-
er, because the activity of the catalyst had to be balanced with the number of moles of
initiator required to prepare low-molecular-weight functional oligomers of commercial
importance. Dr. Matyjaszewski's group overcame this limitation with hybrid catalysts and
two recent improvements: "Simultaneous Reverse and Normal Initiation" and "Activators
Generated by Electron Transfer". As a result, Dr. Matyjaszewski's group can now apply their
expanded understanding of ATRP catalysis to develop aqueous and bulk ATRP processes.
The combined process controls the activity of the hybrid catalyst fully over extended time
periods; it also allows recycling of the catalyst residues present in the process effluent back
into reactor feed streams. Overall, the combined process eliminates all hazardous substances
from the products made by ATRP and from industrial production waste streams.
Direct Step Olefm-to-Polyolefm Process with Toxic
Solvent Elimination
Dr. Vasileiadis's nomination presents new catalytic processes for aliphatic (paraffin) hydro-
carbon dehydrogenation into olefms and for subsequent polymerization into polyolefms.
10
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These processes use catalytic dehydrogenation reactors in conjunction with polymerization
reactors and coordination-type metal catalysts, such as titanium trichloride. In developing
these processes, Dr. Vasileiadis considered materials and energy conservation coupled with
environmentally benign modifications (e.g., the elimination of toxic or hazardous solvents,
catalysts, and other media). Process improvements include increased polymer and olcfin
product yields, recycling of reactants and intermediate products for utilization within the
process, reduction of toxic solvent generation, reduction of process steps, and reduction of
capital and operational costs (including materials and energy costs). In 2004, Dr. Vasileiadis's
technology received a U.S. patent. Dr. Vasileiadis is currently in the process of commercial-
izing this technology.
Effective, Economical, and Relatively Benign Totally
Organic Wood Preservatives to Replace the Current
Copper-Rich Systems
Lumber for U.S. residential applications is currently treated with copper-rich preserva-
tives. Environmental concerns have been raised about these "new" systems, however, and
future disposal of metal-treated lumber may be difficult. Thus, in the future, totally organic
wood preservatives will likely be required. Several problems exist with totally organic preser-
vatives, principally: (1) the high cost of the newer organic biocides relative to the old metallic
biocides; and (2) the biodegradation of organic biocides by various microorganisms, unlike
metallic biocides.
Wood-decaying fungi use free radicals to degrade wood. With this basic knowledge,
Professors Schultz and Nicholas combined various commercial organic biocides with an eco-
nomical, benign, and commercially available antioxidant: butylated hydroxytoluene (BHT).
They found that the combination was more effective than either component alone in short-
term laboratory tests. Results from long-term outdoor exposure tests were even more
promising. Further, they have recently confirmed their earlier hypothesis that BHT helps
protect a commercial biocide against microbial degradation. Because BHT and organic bio-
cidc mixtures are synergistic and BHT reduces biodegradation of the biocide, less of the
relatively expensive organic biocide is necessary to protect wood. Unlike most biocides, BHT
is low-cost and safe to humans. Thus, wood treated with a biocide/BHT mixture will likely
be safer to humans, have a reduced environmental impact, and be easier to dispose of than
metal-treated wood. A preliminary economic analysis suggests that this concept is economi-
cal: the saving from the reduced biocide level is greater than the BHT cost.
Feedstocks for Catalytic Asymmetric Synthesis: New
Route to (S)-Ibuprofen and Other 2-Arylpropionic Acids
from Ethylene and Styrene Derivatives
One of the major challenges facing organic synthesis is the selective incorporation of
abundantly available carbon, hydrogen, oxygen, and nitrogen sources into other common
substrates. Professor RajanBabu and his group have discovered new, highly catalytic (sub-
strate:catalyst ratio up to 1450) protocols for nearly quantitative (isolated yields up to >99%)
and highly selective (100% regioselectivity, up to 96:4 enantiomeric ratio) codimerization of
ethylene and various functionalized vinylarenes (hydrovinylation). These reactions proceed
under exceedingly mild conditions (-52 °C, 1 atmosphere of ethylene) and produce highly
valuable 3-arylbutenes. They consume both starting materials and leave no side products:
Professors Tor P.
Schultz and Darrel D.
Nicholas, College of
Forest Resources,
Mississippi State
University
Professor T. V. (Babu)
RajanBabu, Department
of Chemistry, The Ohio
State University
11
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Professor Michael J.
Krische, Department of
Chemistry and
Biochemistry,
Uniwersity of
at Austin
Professor Richard P.
Wool, Department of
Chemical Engineering,
University of Delaware
and Affordable
Composites from
Renewable Resources
Center for Composite
Materials
ideal criteria for an environmentally friendly process. A prototypical example of this
hydrovinylation chemistry is the enantioselective synthesis of the widely used anti-inflam-
matory agent, ibuprofen, from 4-isobutylstyrene and ethylene. Several other profen drugs
(e.g., naproxen, ketoprofen, flurbiprofen) could, in principle, be synthesized by this route.
During these investigations, Professor RajanBabu prepared several new ligands. He also dis-
covered new control elements that may have broader applications in the discovery of other
highly selective catalytic processes. Examples include: (1) the effects of electronic and steric
tuning of ligands; and (2) the role of hemilabile ligands and highly dissociated counterions
in enhancing selectivity. Since the publication of Professor RajanBabu's original results, oth-
ers have shown that the hydrovinylation reaction can be run in environmentally friendly
supercritical
Hydrogen-Mediated Carbon-Carbon Bond Formation:
Catalytic Cross-Coupling with Complete Atom Economy
Elemental hydrogen is the cleanest and most cost-effective reductant available to
humankind. Although catalytic hydrogenation is practiced industrially on an enormous scale,
the use of hydrogen as a terminal reductant in catalytic C-C bond formation has been
restricted to processes involving migratory insertion of carbon monoxide: for example, alkcnc
hydro formylation and the Fischer-Tropsch reaction. In the absence of carbon monoxide, the
capture of hydrogenation intermediates becomes untenable due to rapid CH reductive elim-
ination of the (alkyl) (hydrido) metal intermediates. The Krische group has demonstrated that
direct C-H reductive elimination manifolds are disabled upon heterolytic activation of
hydrogen (Ha + M-X — » M-H + HX). This extends the lifetime of the organometallic inter-
mediates obtained upon hydrometallation and facilitates their capture. The diverse
hydrogen-mediated C-C bond formations developed in Dr. Krischc's laboratory proceed with
complete atom economy; several transformations have been rendered enantioselective.
Moreover, implementation of this emergent technology should be expedited by the enor-
mous infrastructure already in place for industrial-scale hydrogenation.
Materials from Renewable Resources
Professor Wool and his Affordable Composites from Renewable Sources (ACRES)
research group use genetic engineering, composite science, and natural fibers to develop new,
improved green materials from renewable resources. His green materials are optionally recy-
clable and biodegradable, thereby enhancing global sustainability. He has made a wide range
of new high-performance, low-cost materials using plant oils, natural fibers, lignin, nan-
oclays, and carbon nanotubes. By selecting the fatty acid distribution of plant oils
(triglyce rides) and the molecular connectivity, he controls the chemical functional groups and
molecular architecture to produce linear, branched, or cross-linked polymers. His work
describes the chemical pathways used to modify plant oils and allow them to react with each
other and with various co-monomers to form new materials with useful properties. "When
Professor Wool combines biobased resins derived from natural oils with natural fibers (plant
and poultry), glass fibers, carbon nanotubes, nanoclays, and lignin, he produces new high-
performance composites that are economical in many high-volume applications. His
composites are used in hurricane-resistant housing, agricultural equipment, automotive sheet
molding compounds, civil and rail infrastructures, marine applications, electronic materials,
and sports equipment. In addition, Professor Wool uses genetically engineered oils to make
soft materials, such as pressure-sensitive adhesives (PSAs), foams, coatings, and elastomers.
12
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The market for biobased materials is conservatively 100 billion pounds per year; Professor
Wool's inventions are attracting considerable attention from industry.
N-Vinyl Formamide: The "Greening" of a Green
Replacement for Acrylamide
Acrylamide is produced at volumes of over 200 million kg/year and is used worldwide to
generate polyacrylamide. Acrylamide has been documented as a neurotoxin in human epi-
demiological studies; it is also a potential carcinogen. The 1998 Toxics Release Inventory
(TRI) shows that 85 facilities released over 6.3 million pounds of acrylamide into the envi-
ronment. N-vinyl formamide (NVF), an isomer of acrylamide, is readily polymerized to
poly(N-vinyl formamide). NVF is neither a carcinogen nor a neurotoxin. Polymers incor-
porating NVF can perform most of the same applications as acrylamide polymers.
Unfortunately, the current commercial production process for NVF exhibits a cost disad-
vantage that is tied to "green disadvantages". Professor Beckman has created an NVF
synthesis that is intensified, uses lower process temperatures, produces less waste, and uses less
hazardous raw materials than the current commercial synthesis. He has also found that
hydrolyzed homopolymers and copolymers of NVF form covalent gels in the presence of
reducing sugars. These gels are sufficiently robust to allow their use in oil recovery, replacing
currently used polyacrylamide-chromium(III) gels in preventing the production of waste
water during oil production. Polyvinyl amine-sugar gels can also replace chlorinated com-
pounds during the processing of paper.
A One-Step, Anti-Corrosion, VOC-Free, Primer System
to Replace Cbromate Pretreatment and Pigments
Corrosion protection by paints and organic coatings is a common practice.
Approximately 600,000 metric tons of chromates are used in the paint industry for chromate
conversion coating and as pigments annually. The U.S. EPA, however, has identified chro-
mates in the hcxavalcnt state of oxidation as both toxic and carcinogenic. Chromate
exposures cause a gamut of health problems, such as ulcers, irritation of the nasal mucosa,
holes in the nasal septum, skin ulcers, allergic reactions, and nasal and lung cancer. The "self-
healing" property of chromate makes it difficult to replace, however.
Paints are formulated with high-molecular-weight polymers for good anticorrosion prop-
erties. 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's invention is a one-step, very low VOC, anticorrosion primer system
that totally eliminates chromates, yet performs as well as chromate-containing paints. He has
successfully demonstrated that mixtures of organofunctional silanes and waterborne resins
can be applied directly to metals as self-priming primers. His primer mimics the "self-heal-
ing" property of the chromates by including a plasma-treated pigment package to release a
corrosion inhibitor slowly. Professor Van Ooij is currently commercializing this technology
through a small company, ECOSIL Technologies, LLC.
Professor Eric J.
Beckman, Chemical
Engineering Department,
University of Pittsburgh
Professor Wim J. Van
Ooij, Department of
Chemical and Materials
Engineering, Uniyersity
of Cincinnati
13
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Professor Xumu Zhang,
Department of
Chemistry, The
Pennsylwania State
Uniwersity
Practical Asymmetric Catalytic Hydrogenation
Over 50% of the world's pharmaceu deals are single enantiomers; sales of chiral drugs were
$159 billion in 2002. A growing challenge is to develop cost-effective, green chemical cat-
alytic 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. Among commercial asym-
metric chemocatalysis methods, asymmetric hydrogenation is dominant, accounting for over
70% of these methods. Fundamental, innovative chemical methods are needed to develop
these green chemical processes. Breakthroughs in this area will have broad applicability in
industry. Dr. Zhang's laboratory has developed novel transition-metal-reduction catalysts for
the practical synthesis of chiral alcohols, amines, acids, amino alcohols, diols, and a- and |3-
amino acids. He has also investigated the fundamental factors controlling enantioselectivity.
His group has invented a toolbox of practical chiral ligands for the asymmetric hydrogena-
tion of ketones, alkenes, imines, and aromatic compounds. He has observed high activity (up
to 50,000 turnovers) and enantioselectivity (up to 99% enantiomeric excess) for hydrogena-
tion of some substrates. He demonstrates the synthetic utility of asymmetric hydrogenation
in the green chemical processes with challenging asymmetric transformations for important
biologically active compounds such as Lipitor*', Cymbalta®, and carbopenem.
Professor Jefferson W.
Tester, Chemical
Engineering Department,
Massachusetts Institute
of Technology
Replacing Organic Solvents and Homogeneous Catalysts
with Water and Carbon Dioxide
Professor Tester and the MIT Supercritical Fluids Research Group have made significant
advances in the field of green chemistry over the past five years. Their approach uses pure
water, pure carbon dioxide, and water-carbon dioxide biphasic mixtures as reaction media for
a range of carbon-carbon forming, oxidation, and hydrolysis reactions. Their major contri-
butions include novel experimental apparatus designs and protocols, as well as validated
models that provide technology to enable the use of water and carbon dioxide as green sol-
vents. They have coupled experiments conducted under well-defined conditions to multiscale
modeling to improve their understanding of reaction rate, selectivity, and mechanistic phe-
nomena relevant to carrying out synthetic chemistry in these green media. They have
demonstrated the feasibility of a surfactant-free acoustic technique that naturally segregates
catalysts from reactants and products. This technique affords the opportunity to reduce oper-
ating costs for industrially important processes using homogeneous catalysts. Their efforts
have produced new scientific methodologies and data regarding the chemical kinetics, phase
kinetics, and equilibrium behavior of many model supercritical fluid mixtures. They have
documented their results in over 100 publications. Other laboratories in the U.S. and other
countries now utilize many of their methods, underscoring the usefulness of their experi-
mental and theoretical methods for quantitative physical chemical kinetic analysis in
hydrothermal and supercritical fluid media.
14
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Research, Development, and Commercialization of
Environmentally Benign Thermoplastic Pressure-
Sensitive Adhesive Label Products
Eliminating the problems created by pressure-sensitive adhesives (PSAs) in post-consumer
waste is the most important technical barrier to expanding the use of recycled paper.
Estimates are that replacement of current PSA technology with benign formulations can save
tens of trillions of BTLJs per year, increase the quantity of paper that can be recycled, and save
the industry $650 million in non-energy-related expenses, A promising approach is the
redesign of adhesive products to diminish their negative impact on paper recycling opera-
tions. Dr. Severtson has designed thermoplastic PSA products for which fragmentation of
PSA films are inhibited during repulping operations. The adhesive particles that form are eas-
ily removed by standard cleaning equipment early in the recycling process, eliminating the
PSA contamination. This iterative research included the study of model PSA systems and
eventually led to the development of commercial products. PSA properties have been thor-
oughly characterized and their screening removal efficiencies have been tested when attached
to various facestocks. This research has identified the surface and bulk mechanical properties
of label components and the interactions between them that govern film fragmentation. Dr.
Severtson's research is allowing label manufacturers to produce commercially viable, environ-
mentally benign thermoplastic PSA labels that meet any customer requirement. This project
is an impressive demonstration of academic-industrial collaboration on green technology and
its successful promotion from the laboratory to the marketplace.
Solvent-Free, Crystal-to-Crystal Photochemical
Reactions: The Synthesis of Adjacent Stereogenic
Quaternary Centers
Chemical structures with adjacent stereogenic quaternary carbon centers are common in
biologically active substances, including natural products, pharmaceuticals, and specialty
chemicals. Despite recent advances in preparative chemistry, there have been no satisfactory
procedures for preparing these structures, much less so for preparing them using environ-
mentally benign processes. At present, most structures are obtained in low yields by circuitous
routes with waste-generating purification steps. The technical challenge stems from the lim-
itations that arise when six groups must converge with precise stereochemistry within 1.54 A,
which is the bond distance between two adjacent carbons. The method developed by
Professor Garcia-Garibay consists of exposing a finely powdered crystalline ketone to a light
source. Within hours, the ketone transforms into the desired product with no need for purifi-
cation. Notably, the addition of six groups at the ketone a-carbons (now -2.56A apart) can
be easily accomplished with excellent steric control by conventional methods. These sub-
stituents weaken the ketone a-bonds to extrude a CO molecule when a photon is absorbed.
A short-lived biradical intermediate retains the stereochemistry of the ketone and makes the
desired bond with stereoselectivity and stereospecificity that rival enzymatic processes. As an
emergent technology, the photodecarboxylation of crystalline ketones is one of the most gen-
eral and promising methods for synthesizing structures with adjacent stereogenic quaternary
centers.
Dr. Stewen J. Sewertson,
Department of Bio-
Products,
University of
Minnesota
Professor Miguel A.
Garcia-Garibay,
Department of
Chemistry and
Biochemistry,
University of
California, Los Angeles
15
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Professor Joseph M.
DeSimone, Department
of Chemistry,
Uniwersity of North
Carolina at Chapel Hill
and Department of
Chemical Engineering,
North Carolina State
Uniwersity
Professor Ajay K. Bose,
Department of
Chemistry and
Chemical Biology,
Stevens Institute of
Technology
Surfactant-Free Supercritical Carbon Dioxide
Fluoroolefin Polymerization Technology
Fluoropolymers exhibit a balance of high-performance properties that makes them ideal
for many technologically demanding applications. Commercial fluoropolymer manufactur-
ing practices use aqueous emulsion or suspension processes that require fluorinated
surfactants that are now environmentally suspect (see ''Perfluorinatcd Pollutant Puzzle" in
Chemical & Engineering News, August 30, 2004). Moreover, these traditional water-based
manufacturing processes strain local community water supplies and pose real health concerns
when residual surfactant is not adequately isolated from the water supply. A team of
researchers at UNC-Chapel Hill and NC State University has developed a more environ-
mentally compatible process for producing fluoropolymers that uses supercritical carbon
dioxide and does not require any surfactants. The process also yields more uniform products
and enables easy, one-step isolation of the final polymer product. DuPont has recently
licensed the technology and commercialized the process at its Fayetteville Works site in
Bladen County, NC. DuPont brought the plant on line in March of 2002. The test and
demonstration phase of the plant was highly successful and the Fayetteville Works site cur-
rently operates at plant-production capacity.
Unconventional High-Efficiency Green Synthesis
In the area of alternate reaction conditions. Professor Bose and his group have conducted
microwave chemistry with limited amounts of solvents or even no solvents. Many useful syn-
thetic reactions are exothermic and require only initiation by a short burst of microwrave
energy to go to completion. This "Microwave Jump Start", as devised by Professor Bose,
would save energy and, thus, reduce the cost of producing pharmaceuticaJs. Second, Professor
Bose has developed ''Grindstone Chemistry" for conducting solvent-free exothermic reac-
tions for pharmaceuticals on small and large scale by grinding reagents together. Using
friction-activating agents, he has extended this method to solid/liquid and even liquid/liquid
reagents. Third, he has devised water-based biphasic media for exothermic synthetic reactions
that are complete in approximately 20 minutes, as compared to several hours for classical
methods. For these exothermic reactions, he stirs the reagents (no solvent) and a catalyst in a
large volume of water. Solid products separate as crystalline material in good yield. These sol-
vent-free techniques constitute energy-efficient green chemistry. Indofinc Chemical
Company has tested Professor Bose's water-based biphasic media for the synthesis of
coumarin-3-ester, obtaining excellent yield and high purity.
In the area of alternate pathways, Professor Bose and his group have used nontoxic
reagents and new oxidizing agents to develop an eco-friendly alternative synthesis of
Dapsone, an anti-leprosy drug also used for AIDS patients.
16
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Advanced Marine Technologies (AMT): Reducing
Nitrates in Buzzards Bay by Producing Organic Gem®
Fertilizer from New Bedford's Fish Processing Wastes
(A Sustainable Greater New Bedford Project)
AMT manufactures Organic Gem* fertilizer in New Bedford, Massachusetts using
approximately 7% of the 50 million pounds of fresh fish scraps typically generated by the
30 to 35 local processors each year. Organic Gem® (OG), certified by the Organic Materials
Review Institute, was first made from the byproduct of AMT's nutraceutical extraction of
marine cartilage. AMT has developed a unique enzymatic digestion engine (EDE) using pro-
prietary enzymes that accelerate optimal digestion. The EDE strictly controls factors that
could potentially denature enzymes and proteins; it also leaves oils, collagens, and lipids in
their natural state. It is a fast, "cold" process that delivers a low-odor, efficiently absorbed fer-
tilizer to increase plant yield and pest resistance. Presently, its markets include golf courses,
turf farms, vineyards, hops, fruit trees, potatoes, cranberries, home gardens, and other crops.
In New Bedford, the Increased manufacture and use of OG delivers a triple economic and
environmental benefit: (1) OG decreases the quantities and costs offish wastes going to land-
fill illegally; (2) OG reduces nitrate discharges from the wastewater treatment plant into
Buzzards Bay, a prime recreation area; and (3) OG minimizes agricultural runoff of nitrates
from petrochemical-based fertilizers. With their innovative processor supply chain approach,
AMT anticipates servicing 100% of the local wastes within the decade. Their plans now call
for new EDE installations to bring cost savings to other processors and environmental bene-
fits to other ports.
Biocatalytically Synthesized High-Performance Novel
Antioxidants for Materials
NOTE: This project is the result of a partnership between Polnox Corporation and Dr.
Ashok L. Cholli of the University of Massachusetts. This project was judged in both the aca-
demic and Industry categories. The project summary appears in the academic entries section
on page 9-
A Clean and Economic Biocatalytic Process for the Key
Chiral Intermediate for Atorvastatin Using Three
Evolved Enzymes
Codexis has designed, enabled, and developed an innovative green process for commer-
cial production of ethyl (7f)-4-cyano-3-hydroxybutyrate, the key chiral intermediate in the
synthesis of atorvastatin (Lipitor®). Previous commercial processes involve kinetic resolution
(50% maximum yield) or syntheses from chiral pool precursors involving bromine chemistry.
These processes ultimately substitute cyanide for halide under heated alkaline conditions,
AMI BioProdycts
Corporation
Polnox Corporation
Codexis, Inc.
17
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MeasureNet
Technology, Inc.
forming extensive byproducts and requiring high-vacuum fractional distillation of the final
product.
The nominated technology is an alternative process using basic feedstocks and two exquis-
itely clean biocatalytic reactions under neutral conditions. Codexis developed each of three
enzymes using directed evolution technologies to provide the activity, selectivity, and stabili-
ty required for a practical and economic process. In the first step, two enzymes catalyze the
exquisitely enantioselective reduction of a prochiral chloroketone to an enantiopure chloro-
hydrin. In the second step, the third enzyme catalyzes the novel biocatalytic cyanation of
the chlorohydrin to the cyanohydrin under neutral conditions. The evolution and develop-
ment program has improved the volumetric productivity of the reduction reaction on a
biocatalyst basis by approximately 100-fold and that of the cyanation reaction by approxi-
mately 1000-fold. Codexis has used the evolved biocatalysts to produce ethyl
(/?)-4-cyano-3-hydroxybutyrate at semiworks scale in such purity that there is no need for
fractional distillation of the product. In July 2004, Codexis shipped over 1,000 kg of this
product to a customer for testing.
Data-Collection Technology that Minimizes
Environmental Impact through Intelligent Design
With the growing emphasis on science education at all levels of academia, more and more
educators are using electronic data collection in the laboratory. PC-based systems have advan-
tages over traditional analog methods, but the operational and environmental costs are
difficult to justify. Educators are burdened with the high energy costs, maintenance, and
replacement of PCs; the environment is burdened with society's lack of a refined recycling
infrastructure for the disposal of electronic equipment. Institutions face a dilemma: how to
modernize their laboratories without inflating their operational and administrative overhead
while remaining responsible stewards of the environment.
MeasureNet Technology's innovative design Introduces students to the advantages of elec-
tronic data collection without the costs, waste, and pollution associated with PC-based
systems. MeasureNet Technology's unique network design replaces up to 12 conventional
PCs and interfaces with a single network controller and MeasureNet PC. This system com-
bines improved energy efficiency, high-quality measuring capability, simplified instrument
operation, and reduced maintenance. MeasureNet Technology was a winner of the 2002
Ohio Governor's Award for Excellence in Energy Efficiency. Each year, one MeasureNet
System saves 16,000 kWh of electricity, prevents 18.9 tons of CC>2 emissions, saves 8.5 tons
of coal, and saves $1,700 in energy costs compared to PC-based systems. Replacing just one
MeasureNet PC at its obsolescence, instead of 12 PCs, keeps 26 cubic feet of waste,
66 pounds of lead, and other environmental toxins associated with PC disposal away from
the nation's landfills. Simplified instrument operation and reduced maintenance allow stu-
dents and educators more time for analysis and discussion, as well as more time for real
learning.
Wentana Research
Corporation
Development of High-Performance Environmentally
Benign Lapping Fluids for Hard Disk Drive
Manufacturing Applications
Magnetic hard drives are an essential component of computer hardware and handheld
consumer electronic devices today. At the heart of these drives lies a giant magnetorestrictive
(GMR) read/write head situated closely above a rapidly rotating magnetic hard disk. The
18
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GMR head surfaces must be highly polished to ensure their reliable operation within hard
drives. Conventional lapping fluids used to polish heads are composed of fine diamond abra-
sive powder dispersed within toxic nonaqueous solvents such as ethylene glycol. These
solvent-based lapping fluids pose significant handling and disposal concerns for hard disk
manufacturers.
Ventana Research has developed a new class of benign synthetic copolymers whose aque-
ous solutions have been shown to be highly effective at lapping GMR read/write heads. These
copolymers have an aspartate/aspartamide backbone and pendant combs containing a phe-
nolic oligomer photochemical functionality (i.e., gallate esters). Besides being nontoxic and
environmentally friendly, these copolymers are capable of polishing GMR read/write heads
more rapidly and efficiently than conventional lapping fluids. This affords manufacturers
considerable savings by increasing production rates and reducing waste disposal costs. Pace
Technologies, a major worldwide distributor of polishing consumables, has begun distribut-
ing Ventana's lapping fluid to manufacturers of hard drives as well as to manufacturers of
other products that require precision polishing, such as optical lenses and flat-panel displays.
A Dry and Environmentally Superior Process for the
Recovery of Phosphoric Acid from Phosphate Ore
The current processes used to manufacture phosphoric acid from phosphate rock are the
thermal process and the wet-acid process. The thermal process is an electric reduction process
that requires low-cost electricity; it is somewhat uncompetitive with the cheaper wet process.
The wet process uses sulfuric acid to acidulate the phosphate rock, however, and produces
vast quantities of both phosphogypsum (i.e., calcium sulfate) and process pond water. The
phosphogypsum and pond water are both significant environmental problems. Currently,
there are about one billion tons of waste phosphogypsum in Florida, clustered in the major
phosphate-producing areas in the center and north of the state. This waste phosphogypsum
contains radioactive radium sulfate and so is unsuitable for common phosphogypsum uses,
such as wallboard.
The process developed by Carolina Process Associates uses almost-worthless high-magne-
sium phosphate rock as its first component. The poor quality of this rock makes it unsuitable
for either the wet process or the thermal process. The second component is either rejected
sand from the phosphate beneficiation process or another low-grade silica. The third com-
ponent is a high-sulfur carbon source, such as waste petroleum coke. Carolina Process
Associates uses binders to form these three components into pellets. It then roasts the pellets
to generate a mixed phosphoric and sulfuric acid product and a clinker material, used as a
raw material for aggregates. After chemical separation from the sulfuric acid, the phosphoric
acid is suitable for commercial use in both technical and food-grade applications. Overall,
the Carolina process uses waste materials, obtains a 98% yield at temperatures at least
100 to 150 °C lower than competing processes, and generates no wastes. The next step is a
pilot plant to process about 500 pounds per hour.
Ecological Paint
Innovative Formulation Company has developed Ecological Paint as a safe alternative to
all those existing paints that do not comply with the requirements of Federal Regulation 29
CFR 1910-1200 and that also contain hazardous substances listed in California's Proposition
65- Ecological Paint was developed for chemically sensitive people and for those who suffer
long-term exposure to the hazardous substances commonly found in other paints. The paint
Carolina Process
Associates, Inc.
Inncnratiwe
Formulation Company
19
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METSS Corporation
Harris Labs
contains no known carcinogens, neurotoxins, or volatile organic compounds (VOCs); it has
no hazardous metals, formaldehydes, leads, mercury, chrome, ethylene glycol, phthalates,
benzenes, hazardous air pollutants (HAPs) or APES. It has virtually no odor and is hypoal-
lergenic. Its only solvent is water. It sacrifices no performance in achieving this and actually
outperforms most other paints in many areas such as coverage, hide, and ease of application.
It has none of the blocking or adhesion problems normally associated with other low- or zero-
VOC products.
Ecological Paint is a multishcllcd, acrylated nanopolymcr that is 100 percent acrylic. Its
unique formulation and pigmentation shift the heat spectrum off the paint without affecting
the visible color, even in the darker color spectrum; these features provide significant energy
savings during the warmer months. Ecological Paint is being manufactured at the company's
facility in Tucson, Arizona. It has been used in historical restorations as well as in environ-
mentally sensitive locations.
Environmentally Friendly Aircraft Deicing Fluid
METSS Aircraft Deicing Fluid-2 (ADF-2) represents a new class of aircraft deicing fluid
designed as an environmentally friendly alternative to traditional ethylene and propylcnc gly-
col-based fluids. METSS ADF-2 is composed primarily of food-grade materials derived from
abundant and renewable agricultural feedstocks that are both economical and readily avail-
able. Unlike ethylene glycol-based fluids, METSS ADF-2 is nontoxic and nonhazardous to
plant and animal life. It contains neither phosphates nor urea, which tend to promote
eutrophication of natural waterways and may lead to fish kills. METSS ADF-2 biodegrades
readily and completely to carbon dioxide and water. METSS ADF-2 has a lower Biological
Oxygen Demand (BOD) and biodegrades at a slower rate than propylene glycol.
Commercial airports and military bases are increasingly concerned about the quality of
storm water runoff and the effect of deicing chemicals on receiving waters. If storm water
drains directly from runways and taxiways into a body of water, discharge permits require reg-
ular monitoring to determine BOD, contaminants, and other properties. Due to its low
BOD, METSS ADF-2 can help airport managers achieve environmental compliance.
METSS ADF-2 meets all requirements of the SAE AMS 1424D for aircraft deicing fluids.
The U.S. Air Force, the Federal Aviation Administration, and Transport Canada have all
approved METSS ADF-2; this product has been in commercial use since October 2003-
Evapo-Rust™: Nonhazardous Rust Removal by
Selective Chelation
Economic loss in the U.S. to corrosion costs $276 billion annually. Traditional methods
of corrosion (or rust) removal include acids, caustics, converters, electrolysis, and mechani-
cal. Their low purchase price is only a small portion of their true cost. These methods are
major contributors to hazardous disposal, emissions, and human health problems. They use
materials that are toxic, are corrosive, and can create explosive gasses and release volatile
organic compounds (VOCs) and hazardous air pollutants (HAPs). Waste from these meth-
ods may contain heavy metals, paint, grease, oil, and various organic materials.
Harris Labs has invented an industrial replacement to remove and control corrosion in
iron preparations. Evapo-Rust1M is nontoxic, nonhazardous, nonflammable chemical with a
targeted process of removing rust (iron oxide). Evapo-Rust™ removes the iron oxide into
solution by a proprietary process called selective chelation. The active ingredient in Evapo-
Rust™ is an ester of a polyphosphoric acid with an amine. Following chelation, a sulfur
20
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compound removes the iron from the chelator to form a ferric sulfate complex, regenerating
the chelator. As the normal operational pH is between 6 and 7, the solution is never haz-
ardous to handle, store, or dispose of in neat form. Personal protective equipment (PPE) is
not required with Evapo-Rust™, making it an excellent industrial and consumer product.
There are no air or ground transportation restrictions for Evapo-Rust1M. Waste generated by
Evapo-Rust1M is typically nonhazardous; the spent ferric sulfate has potential for use as a lawn
and garden fertilizer. Evapo-Rust1M has been implemented in general industrial and strategic
Department of Defense installations.
GreenEarth Cleaning: Dry Cleaning With
Silicone Solvent
Historically, solvents used for dry cleaning fabrics have been hazardous to soil, ground-
water, air, and industry employees. GreenEarth Cleaning (GEC) has developed and patented
a process using a cyclic siloxane (i.e., decamethylcyclopentasiloxane) that is a safe and viable
alternative.
Prior to commercializing this process, GEC conducted beta-testing at 27 retail dry clean-
ing sites in the U.S. over a 10-month period. During this period, 2,000,000 pounds of
clothing were processed, and independent, certified testing laboratories performed more than
26,000 test measurements on air and waste streams, proving the process is safe for the envi-
ronment and employees. Beta-test sites also reduced the volume of their solid waste by
40-65%. The GEC silicone does not impact air quality because it is not volatile. Tests con-
firm that it will not impact soil or groundwater, as it degrades to SiCh, CO;?, and HbO within
28 days.
GEC has licensed this process at 727 locations in the U.S., Canada, England, Ireland,
Sweden, Japan, Brazil, and Germany, with growing acceptance based on its health, safety, and
environmental profile, as well as its operational advantages.
GreenEarth Cleaning,
L.L.C.
Green Product and Munitions Compliance Analytical
Systems
Until recently, manufacturers and regulatory agencies were restricted to qualitative, gener-
ic, and intuitive considerations of green chemicals and products (e.g., less harmful to human
health and the environment) because no one had defined quantitative criteria for them.
Chemical Compliance Systems has overcome this deficiency by compiling more than
75,000,000 data elements for over 210,000 chemicals and 250,000 products over the past
20 years. They have synthesized these data into quantitative green chemical and product rat-
ings with their Green Products Compliance Analytical System (GP-CAS) and their Green
Munitions Analytical Compliance System (G-MACS). G-MACS also uses the MIDAS
munitions characterization database from the U.S. Army Defense Ammunition Center. Both
GP-CAS and G-MACS are based upon 46 green chemical criteria, each normalized on a scale
of 0% (least green) to 100% (most green). These criteria encompass a broad spectrum of eco-
logical, health, and safety hazards. Both of these systems also identify which of 475 state,
federal, and international regulatory lists include each chemical constituent of a product.
Both systems can complete green analyses in 10-30 seconds. Any industry, facility, or loca-
tion can utilize these systems, which have been available on the Internet since November
2003. GP-CAS and G-MACS can reap economic benefits throughout the product lifecycle.
Chemical Compliance Systems can readily customize either system for special requirements
and maintain confidentiality. Incorporation of these green analyses into complementary ana-
Chemical Compliance
Systems, Inc.
21
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Montana Biotech SE,
Inc.
W.F. Taylor Co., Inc.
lyrical systems is underway (e.g., their MSDS retrieval and manufacturing—import—export
systems). No other capabilities of this type currently exist.
Levan: A Renewable Raw Material for Several
Industries
Levan, a polyfructan produced from sugar, can replace petrochemicals in many applica-
tions. For example, all industrial sectors use adhesives in everything from book bindings to
automobiles, yet, 96% of adhesives are currently derived from a single nonrcncwablc
resource: petroleum. A search tor an environmentally friendly adhesive identified levan with
a tensile strength up to 1,500 psi on aluminum. Montana Biotech SE has devised a cost-effec-
tive method to produce levan by large-scale fermentation.
Montana Biotech SE has developed two forms of levan. The water-soluble version is use-
ful for temporary bonds and for select indoor applications. The cross-linked version can
survive soaking in water for an extended time and can join difficult-to-bond plastics. Water-
resistant levan can be used in the high-volume wood adhesive market. Levan could
potentially be extruded to make a biodegradable plastic. Levan is safe to eat; it occurs natu-
rally in many plants. In lab studies, levan has been shown to lower cholesterol.
Levan is a multifunctional, green, raw material. It meets three standards: (1) Safety: levan
is safe for users and the environment. (2) Sustainability: levan is derived from a renewable
resource. (3) Security: the feedstock is obtained from sugar beets and sugar cane, both pro-
duced in the U.S. and many regions around the world.
Meta-Tec™ Low-VOC, One-Component, Cross-Linking
Adhesive: Innovative Science—Applied Technology
Traditional flooring adhesives (defined as one- or two-part reactive systems that are ure-
thanc-, cpoxy-, solvent-, or water-based) include various industrial solvents and consume
nonrenewable resources. The manufacturing and application processes for these adhesives can
also create large amounts of hazardous waste byproducts and emissions. It is estimated that
over 23 million pounds of volatile organic compounds (VOCs) are released to the environ-
ment annually from these products.
Meta-Tec™ technology is a unique class of adhesive chemistry properly designated as a
low-VOC, reactive, one-part, self-cross-linking adhesive. The adhesives based on this chem-
istry consist of a viscous mixture of drying oils (such as soybean oil, linseed oil, and sunflower
oil), inorganic fillers, renewable tackifiers (such as rosins), polymers with carboxyl function-
alities, metal catalysts, and a nontoxic cross-linking agent. Although these adhesives have
performance characteristics previously exhibited only by reactive systems such as urcthancs
and epoxies, they contain very low VOCs and use more renewable resources. With the high
volume of adhesives used throughout the flooring industry, the ability ofTaylor's Meta-Tec™
technology to eliminate the risks associated with volatile hazardous chemicals through reduc-
tion of VOCs promises to have a significant positive impact upon the environment and on
human health. The use of just one product, Meta-Tec™ 2071 Wood Flooring Adhesive,
would potentially prevent over 9 million pounds of solvents from entering the atmosphere.
This product is projected to capture over 25% (25 million pounds) of the market share by
the end of 2005.
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MYCELX Technology: Synthesis and Use of a Curable
Viscoelastic Polymeric Surface-Active Agent in the
Removal of Organic Pollutants from Aqueous and
Airborne Influent Streams
MYCELX technology uses biomimetic pathways to produce MYCELX chemistry, which
is the reaction product of drying oils and methacrylate polymers. MYCELX chemistry can
be considered one of the first commercially available products utilizing self-assembling syn-
thetic pathways similar to those used by biological systems. The combination of biomolcculcs
and synthetic acrylates in MYCELX chemistry results in novel properties that are not pos-
sessed by conventional synthetic polymers. MYCELX chemistry possesses a combination of
novel properties: broad affinity, curability, and viscoelasticity. Affinity refers to the ability of
MYCELX-infused substrates to bind together and immobilize disparate phases of organic
compounds without future separation or desorption. Curability allows the MYCELX chem-
istry to be cured into practically any filter substrate and cured dry with full transfer of
properties. Viscoelasticity allows MYCELX-infused filters to capture and immobilize organ-
ic compounds to filter saturation without any additional differential pressure across the filter.
MYCELX-infused filters are able to remove emulsified organic compounds (e.g., from naval
and marine bilge water), PCBs and other persistent organic pollutants, oil mists from air, and
tramp oils in less than one second contact time without desorption. MYCELX technology
has been commercialized and is used in a wide variety of industrial, marine, and commercial
applications, both in the U.S. and internationally.
Mycopesticides and Mycoattractants
Entomopathogenic fungi kill insects and use their carcasses as platforms for disseminat-
ing spores. Because spores of certain entomopathogenic fungi repel termites and ants,
however, widespread commercialization by the pesticide industry has been limited.
Fungi Perfect! has discovered that ants and flies are attracted to entomopathogenic fungi
in their mycelial state, prior to sporulation. The company has received a patent for a tech-
nique to deploy the presporulating mycelium of the entomopathogenic fungus Metarhizium
anisopliae as a natural agent to attract and kill termites and ants. More patents arc pending.
They have isolated cultures of fungi from naturally infected insects, cultured these fungi in
the laboratory, and used a selection process to create strains that delay spore production for
several weeks. The presporulating entomopathogenic mycelia emit powerful attractants and
feeding stimulants, drawing select pests to a chosen locus, from which they then spread the
infectious fungi throughout the targeted nest and ultimately to the queen. In choice tests, ter-
mites prefer the presporulating mycelium of Metarhizium anisopliae to wood as food.
Research shows that diverse insect species share specific affinities to these fungi in their pres-
porulating state. This discovery may well lead to novel methods for controlling insect pests
worldwide. This mycotechnology is economical, is scaleable, and uses cell culture methods
currently in practice.
New Biomass Catalytic Reforming Process for Solid
Oxide Fuel Cell Power Generation
Zivatech's technology is based on analyzing, testing, and evaluating a newr reforming
process for converting biomass and other secondary waste streams into a syngas outlet stream
rich in hydrogen gas for powering a directly interconnected solid oxide fuel cell (SOFC).
MYCELX Technologies
Corp.
Fungi Perfect!, LLC
Zivalech
23
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The LATA Group, Inc.
Specialty Fertilizer
Products
These waste sources are rich in methane and carbon dioxide; the new process uses an effec-
tive catalytic reformer to convert them efficiently into a syngas outlet stream. The stream is
used as feed into the anode of an integrated fuel cell of a solid oxide structure.
Conversion of these waste streams to synthesis gas for use in SOFC-based electricity gen-
eration systems is of increasing importance to both commercial and remote residential energy
consumers from energetic, economic, and clean energy points of view. Renewable waste bio-
gas resources are of increased interest to the clean and highly efficient energy generation
market. In addition, Zivatech's innovative process to convert carbon dioxide-rich methane gas
inside an in-situ reactor using their reaction and catalysis system is under increased consider-
ation in current and future industrial efforts. This is considered an additional benefit of
Zivatech's work. Projected energy and capital savings from the use of the integrated new
process are in the 30 to 35% range compared to existing natural gas- and diesel-based direct
combustion technology.
New Green Technology for Eliminating Hydrogen
Sulfide in Aqueous Systems, Especially Petroleum
Industry Systems
Geo-Microbial Technologies and its subsidiary, the LATA Group, have been pioneers in
biological research and development for nearly 20 years. Their work has resulted in biologi-
cal processes and products that destroy and prevent biogenic hydrogen sulflde (H^S) in
petroleum reservoirs and water systems inherent in oil and gas production and other indus-
trial operations. Their technology is important because deadly Hj.S emissions have caused
innumerable deaths and injuries, especially in the oil and gas industry.
LATAs Bio-Competitive Exclusion (BCX) technology is designed to attack the source of
H;>S: the reduction of soluble sulfate (SCXj) in the water by indigenous sulfate-reducing bac-
teria (SRB). The BCX process is initiated and sustained by patented, environmentally
friendly inorganic nitrate and nitrite formulae (named Max-Well 2000) that target and
directly manipulate the indigenous microflora of hydrocarbon-bearing reservoirs and a wide
variety of surface water systems. Max-Well 2000 formulae act at low concentrations as alter-
nate electron acceptors for targeted nitrate-reducing bacteria (NRB) that flourish and
out-compete SRB for essential growth nutrients needed to reduce sulfate to sulflde. The
nitrite component reacts chemically with existing Hj.S to form soluble, nonhazardous sulfate
(SO/O; in addition, it is toxic to SRB. Certain Thiobetccillus NRB species that are stimulated
by the nitrate in Max-Well 2000 also attack and degrade existing H^S. The results of the
growth of beneficial NRB microbial populations are the production of nonhazardous nitro-
gen gas, the elimination of existing H^S, and continuous blocking of HjS production. The
oil and gas industry has responded favorably to the BCX technology, as evidenced by a grow-
ing commercial business.
A New Polymer Coating for Increasing Efficiency of
Phosphorous Use and Reducing Environmental Impact
Although phosphorus is an essential nutrient for plant growth, it can be toxic to man and
the environment. Some sources of phosphorus fertilizer contain high levels of cadmium,
which can accumulate in crops and have long-term toxicity to man. Phosphorus fertilizers are
inefficient: crops typically take up no more than 20-25 percent of the applied phosphorus
during the first year of application due to fixation of the phosphorus by antagonistic cations
24
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ill the soil. As a result, phosphorus accumulates in the soil, runs off into waterways, and caus-
es toxic algae blooms that deplete oxygen for aquatic life.
Specialty Fertilizer Products has developed and patented a family of water-soluble, non-
toxic, biodegradable copolymers made from itaconic acid (a monomer derived by
fermentation of renewable agricultural resources) and maleic acid. These copolymers are
applied directly to granular phosphorus fertilizers as a coating or mixed into liquid fertilizers.
Used along with phosphorus fertilizers, these dicarboxylic anionic copolymers lessen or elim-
inate the fixation of phosphorus, increasing the availability of phosphorus to crops. The high
cation-exchange capacity of these polymers interferes with the normal phosphorus fixation
reactions in soil. As a result, more of the applied phosphorus accumulates in crop biomass,
crop yields increase, farm profits improve, less cadmium accumulates in crops, and negative
environmental impacts are lessened.
On-Site Generation of Mixed Oxidants Using Sodium
Chloride Brine as a Safe Alternative for Chlorine Gas
Disinfection
Water disinfection using chlorine gas has saved countless lives in the U.S. and the world
over the past 100 years. Chlorine gas is a hazardous material that is pervasive in U.S. com-
munities and around the world. MIOX has demonstrated that on-sitc generation of
chlorine-based mixed oxidants from low-cost sodium chloride brine is superior to chlorine
gas for disinfection, even inactivating waterborne pathogens immune to chlorine gas disin-
fection. The MIOX process eliminates all of the hazards associated with chlorine disinfection.
The technology is scalable from individual use to large municipalities. It offers significant
chemistry benefits: a microflocculating effect that improves water clarification processes,
reduction in byproducts of chlorine disinfection, elimination of taste and odor, maintenance
of required residual chlorine in water distribution systems, and elimination of biofllms.
MIOX now has over 1,000 large installations across the U.S. and in 20 foreign countries,
replacing over 20 tons of chlorine gas per day, with a capacity to treat over 1 billion gallons
of water per day and serve 6 million people. Since 2003, MIOX has teamed with Cascade
Design, Inc./Mountain Safety Research to offer its purifier to the U.S. military, the camping
and recreation markets, foreign travelers, disaster relief workers, and others.
PICKLEX®: An Environmentally Safe Metal Surface
Preparation and Pretreatment Chemical
Governments all over the world are trying to ban the use of chromate conversion coating
on aluminum and other nonferrous metals. PICKL-EX*' replaces this traditional chromate
process as well as the zinc phosphate process used to pretreat steel. PICKLEX* is an envi-
ronmentally safe, nonhazardous, water-based product. In one treatment, it removes surface
rust, white rust, weld scale, and laser scale from metal surfaces and also provides coating.
Applied to a metal surface, PICKLEX® provides long-term rust protection. Used to prepare,
treat, and coat metal surfaces prior to finishing, it requires no waste treatment or disposal at
all. PICKLEX® works at room temperature and, therefore, requires no special heating system.
Users can apply it easily to a metal surface with a sprayer, with a brush, or simply by dipping
the metal item into a bath of PICKLEX®. The U.S. EPA's laboratory in Cincinnati, Ohio has
tested this product and validated it as a nonpolluting, cost-effective conditioner for metal sur-
faces.
MIOX Corporation
International Chemical
Products, Inc.
25
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Pantheon Chemical
Recovery Systems, Inc.
This single product is the answer to a host of pollution problems associated with many of
today's metal treatment chemicals. Many small and medium-sized companies have been
using PICKLEX® in its various grades since 1997 and have experienced exceptional results
with zero waste for disposal. In addition, PICKLEX® 20 (a derivative of PICKLEX®) has
been used by several large companies, including one that fabricates steel structures for the
military.
PreKote® Surface Pretreatment: Replacing Hexavalent
Chrome with an Environmentally Safe Solution
Hexavalcnt chrome (Cr(VI)) is the industry standard for corrosion protection on aluminum
substrates prior to painting. Cr(VI) is toxic and hazardous. Discontinuing its use has been an
EPA pollution prevention priority through Executive Order 12856 since 1993- Cr(VI) is also on
the European End of Life Vehicles (ELV) Directive of nonallowable materials. In 1994, Pantheon
Chemical began an extensive research program to find an environmentally safe replacement for
chrome-based chemistries. Pantheon designed PreKote® Surface Pretreatment on the molecular
level from environmentally safe chemicals to clean and promote paint adhesion to substrates to
be coated. PreKote*' is a neutral, alkaline, non-metal-based solution. After years of extensive lab-
oratory and field tests utilizing highly advanced techniques of surface analysis and molecular
modeling, Pantheon introduced PreKote® to the United States market as an efficient and green
substitute for chromatc chemistry.
The U.S. Air Force (USAF) has approved and implemented the use of PreKote® as an alu-
minum prepaint surface pretreatment process to replace Cr(VI). Following this success, the
commercial aerospace market tested and has begun to use PreKote®. This technology decreas-
es operational costs significantly (by simplifying and reducing process procedures), eliminates
heavy metal waste streams, replaces toxic acids and solvents, improves the safety, health, and
morale of workers, provides superior performance, and is environmentally compliant.
Process for Treatment of Hog Waste and Production of
Saleable Products from This Waste
Industrial hog production creates a large amount of liquid and solid waste, which is typ-
ically flushed into an open lagoon or sprayed onto fields, causing a number of environmental
and human health problems. Recovery Systems has developed an alternative process to treat
the waste and recover valuable products from it. The overall scheme consists of a processing
unit on each farm and a central processing plant serving 15 to 20 farms. This process is
expected to satisfy the state requirements for a waiver of the current moratorium on the
expansion of hog farms in North Carolina.
In the Recovery Systems process, the waste is flushed out of the bam to a surge tank and
pumped to mix tanks, where lime slurry is added to raise the pH. At this higher pH, the col-
loidal bonds of the solids and the urea break down to release ammonia. The lime treatment
kills over 99% of all pathogens. The slurry is then pumped through an ammonia stripper; the
ammonia-laden air is exhausted through a phosphoric acid reactor and the resulting ammo-
nium phosphate is pumped to a storage tank. Next, the slurry is pumped to a solids
separation tank, where coagulant and flocculcnt arc added to separate the solids from the liq-
uid. The solids are pumped to a vibrating screen washer, where the undigested feed is
separated from the digested fecal solids. The liquid from the solids separation tank is pumped
to a storage tank to be used in the flushing process. The digested solids are processed in a
methane generator, which also concentrates the nutrients to produce organic fertilizer. Tests
26
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by North Carolina State University show that the undigested feed is suitable as cattle feed and
poultry litter. Well water is used to dilute the supersaturated salts in the flushing liquid.
Recovery Systems will be testing its process on a one-of-a-kind U.S. EPA test hog farm in
Lizzie, North Carolina.
Renewable Feedstock to Marketable Products
Changing World Technologies, Inc. (CWT) has successfully developed and patented a
thermal conversion process (TCP) that converts renewable feedstocks into clean fuels and
specialty chemicals for industrial and commercial use. The basic technology emulates the
Earth's natural geological and geothermal processes: it uses heat and pressure to convert
organic material into fossil fuels. The TCP accelerates these natural processes using basic
chemistry and process technology in a completely enclosed system, thereby reducing the
bioremediation process from millions of years to mere hours. The design of the system
ensures that there is minimal odor, dust, fumes, smoke, gas, or excessive noise in the system.
The TCP product streams include a clean fuel-gas, light organic oil, a carbon product, an
aqueous nitrogen fertilizer, and a mineral soil amendment. The TCP does not create any neg-
ative byproducts.
A 200-ton-per-day demonstration biorefmery plant is now operating in Carthage,
Missouri, using renewable turkey offal from a nearby processing plant. CWT projects that
this plant will produce oil at a cost of approximately $33 per barrel with tipping fees and pro-
duction credits. CWT is designing and constructing a larger plant that will operate on mixed
agricultural waste. CWT estimates that large plants operating with mature versions of TCP
technology using shredder residue and scrap tires could have an oil production cost of as lit-
tle as $14 per barrel with tipping fees and production credits.
Renewable-Resource-Based, Environmentally Benign
DeicinglAnti-Icing (D/A) Agents
The new METSS/MLI technology for Deicing/Anti-Icing (D/A) agents is a fundamen-
tal, innovative chemical method that prevents pollution through source reduction. It uses
abundant natural resources and agrichemical waste streams, such as biodiesel and biobased
polymers. These D/A agents represent a new class of materials designed and used as alterna-
tives to traditional glycol-based fluids. The first technical focus of the project has been to
understand the synergism between components of D/A agents in order to reduce the use of
environmentally destructive D/A agents, such as chloride salts and glycols. A second focus has
been to use waste streams from critical biofuel energy independence products in D/A for-
mulations.
This chemistry has led to a wide array of products, many of which are now in or near
commercial use. The METSS/MLI biomass-based fluids are infinitely soluble in water, are
nontoxic, and act as corrosion inhibitors for ferrous metals. They can be applied to a wide
variety of surfaces. Sales of these fluids in the highway and facilities market have reached over
16 million gallons per year. METSS's aircraft deicing fluid has Federal Aviation
Administration (FAA) approval and has begun commercial sales; a deicing product for run-
ways has been sold to the U.S. Air Force. These products reduce the nations reliance on
petroleum, assist the use of biofuels, and reduce impacts on health and the environment rel-
ative to traditional glycol-based fluids.
Changing World
Technologies, Inc.
MLI Associates
-------
Cleary Chemical
Company
Rynex Holdings, Ltd.
Atmospheric Glow
Technologies, Inc.
ROACH TERMINAL'™ Insect Control: A Nontoxic
Alternative that Prevents the Development of Pest
Cockroach Populations
Cleary Chemical Company has developed and commercialized Roach TerminalIM, an
insecticidal bait supplied as a gel or in a bait tray. In 1999, the U.S. EPA registered Roach
Terminal™ as a biopesticide. Roach Terminal™ has been tested successfully on the German
cockroach, the most important household pest worldwide. This insect, like many others,
stores uric acid as a source of nitrogen for retrieval during neogenesis of tissue and embryo
development.
Roach Terminal™ has a novel mode of action. The active ingredient, termed a nutrition-
al metabolism disrupter, is a composition of oxypurinol and xanthine, which act in concert
to inhibit xanthine oxidase, a key enzyme in the metabolic pathway that produces uric acid.
Oxypurinol is a metabolite of a human gout medication; xanthine is found naturally in foods.
Cleary incorporates this active ingredient into an inert bait matrix designed to enhance the
effects of the active ingredient and to attract the target pests. The insects founder when they
deplete their reserves of uric acid precipitately during mating, molting, or embryo develop-
ment and then cannot replenish their uric acid supply. Because they are not killed by direct
toxic action, the dead insects do not contain any toxin that can move into the environment
by secondary consumption. Roach Terminal1M affects insecticide-resistant and susceptible
cockroach strains equally, indicating that there is no cross-resistance from other mechanisms.
RYNE^Dry Cleaning Solution
Rynex Holdings, Ltd. has developed, demonstrated, and implemented an environmen-
tally safe and effective dry cleaning solvent that is economical and recyclable. RYNEX®
replaces traditional hazardous dry cleaning solvents including perchloroethylene and
Stoddard solvent. It is composed of an oxygenated surfactant, specifically dipropylene glycol
f-butyl ether (DPTB), and water. This patented technology effectively removes water- and
oil-soluble stains without the damage to delicate fibers that can occur with other dry clean-
ing and wet cleaning methods. RYNEX® is a complete solvent with no hazardous air or water
pollutants. It has the advantage of attracting water molecules to form a water-solvent com-
plex that exhibits extraordinary cleaning capabilities. The performance of RYNEX® is better
than that of all other solvents available to the dry cleaning industry today. RYNEX® has low
volatility and is not flammable, carcinogenic, bioaccumulative, or persistent in the environ-
ment. It separates from water to allow the removal of dirt, grease, and soil without additional
soaps. RYNEX® cleans water-soluble and oil-soluble stains, providing effective detergency
and compatibility with existing machinery. It has superior cleaning abilities; it does not cause
fabrics to shrink or cause any types of dyes to bleed. Its enhancements include greater opti-
cal brightness in garments that are also softer to the hand. Twelve major dry cleaning
distributors are currently selling RYNEX®. It is being used in over 100 locations in the U.S.,
Europe, and Asia.
Sterilization of Medical Devices with Atmospheric
Plasma
Atmospheric Glow Technologies (ACT) has developed an innovative method for cold
sterilization of medical and dental devices using the exhaust of the patented One Atmosphere
Uniform Glow Discharge Plasma® (OAUGDP®). The OAUGDP® operates in air at atmos-
28
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pheric pressure to produce reactive chemical species that include oxygen species, excited mol-
ecular oxygen species (singlet oxygens), superoxide, ozone, and oxygen radicals. The
longer-lived species can be converted outside of the plasma device to sterilize objects beyond
the plasma volume. AGT has performed studies that demonstrate the ability of this technol-
ogy to neutralize bacterial endospores on objects with complex shapes, such as hemostats and
quick disconnects. Recently, AGT successfully passed the Association ot Analytical Chemists
(AOAC) Sporicidal Activity of Disinfectants Test (Official Method 966.04). This test
requires the sterilization of 720 successive carriers. Analysis by AGT indicated that the carri-
ers harbored extraneous organic debris and loads of up to 109 endospores per carrier before
treatment. Materials compatibility studies performed by AGT indicated no obvious alter-
ation in high-density polyethylene or stainless steel following treatment. AGT is maturing the
OAUGDP® technology to provide an alternative means ot low-temperature sterilization that
will ultimately reduce reliance on chemicals such as ethylene oxide and its common nonre-
active diluent, dichlorodifluoromethane (CFC-12), that pose a threat to human health and
the environment.
Stoller ROOT FEED for Crop Production: Reduction in
Fertilizer Pollution, More Efficacy of Pesticides,
Increased Yield, Increased Quality, and Increased Crop
Plant Disease and Insect Tolerance
Stoller ROOT FEED is a proprietary crop health product, formulated to improve the use
of fertilizer nutrients and, therefore, to decrease nutrient pollution by using minerals, sun-
light, and crop production inputs more efficiently. The technology is based on signaling
mechanisms for enhanced crop production. It recognizes that our crop systems are produc-
ing at about one-fourth to one-third of the genetic potential of the crop seed.
Fundamental to Stoller's technology is an understanding of: (1) the transcriptional regu-
lation of DNA (crop genes) by plant growth regulators, minerals, and small molecules; (2)
the management of translation (synthesis and functionality of proteins—the '"workers" in cells
that make growth happen); and (3) the physiological control of cell growth to enhance crop
performance. Included in Stoller's model is an understanding that the plant growth regula-
tor, auxin, has a major influence on plant growth and that the mineral calcium acts as a
second messenger to assist with the signaling mechanisms.
The Stoller ROOT FEED technology is also innovative with development of an under-
standing that roots of the crop plant are the "control center" ("brains") ot the plant, both
practically and scientifically. ROOT FEED is delivered directly to the roots by drip irriga-
tion, the most efficient and wrater-saving way of irrigating crops, tor maximum crop
regulation and performance.
Stoller STIMULATE: A Natural Product for Improving
Crop Plant Performance and Enhancing Pest Resistance
Stoller formulates STIMULATE with the natural plant growth regulators, auxin, kinctin,
and gibberellin. These plant growth regulators are present in fruits and vegetables; Stoller
often uses them at concentrations lowrer than are present naturally in food.
The focus in crop production has been on ameliorating the imbalance of nitrogen, phos-
phorus, and potassium in fertilizers. By focusing on fertilizer, farmers are generally producing
at only a small fraction of the genetic potential of crop seeds. Stoller has developed a model
Stoller Enterprises, Inc.
Stoller Enterprises, Inc.
29
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Coastwide Laboratories
Microcide, Inc.
that places the growth regulator auxin at the top of plant growth and development control,
an accurate estimate based on recent scientific literature. At least two premises of the Stoller
model are critical to improving crop production. The first is that stress (environmental or bio-
logical) or lack of crop performance is most likely the result of an imbalance of the plant
growth regulators (often referred to as hormones) in a crop plant. The second is that the half-
life of the hormones has to be short in a particular organ of the plant for the rapid signaling
required for "on time" plant growth control. The hormones are either hydrolyzed or conju-
gated after they signal a particular physiological event.
Judicious and timed application of Stoller STIMULATE in drip-irrigated crops increases
crop yields; it reduces fertilizer and water use by 50% per unit of crop production. It also
reduces the use of insecticides and fungicides by 50 to 100% by enhancing a plant's resistance
to insects and tolerance to disease organisms.
Sustainable Earth® Cleaning Products Designed for
Health and the Environment
Commercial cleaning products are used daily by professionals in schools, hospitals, and
commercial facilities. Although cleaning is beneficial, cleaning products commonly contain
chemicals harmful to human and environmental health. High concentrations of these chem-
icals can negatively impact ground-level ozone concentrations, aquatic ecosystems, worker
safety, and human health. Coastwide Laboratories has adopted a strategy that uses green
chemistry to develop products that meet rigorous performance, environmental, and human
health criteria. The strategy involves: (1) fully assessing all ingredients to understand their
potential human health, environmental health, and lifecycle impacts; (2) creating a product
development standard, Sustainable Earth® Green Chemistry standard 114 (SEGC 114), to
establish positive criteria for product efficacy as well as human and environmental health ben-
efits; and (3) formulating products to meet SEGC 114. This strategy results in entirely new
formulations with remarkable benefits. Sustainable Earth® (SE) cleaning products combine
reagents determined to be safer for human and environmental health with a hybrid surfac-
tant system containing a stabilized oxidizing compound. This system eliminates
conventional, potentially problematic ingredients such as alkyl glycol ethers, alkali builders,
alkylphenol ethoxylates, EDTA, and ethanolamine. SE products have increased functionali-
ty and performance, use fewer, more benign ingredients, and reduce waste and emissions.
Current SE products include cleaners for glass, floors, carpets, and washrooms, as well as an
odor eliminator, floor finish, wax stripper, and dust mop treatment. In 2004, sales of SE
products were $1.1 million.
Technology of Safe, Biodegradable, Non-Polluting
Products as Alternatives to Toxic Microbicidal
Chemicals
Almost all traditional, widely used disinfecting and sanitizing products contain ingredi-
ents that are toxic or potentially toxic, are environmentally hazardous, or have a high
potential for accidents. For example, oxidizing chemicals, such as hypochlorite, peracetic
acid, hydrogen peroxide, ozone, and chlorine dioxide, kill microorganisms by indiscriminate
oxidation of organic matter, potentially destroying antioxidants, nutrients, and vitamins
while forming unknown or toxic byproducts, including cancer-causing free radicals. The
non-oxidizing microbicidal quaternary ammonium compounds (QACs; other traditional
30
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disinfectants) inhibit butyl cholinesterase in blood plasma, liver, pancreas, and the white mat-
ter and are unsafe for use on fruits and vegetables because they leave large residues.
Microcide uses ingredients listed by the FDA and EPA in volumes 21 and 40 of the Code
of Federal Regulations (CFR) as biodegradable, generally recognized as safe (GRAS), food
additives, safe, and/or nonpolluting. With these ingredients, Microcide develops broad-spec-
trum microbicidal products as alternatives to toxic and oxidizing chemicals tor the food
processing, personal care, and health industries. Their products use surface-active agents at
low pH. Raising the pH diminishes the microbicidal properties, allowing safe environmen-
tal disposal and biodegradation of the products after use. These products selectively kill
microorganisms on food-contact surfaces, on fresh fruits and vegetables, and on body parts
(including mucosal and skin surfaces) without covalent chemical reactions. The technology
presents alternative products safe for manufacturing, transportation, and use without acci-
dent potential. Two of Microcide's products, PRO-SAN and PRO-SAN L, are EPA-registered
pesticides.
WaterSavr™ Evaporation Control
WaterSavr™, as first developed, reduces drinking water evaporation from reservoirs and
canals effectively and economically. It is a process-controlled powder that is a mixture of cal-
cium hydroxide and long-chain fatty alcohols (w-cetyl and w-stearyl alcohols). "When added
to water, WaterSavr™ yields a self-spreading and self-assembling monolayer film that is two
nanometers thick and has unlimited width and length. WaterSavr™ reduces evaporation by
up to 40%. The United Nations Environmental Programme Centre has designated
WaterSavr1 M as an Environmentally Sound Technology. WaterSavr1 M has been tested in the
Western U.S., as well as in China, India, Morocco, and Spain.
Research is continuing to expand the usefulness of this rapid-spreading monolayer by
adding functions to it. Following successful field and lab trials, WaterSavr Global Solutions
submitted a mosquito larva control version to the U.S. EPA for registration as a pesticide.
Other research focuses on pathogen and pollutant detection through thin-film optimization
of the air/water interface and the inherent advantage of surface sensors over volume sensors.
All versions of WaterSavr™ are biodegradable. The basic WaterSavr™ product reduces evap-
orative losses at a fraction of the cost of new water production, whereas the mosquito-control
version reduces the use of less environmentally friendly chemicals and maintains the active
ingredients at the air/water interface where larvae must breathe.
WT-HSC13: A High-Strength, Low-VOC Aerosol
Adhesive
Westechs WT-HSC13 high-strength canister adhesive is formulated to limit volatile
organic compounds (VOCs), dramatically reducing toxicity and air pollutants. WT-HSC13
contains no chlorinated or cancer-causing solvents (e.g., methylene chloride). Methylene
chloride is a concern in some geographical areas and Westcch has excluded it from the for-
mula. The South Coast Air Quality Management District (SCAQMD) for Los Angeles,
Orange County, Riverside, and San Bernardino requires the VOC level to be less than 80
grams per liter. WT-HSC13 is the only solvent-based canister adhesive on the market that
complies with this regulation. Using an alternative solvent, cyclohexane, "Westechs new for-
mula makes the manufacture of furniture, countertops, RVs, automotive headliners,
manufactured homes, and many other products a safer process for workers, the environment,
and the local population. This product provides a substantially high bonding strength and
WaterSawr
Solutions, Inc.
Westech Aerosol
Corporation
31
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contains more than double the solids or rubber content of other adhesives currently on the
market, resulting in double the coverage. This new technology in chemistry provides a much-
needed solvent-based adhesive. It is strong, affordable, environmentally safe, and adheres to
even the strictest regulations with regard to emissions and pollutants.
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3D Trasar Bio Control
Open recirculating cooling water systems are used by industry for heat rejection. They are
one of the largest users of fresh water (5% of total use); in industrial/power generation sys-
tems, they account for up to 70% of a plant's water use. The warm, nutrient-rich waters of a
cooling system provide an ideal growth medium for microbes. Unchecked, microbial prolif-
eration increases the use of water and energy, shortens equipment life, and increases health
risks.
The biocides used to control microbial activity in cooling systems are among the most
toxic chemicals added to or discharged from these systems. The necessary dose of biocide
depends on time-variable factors such as water chemistry and microbial activity, but opera-
tors often dose systems with excessive biocides to ensure control and preserve a margin for
error. Nalco's 3D Bio Control puts a fluorescent BioReporter molecule, resaumrin, in the
water to continuously monitor the total microbial activity throughout the system. Nalco then
adds biocide only when the BioReporter molecule responds to microbial activity. This
method of continuous monitoring and control allowrs the most efficient use of biocide,
ensures microbial performance, reduces absorbable organic halide (AOX) formation, and
reduces toxic discharge. Following commercialization in April 2004, Nalco had deployed 550
units capable of 3D Bio Control to the field by the end of the year.
Airflex® EF811 Vinyl Acetate Etbylene (VAE) Emulsion
Polymer: A Binder for Environmentally Friendly, High-
Performance, Cost-Effective Architectural Coatings
Air Products Polymers, L.P has solved a regulatory compliance problem for paint manu-
facturers by developing a safer chemical. The architectural coatings industry is being
challenged to implement strict environmental regulations that significantly reduce the level
of volatile organic compounds (VOCs) added to water-based paints as solvents. Vinyl
acrylics, the workhorse polymer for architectural coatings, typically require significant levels
of added solvent. Many of the polymers used in paints currently require added solvent to
form a film that will adequately protect the painted surface. Historically, paint performance
has been significantly compromised as solvent levels are reduced.
Air Products Polymers has developed Airflex® EF811 emulsion, a new vinyl acetate—
ethylene (VAE) copolymer that solves this formulation challenge. Airflex® EF811 emulsion
can be formulated at very low solvent levels, replacing vinyl acetate. Airflex® EF811 emulsion
provides superior performance and is priced similarly to vinyl acrylics. Prior to the develop-
ment of Airflex® EF811, the higher cost of VAEs versus vinyl acrylics had inhibited adoption
of this technology into the large coatings market and its vinyl acrylic segment. Airflex®
EF811 is being purchased or evaluated by most major U.S. paint companies. Broad replace-
ment of vinyl acrylics with Airflex® EF811 emulsion will significantly reduce solvent use,
improving indoor and outdoor air quality.
Nalco Company
Air Products Polymers,
L.P.
33
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DuPonl Company
Savannah River
National Laboratory
Broin Associates
Bioderived Solvents, Surfactants, Fuel Additives, and
Monomers
Many applications of renewable resources require their transformation into platform mol-
ecules, followed by their ready conversion into commercial products. Levulinic acid is one
such platform molecule. Biofine, Inc. (winner of the 1999 Presidential Green Chemistry
Challenge Award in the Small Business Category) discovered a manufacturing process to
make levulinic acid from cellulosic biomass. This process is currently moving toward large-
scale commercial production.
DuPont is taking the next step by developing commercially viable processes that use lev-
ulinic acid, converting it into a host of desired products. DuPont uses novel catalytic
transformations along with other techniques of green chemistry. DuPont is developing
processes to replace petroleum-derived solvents, monomers, and transportation fuels with
products derived from levulinic acid. For example, DuPont has discovered several new, high-
yield routes to levulinic acid esters that are attractive additives to either diesel fuel or gasoline.
Using levulinic acid in ways such as these can reduce dependency on petroleum while con-
suming cellulosic waste.
BioTiger™: Biocatalyst for Accelerated Cleanup of the
Environment
BioTiger™ is a novel, surfactant-producing consortium of 12 nontoxic microbial strains
that remediates polycyclic aromatic hydrocarbons (PAHs) and heavy metals. The BioTiger1M
consortium is highly resilient and effective; it was isolated from an oil refinery in Poland that
had been exposed to extreme environmental conditions, petroleum hydrocarbons, heavy
metals, and associated solvents for over a century. This environmental biocatalyst has prop-
erties and capabilities not demonstrated elsewhere.
The BioTiger™ strains produce biosurfactants during in situ and ex situ remediation. The
biosurfactants increase the solubility of PAHs, increasing both the access of the bacteria to
PAHs and the efficiency of bioremediation. The biosurfactants also bind metals and other
contaminants, allowing them to be flushed from contaminated soil. Potentially, the biosur-
factants could be used as cleaning or degreasing agents. Using microbes can reduce treatment
time for petroleum-contaminated soil to as little as 90 days, producing cost savings.
BioTiger™ can also save money by removing petroleum products from mixed radioactive
waste, allowing its less costly disposal as low-level radioactive waste.
Broin Project X™: A Method for Producing Ethanol
Using Raw Starch
Broin and Associates has created a unique, novel process for the large-scale production of
ethanol and its coproduct, distiller's dried grains. The process represents the next step in the
evolution from the conventional, high-temperature liquefaction process. Broin's new tech-
nology delivers fermentable sugars from granular starch directly to the yeast (the production
organism) in a controlled manner, avoiding the high-temperature starch liquefaction step.
The Broin Project XIM (BPX) ethanol production process addresses several principles of
green chemistry. It uses novel biocatalysts; it results in higher ethanol yield, lower energy
input, reduced safety issues (due to reduction in ammonia), reduced plant capital costs,
reduced use of fresh water, reduced environmental emissions, increased flexibility in coprod-
34
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uct applications (due to improved quality), and reduced transportation costs (due to
increased density and flow properties of the coproduct). The nominated process represents a
new dislocating technology that owes its existence to the realization of several manufacturing
and environmental benefits. It is the most novel development in the history of the fuel
ethanol industry, the nation's largest renewable-based industry. Since the spring of 2004, the
BPX™ process has been implemented in three U.S. commercial ethanol facilities totaling
almost 150 million gallons in annual ethanol capacity.
Chemistry-Based Design Process to Create
Environmentally Benign Consumer Products: The
Greenlist'™ Process
SC Johnson is a chemical user, not a manufacturer, but is working to minimize the haz-
ard of the chemicals it uses. The Greenlist™ process is an environmental classification system
for chemicals; it is based on four to seven specific criteria for chemicals within functional
material categories. These categories include surfactants, solvents, propellants, resins, packag-
ing, chelants, insecticides, antimicrobials/preservatives, fragrance raw materials, waxes and
candle fuels, and thickeners. SC Johnson may add others, such as colorants and inks, in the
future. SC Johnson selected criteria to be meaningful and discriminating within each func-
tional category. These criteria include biodegradability, aquatic toxicity, human toxicity,
European Union environmental hazard classification, preferred source/supply, vapor pressure,
octanol/water coefficient, and others appropriate for specific categories. The Greenlist™
process assigns an environmental classification (EC) score for each raw material based on its
average score against the criteria used for its category. SC Johnson lowers the final EC score
for some chemicals to account for other significant concerns including persistence, bioaccu-
mulation, and toxicity (PBT); endocrine disruption; carcinogenicity; reproductive toxicity;
and others. The final EC scores range from Best (3) to SC Johnson Restricted Use Material
or RUM (0).
Greenlist™ sets new environmental standards that surpass regulatory requirements and
drive product Innovation. Product formulators may access the company's global databases to
find the EC score of each chemical. Formulators have increased their use of Better or Best
chemicals in products by over 13,000,000 kg in the past three years. In addition, SC Johnson
has replaced all polyvinylchloride (PVC) and chlorine-bleached paperboard in its product
packaging, eliminating over 1,700,000 million kg of PVC and 100,000 kg of chlorine-
bleached paperboard. By measuring its progress with Greenlist™, SC Johnson is
institutionalizing sustainability and improving its environmental footprint.
Cylinderized Phosphine as a Safer, More
Environmentally Friendly Alternative to Traditional
Fumigants for Stored Products
Agricultural fumigants are used to control pests that infest stored products such as dried
fruits and nuts, grains such as wheat, rice, and corn, and nonfood commodities such as tobac-
co. For over fifty years, stored products have typically been fumigated with methyl bromide
or metallic phosphides. Methyl bromide is being phased out in accordance with the Montreal
Protocol on ozone-depleting substances; therefore, an alternative fumigation method is need-
ed. Metallic phosphides (typically aluminum or magnesium phosphide) release phosphine
gas when exposed to the ambient moisture in the air. Phosphine gas by itself is a very effec-
SC Johnson
Cytec Industries
Incorporated
35
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Solutia Inc.
Nowartis
Pharmaceuticals
Corporation
tive fumigant with no known chronic toxicity. The efficient release of phosphine gas from the
metallic phosphides, however, requires certain temperature and humidity levels that may not
be reached in practice; as a result, unreacted phosphide residues are often left after fumiga-
tion. These residues must be deactivated and disposed of in a time-consuming and often
dangerous process. Typically, they are hazardous waste.
Cytec Industries has developed and commercialized a new technology for the stored prod-
uct fumigation market. Cytec supplies phosphine gas in recyclable cylinders. With
cylindcrizcd phosphine, workers can easily adjust phosphine concentrations from outside the
fumigation space, applying only the amount necessary for complete fumigation. As a result,
fumigation requires less phosphine. Further, cylinderized products leave no unreacted residue
or byproducts. Cytec's cylinderized phosphine products are inherently safer than traditional
fumigants: they require less worker exposure and do not significantly impact the environ-
ment. Cytec's two products, ECOiFUME and VAPORPHsOS, are currently used by some
of the largest food processing, milling, and storage facilities.
Dequest PB—Carboxymethyl Inulin: A Versatile Scale
Inhibitor Made from Chicory Roots
Fouling of surfaces by mineral salts is a major problem in water-bearing systems, because
scaling reduces heat transfer efficiency and interferes with the operational performance of
industrial processes. Previously, scale inhibitors were either products with poor biodegrad-
ability, moderate toxicity, and good performance (e.g., polyacrylates) or biodegradable
products with limited applicability (e.g., polyaspartates). Carboxymethyl inulin (CMI),
developed by Solutia and Cosun, provides a cost-effective, safe, and versatile alternative to tra-
ditional antiscalants. In 2004, Solutia began marketing this very first inulin derivative, CMI,
in the U.S. under the trade name Dequest PB.
CM! is based on inulin, an oligosaccharide harvested from the roots of chicory. CMI has
excellent scale-Inhibitor properties. It combines good biodegradability, very low toxicity, and
excellent scale-inhibition performance characteristics for various types of scales, particularly
sulfate scales. The product can be used in many applications, but is especially well-suited for
use in environmentally sensitive areas, such as off-shore oil production. For example, CMI is
used in the Norwegian off-shore oil drilling sector of the North Sea. CMI also is a suitable
replacement for poorly biodegradable scale inhibitors in water and process water treatment
applications. In addition to CMI, Solutia and Cosun are developing a wider range of inulin-
based products with different functionalities.
Development of Green and Practical Processes Utilizing
Dialkyl Carbonates as Alkylating Reagents
In the last five years, Novartis's green chemistry project has developed an environmental-
ly friendly methylation process that employs 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) or
1,4-diazabicyclo [2.2.2]octane (DABCO) as novel catalysts to promote methylation reactions
of phenols, indoles, benzimidazoles, and carboxylic acids with dimethyl carbonate under
mild conditions in nearly quantitative yields. Similarly, Novartis has developed a novel and
green process using dibenzyl carbonate with catalytic amounts of DABCO or DBU to ben-
zylate nitrogen, oxygen, and sulfur atoms. Either microwave irradiation or an ionic liquid
provide additional rate enhancement. By combining DBU or DABCO, microwave irradia-
tion, and an ionic liquid, Novartis can perform alkylation reactions that previously took up
to several days efficiently in high yields within minutes. Novartis's technology avoids toxic or
36
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carcinogenic reagents such as methyl iodide, dimethyl sulfate, benzyl chloride, and benzyl
bromide. It also eliminates the use of a stoichiometric amount of base if applicable substrates
contain no acidic protons. Their novel technology has the additional benefit of rapid reaction
times, ease of operation, and use of readily available catalysts and ionic liquids. These features
should make this newly developed chemistry of great benefit to humans and the environ-
ment. The United States Patent and Trademark Office has granted four patents to Novartis
for these novel inventions. In addition, leading peer-reviewed journals have accepted six pub-
lications. By the end of 2004, these papers had been cited thirty times by other scientists,
confirming the utility and value of these inventions.
Development of Nike Brand Footwear Outsole Rubber
as an Environmentally Preferred Material
One of the Nike brand's long-term, corporate environmental goals is to eliminate from its
products all substances known or suspected to be harmful to human health or the health of
biological or ecological systems. To move towards this corporate goal, Nike brand's footwear
organization began an effort to eliminate many of the toxic substances from the process of
manufacturing footwear rubber outsoles, which are common to the athletic footwear manu-
facturing industry. Nike's general strategy included developing an assessment protocol to
identify toxic chemicals to avoid; assessing certain of Nike's rubber formulations against the
protocol; testing; and commercializing the new rubber formulation. The project resulted in
a new environmentally preferred rubber formulation for outsoles that replaces a traditional
Nike rubber formulation (Formula A). A representative sample of the new environmentally
preferred rubber contains 96% fewer toxics by weight than the original formulation, provides
equal performance, looks the same, and costs no more than traditional rubber. Nike contin-
ues to work at improving its formulation. Currently Nike is also trying to establish a
consortium of companies to pool resources to develop an enhanced assessment protocol and
open the protocol to scientific peer review.
Nike implemented an internal footwear sustainability index to measure its footwear devel-
opment teams on their use of environmentally preferred materials. The index helped drive
rapid adoption of the new rubber. After about two years, nearly all footwear development
groups (basketball, soccer, running, etc.) have used the environmentally preferred rubber in
some shoes. In Nike's spring 2005 production season, 58 million pairs of shoes out of approx-
imately 100 million pairs total will contain the newr material. In producing these shoes, Nike
will use approximately 14,415 metric tons of environmentally preferred rubber.
Development of a Water-Eased Adhesive, Primer, and
Release Coating for Post-it® Super Sticky Notes
3M's Post-it® Super Sticky Notes are an excellent example of the benefits of green chem-
istry and the importance of integrating 3M's core values into decision-making. In 2003, 3M
introduced Post-it® Super Sticky Notes: a new, enhanced Post-it® Notes product designed for
use on vertical and hard-to-stick surfaces. In the late 1980s, 3M developed a prototype of this
enhanced Post-it'* Note using solvent-based formulations for the adhesive, primer, and release
coatings. At the same time, 3M launched an initiative to reduce volatile organic compound
(VOC) emissions by 90% by the year 2000. Rather than install pollution control equipment
to control the VOC emissions from the proposed production process, 3M delayed introduc-
ing the product until it could develop new, water-based formulations. 3M's new water-based
microsphere adhesive, primer, and release coating formulations yield the desired perfor-
Nike Global Footwear
3M Office Supplies
DiYision Laboratory
37
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Pfizer Global Research
and Development
GlaxoSmithKIine
mance, generate fewer air emissions, have a reduced environmental risk profile, and are less
expensive to manufacture than the original, proposed solvent-based formulations. The new
formulations result in lower VOC emissions (33,400 pounds controlled or 2,170,000
pounds uncontrolled) and lower Toxic Release Inventory (TRI) emissions (20,500 pounds
controlled or 1,024,000 pounds uncontrolled) annually than if 3M had implemented its pro-
posed solvent-based process.
Discovery and Development of an Environmentally
Benign Commercial Route to Sildenafil Citrate
Pfizer has emphasized green chemistry objectives during the discovery and development
of the commercial route to sildenafil citrate, the active ingredient in the important medicine
Viagra™. The commercial synthesis generates only 4 kg of organic waste per kg of sildenafil,
substantially less than is typical for pharmaceutical products. The key breakthrough in
achieving this exceptional result was the discovery of a new, convergent synthetic route with
a clean cyclization reaction as the final step, eliminating purification operations. Subsequent
careful chemical development and diligent solvent recovery have optimized the environmen-
tal performance.
Achievements include a nine-fold yield increase from the starting pyrazole to sildenafil cit-
rate. The commercial route reduces organic waste by 14-fold, eliminating 4,000 tons of
organic waste; it also reduces aqueous waste by 5-fold, eliminating over 3,900 tons of aque-
ous waste. An environmentally benign catalytic hydrogenation reaction replaces a reduction
using tin chloride (tin is a toxic heavy metal). Hydrogen peroxide (a worker safety issue) has
been eliminated. Three chemical steps are combined, using a single solvent that is recovered.
None of the reactions in eight chemical steps requires a work-up involving extraction, again
leading to low organic waste. Pfizer has implemented many technological achievements at the
outset of commercial manufacture.
Discovery and Development of a Green Process for
Radafaxine
GlaxoSmithKIine has identified and fully evaluated two viable commercial routes of man-
ufacture for Radafaxine, a compound that has shown antidepressant activity in animal
models of depression. Radafaxine is an (S,S)-enantiomer. The corresponding (R,R)-enan-
tiomer is associated with undesirable effects. The key challenge was to separate the two
enantiomers efficiently and minimize the environmental impacts associated with the unde-
sired enantiomer.
Route B3, an initial improvement on the traditional synthesis, uses an original and inno-
vative dynamic kinetic resolution to synthesize the desired single enantiomer. This simple
process has several advantages and produces the desired enantiomer without expensive and
environmentally unacceptable chiral catalysts or templates. It also replaces the environmen-
tally undesirable solvents dichloromethane and acetonitrile.
The second process, multicolumn chromatography (MCC), improves on route B3,
retaining all of its advantages. The MCC process also re-epimerizes and recycles the unde-
sired enantiomer, delivering an overall process with significant environmental benefits.
Detailed analysis demonstrates that the MCC-based process meets all commercial and qual-
ity criteria; in addition, it reduces the use of valuable resources and greatly decreases the
process liquid waste streams.
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The traditional synthesis required 260 kg of input material and 194 kg of solvent per kg
of product. The mass intensity of the MCC process is approximately 20 kg of input materi-
al per kg of product, an incredibly low number for a pharmaceutical product. The MCC
process uses only 19 kg of solvent per kg of product, with potential for further recovery.
GlaxoSmithKlinc performed a pilot study on medium-to-largc scale in-house MCC equip-
ment during 2003. At peak production, GlaxoSmithKline calculates that the MCC process
could reduce the overall waste load by 5,000 metric tons per year.
Duraflame® All-Natural Manufactured Firelog
Duraflame, Inc. is America's leading marketer of manufactured firelogs. Headquartered in
Stockton, California, Duraflame is a privately held company that has been in business for
more than 30 years.
What started out as an effort to recycle the sawdust produced by wood milling operations
has grown into a way of doing business for Duraflame. The company's Research and
Development Department regularly experiments with resources to determine unique
approaches to product development and is continually striving to create convenient, envi-
ronmentally responsible products to meet consumer needs.
Faced with a shrinking supply of petroleum wax and a rise in restrictions on wood-burn-
ing fireplaces by air quality districts (particularly in the Western States), the company has
focused on developing manufactured firelogs using materials that are both cleaner burning
and recycled or renewable. In 2004, Duraflame introduced a new all-natural firelog made
from recycled biomass products such as wood sawdust, ground nut shells, recycled cardboard,
and plant waxes (rather than petroleum wax) as a combustible binder. Standard petroleum
wax-sawdust firelogs produce approximately two-thirds less of the key air pollutants associat-
ed with residential wood combustion than does an equivalent natural wood fire. In contrast,
Duraflame's new all-natural firelogs produce only about one-quarter of the emissions of an
equivalent natural wood fire. The Duraflame® All-Natural Firelog is now available in super-
markets across the U.S. and Canada.
Economic Destruction of Methyl Bromide from Air
Streams Using Nonhazardous Aqueous Solution
Methyl bromide is a critical chemical fumigant used to protect imported and exported
goods from conveying unwanted insect pests. It is also an ozone-depleting substance slated
for elimination by 2015 under the Montreal Protocol, in part because emission control was
not believed to be practical. Efforts to find replacement substances have, to date, not been
successful; thus, methyl bromide remains in use.
The novel technology developed by Value Recovery takes advantage of methyl bromide's
reactivity to separate it from air. The fumigation chamber containing methyl bromide is vent-
ed into a special scrubber filled with an aqueous solution of ammonium thiosulfate and other
nonhazardous compounds. The gas passes through the liquid in tiny bubbles that enhance
gas-liquid mass transfer. The nucleophilic substitution reaction involving bromide (leaving
group) and thiosulfate (nucleophile) takes place in the aqueous phase. Industrial-scale trials
using a container filled with produce fully confirm numerous laboratory results: one pass
through the scrubber removes more than 85% of the methyl. Value Recovery's technology is
very inexpensive due to the simplicity of the process, the low cost of equipment, the inex-
pensive reactants, and the ease of disposal of the used liquor.
Duraflame, Inc.
Value Recoyery, Inc.
39
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U.S. Army Engineer
Research and
Development Center
Bunge North America
Environmentally Friendly Water Treatments for Control
of Corrosion, Scale, and Bio activity in Heating and
Cooling Systems
Presently, heating and cooling water treatment requires manual handling of toxic and cor-
rosive chemicals, some of which (hydrofluoric acid, for example) are extremely hazardous.
The U.S. Army Corps of Engineers Engineer Research and Development Center (U.S. Army
ERDC) led a team of researchers to develop green water treatments to control corrosion, scale
deposit, and microbiological growth in heating systems (boilers and condensate lines) and
cooling systems (cooling towers). The goal was to provide a safer and more environmentally
friendly water treatment program that exceeded industry standard performance criteria and
at a cost equal to or less than conventional water treatments for heating and cooling systems.
U.S. Army ERDC teamed with: the Garratt-Callahan Chemical Company; Trevino
Mechanical, a small business mechanical sub-contactor; SurTech Corporation to perform the
field demonstrations; and the Illinois State Water Survey for verification of field data.
The research team worked to develop, run field demonstrations on, and evaluate three
formulations based on two chemicals previously recognized as Presidential Green Chemistry
Challenge Winners: tetrakis hydroxymethyl phosphonium sulfatc (THPS) for control of bio-
logical growth and polyaspartate for control of mineral scale. In addition, the formulations
contained a filming soya amine to control corrosion in condensate pipelines. The team also
used state-of-the-art automated equipment to minimize the hazards of chemical handling.
The researchers applied the water treatment formulations and monitored their performance
at three military installations for a period of two years. As a result, U.S. Army ERDC devel-
oped performance specifications for the use of green chemicals in water treatment for heating
and cooling systems at public and private central energy plants.
Enzymatic Degumming of Soybean Oil with PLAi
Enzyme
Crude soybean oil contains between two and three percent phospholipids, commonly
known as gums. Following centrifugation to remove most of the gums, the traditional, chem-
ical refining process neutralizes the free fatty acids (FFA) with sodium hydroxide, converting
them to sodium soaps. Sodium hydroxide also reacts with the neutral oil, however. An emul-
sion forms between the sodium soaps, phospholipids, and neutral oil. This heavy phase,
called soapstock, is removed by centrifugation, reducing the yield.
Bunge North America has developed an efficient degumming process using the enzyme
phospholipidase AI (PLAi). PLAi selectively cleaves the SN-1 fatly acid from the phospho-
lipid, yielding a /yw-phospholipid. This /)w-phospholipid is water-soluble and separates easily
from the oil phase without emulsifying any of the neutral oil. The enzymatic reaction occurs
at a buffered pH of roughly 4.5; thus, the neutral oil does not saponify and soaps do not
form. The heavy phase containing the /y50-phospholipids can either be added to soybean meal
as an energy source or possibly purified as a lecithin with new properties. The fatty acids gen-
erated from the enzymatic reaction are recovered along with the FFA originally present in the
oil in a subsequent deodorization step. Bunge is currently using its PLAi process at a refinery
in Indiana with a capacity of 750 metric tons per day. Compared to the chemical refining
process, this one plant is reducing carbon dioxide emissions by over 30 metric tons daily.
40
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Enzyme-Based Technology for Decontamination of Toxic
Organophosphorus Compounds
The U.S. Army Edgewood Chemical Biological Center (ECBC) has developed and
patented a technology designed to neutralize chemicals such as nerve agents and related pes-
ticides. The technology consists of 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 de-icing solu-
tions). The enzymes quickly detoxify these hazardous chemicals before they can contaminate
wider areas. Because the enzymes are catalytic, only small quantities are required, greatly
reducing transportation and storage requirements. They are also nontoxic, noncorrosive, and
environmentally safe. Initially intended to decontaminate equipment, facilities, and large
areas, the enzymes could potentially be used in shower systems to decontaminate personnel
and casualties. Genencor International, the premier manufacturer of industrial and specialty
enzymes in the U.S., will utilize its state-of-the-art fermentation manufacturing technology
to produce the enzymes. 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. Genencor is marketing the enzymes under the general name DEFENZ™.
Equinox® Technology: A Greener Approach to
Microbiological Control
Because of its high biocidal efficacy and low cost, chlorine is one of the most predomi-
nant biocides used by the U.S. papermaking industry, with an estimated 60 million pounds
of chlorine biocides used annually. The widespread use of chlorine in papermaking creates
highly toxic chlorinated byproducts, such as trihalomethanes and dioxin, which are broadly
referred to as absorbable organic halogen (AOX).
Lonza has developed Equinox® as a nontoxic alternative to reduce the amount of chlorine
biocides used by the papermaking industry. Equinox* is based on 5,5-dimethyl hydantoin,
which interferes with the natural tendency of chlorine to random oxidations and in the
process enhances chlorine's bactericidal properties. By markedly improving the stability of
chlorine, Equinox® has shown that it can reduce chlorine use by over 90%. Because chlorine
is reduced, the amount of AOX is similarly reduced by up to 95%. Since its commercial
introduction in 2002, Equinox® has treated over 36 billion gallons of paper mill water, elim-
inating the use of an estimated 2.4 million pounds of chlorine and preventing the generation
and release of over 128,000 pounds of AOX into the environment. Equinox* is now used in
paper mills throughout the U.S. and Europe. Equinox® has other uses as well, but in the
papermaking industry alone it has the potential to eliminate the formation of 3-3 million
pounds per year of AOX pollutants. By reducing the amount of toxic AOX compounds
released into the environment, Equinox® provides an environmentally safer alternative to the
historically high use levels of chlorine biocides.
Formula 1 ™ Laundry System
Formula 1™ is a new, single-product system designed for on-premises commercial laun-
dry operations. Its unique dispensing and packaging system (patent pending) produces a
dilute detergent solution from a 100% active concentrate on-site. The concentrate is a non-
aqueous, heterogeneous slurry that contains Cn-w linear alcohol ethoxylates, two polymeric
water conditioning agents, a proprietary enzyme support matrix, and sodium carbonate. This
U.S. Army, U.S. Army
Edgewood Chemical
Biological Center
Lonza Inc.
Ecolab
41
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Dow AgroSciences and
the U.S. Department of
Agriculture (USDA)
Agricultural Research
Service
single-product system can replace three or tour current products with no loss in performance.
The Formula 1™ technology delivers many benefits to the consumer and to the environ-
ment. These include fewer wash steps and, therefore, water savings, energy savings, and
shorter cycle time; fewer different products required; reduced product waste; reduced plastic
packaging; significantly lower shipping weight; and increased worker safety. Formula 1'1M
contains no caustic soda, chlorine, or nonylphenol ethoxylates. The marriage of product
chemistry, dispenser, and packaging gives on-premise laundry operators a revolutionary new
way to clean that is significantly more environmentally friendly.
The Formula 1™ Laundry System has been in commerce since January 2004; there are
currently over 1,000 users in North America. If half of the over 50,000 potential user loca-
tions in North America used the Formula 1™ Laundry System, they would save 8.2 billion
gallons of water, 47 million therms of natural gas, and 5 million pounds of plastic each year.
GF-120™ NF Naturafyte™ Fruit Fly Bait
Tephritid fruit flies are important quarantine pests that can devastate fruit and vegetable
production and limit movement of produce. Previously, a wide range of insecticide baits had
been used to control these fruit flies; the results were often inconsistent, however, due to a
lack of understanding of fly attractiveness, feeding biology, and quality control. The active
ingredients in these baits were organophosphates. The organophosphates were generally used
at rates as high as 0.5 to 1.0 pounds per acre to overcome their inadequacy. The International
Atomic Energy Association and others had developed irradiated sterile insect techniques
(SIT), but this tool works best with low insect populations. An improved bait system using
an environmentally sound active ingredient was needed (1) to reduce population levels so
that sterile insect and other integrated pest management solutions could be used and (2) to
protect fly-free regions such as the U.S.
Dow AgroSciences had already developed spinosad, a new reduced-risk insecticide active
ingredient that was successful in spray applications. Dow AgroSciences combined its project
management, industrial manufacturing, quality control, and formulation science skills with
USDA's knowledge of fruit fly biology and behavior. Together, Dow AgroSciences and USDA
developed a superior bait technology, GF-120™ NF, to protect fruits and vegetables from
the Mediterranean fruit fly and similar pests. This is the first bait plus active ingredient (spin-
osad) that contains only organically acceptable components; it is so attractive to flies that
farmers need less than 0.003 pounds of spinosad per acre. Between 2000 and 2004, farmers
used GF-120™ NF to treat over six million acres. GF-120™ NF is now the fruit fly bait of
choice in much of the world.
Pfizer Global
and Development
Green Chemistry in the Redesign of the Celecoxib
Process
Pfizer redesigned the celecoxib manufacturing process with green chemistry objectives as
some of the project's primary goals, resulting in dramatic environmental and worker safety
improvements in the manufacture of the active ingredient in the medicine, Celebrex®. These
improvements followed the elucidation of two unprecedented reaction mechanisms respon-
sible for the formation of isomeric impurities whose presence required a subsequent
recrystallization with its concomitant loss of yield and expense for resources. Celecoxib made
by Pfizers new process is pure enough to permit final isolation directly from the reaction mix-
42
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ture; such isolations are very rare in the pharmaceutical industry. Pfizer's new mechanistic
understanding increases the process efficiency significantly with respect to raw materials, sol-
vents, energy, and waste.
The environmental and safety improvements are also significant. In total, Pfizer has elim-
inated 5,200 metric tons per year of organic solvents. Pfizer has also completely removed
tetraliydrofuran and 35% hydrochloric acid (212 metric tons/yr). Pfizer has partially replaced
organic solvent washes during isolation by water. In addition, raw materials have been
reduced by over 150 metric tons per year. By eliminating the rccrystallization and using the
heats of reaction and other temperature parameters judiciously Pfizer is saving more than
4 billion BTUs per year. Pfizer has also improved worker safety by reducing the number of
unit operations required per batch and improving the process payload (product
produced/reactor volume), resulting in the need for fewer batches to fulfill demand.
Green Chemistry in the Redesign of the Pregabalin
Process
Application of green chemistry principles to the synthesis of Pregabalin, the active ingre-
dient in the medicine Lyrica®, has delivered dramatic environmental and worker safety
improvements concomitant with significantly enhanced process efficiency. Lyrica® is used to
treat patients with neuropathic pain, epilepsy, and generalized anxiety disorder. It was
approved in Europe in 2004 and currently is under review by the U.S. Food and Drug
Administration.
Development of high-throughput enzyme screening technology, elucidation of product
inhibition in biocatalysis, and the application of medium- and large-bioreactor engineering
to enhance catalytic efficiency has resulted in a new catalytic and enantioselective process
with all four reaction steps conducted in water. At the projected peak of annual production,
this new process will eliminate 11 million gallons of organic solvents each year, including
tetrahydrofuran, ethanol, methanol, and isopropanol. This process is also projected to elim-
inate 1,600 metric tons per year of (S)-mandclic acid waste associated with classic chemical
resolution and 500 metric tons per year of Raney nickel. Pfizer is recycling the undesired
enantiomer using successful product partitioning, epimerization, and subsequent resubmis-
sion to a biocatalytic transformation. This recycling, combined with overall process
improvements, will save over 800 metric tons of starting material per year. Using a food-grade
enzyme, Pfizer's biocatalytic route has improved process throughput, increased process yield
by over 50%, significantly reduced metal catalyst requirements, and delivered a highly effi-
cient, environmentally responsible process for manufacturing the pharmaceutical Pregabalin.
A Green Process for the Synthesis of Quinapril
Hydrochloride
Pfizer emphasized green chemistry objectives in redesigning its process to manufacture
quinapril hydrochloride (HC1), the active ingredient in the important cardiovascular medi-
cine, Accupril™. The resulting process employs more efficient chemical transformations with
dramatic environmental and worker safety improvements. Process yields have increased by
30%; process throughput has quadrupled. The process has eliminated methylene chloride
and dicyclohexylcarbodiimide. Operations that caused loss of yield due to the intermolecu-
lar cyclization of quinapril HC1 have been minimized. Overall, Pfizer's improvements have
eliminated the isolation of one intermediate, two drying steps, and a hydrogenation step.
Pfizer Global Research
and DeYelopment
Pfizer Global Research
and Development
43
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Eli Lilly and Company
Rohm and
Company
The environmental and safety improvements are dramatic, Pfizer's process has eliminated
the use of approximately 30 metric tons per year of dicyclohexylcarbodiimide and the subse-
quent generation of 30 metric tons per year of solid dicyclohexylurea waste. The process has
also eliminated the use of approximately 1,100 metric tons per year of methylene chloride.
The volume of solvent has been reduced dramatically; aqueous and organic wastes have been
reduced by 90%. Pfizer's process reduces raw material, water, and energy use significantly.
The new process was readily transferred to Pfizer's manufacturing facilities.
An Improved Approach to the Preparation ofDuloxetine
and Atomoxetine
Eli Lilly has developed and demonstrated new, more efficient, synthetic routes for two of
its 3-aryloxy-3-arylpropylamine pharmaceutical products. Duloxetine hydrochloride is the
active ingredient in the product Cymbalta®, used to treat depression. Atomoxetine
hydrochloride is the active ingredient in the product Strattera®, used to treat attention
deficit/hyperactivity disorder. Each of these improved syntheses avoids using an N-methyl
protecting group and produces the drug substance in a direct fashion using a monomethyl-
amine intermediate. Eliminating the traditional protecting group to produce these drug
substances reduces the combined environmental footprint by an average of 44%, as measured
by the weight of materials used to produce one kilogram of product (E-factor). These com-
bined improvements reduce the use of (1) solvents by an average of 27%, (2) water by 58%,
and (3) raw materials by 78%. At peak production volumes for both drugs, estimated in the
tens to hundreds of metric tons per year, these reductions could provide expected savings of
2.5 to 25.5 million pounds ot raw materials per year. Further, manufacturers must often
incinerate pharmaceutical aqueous waste streams to destroy the biological activity associated
with their trace components, necessitating additional fuel consumption. Water reductions
from the new syntheses alone should result in secondary fuel savings of 1.5 to 14.5 million
cubic feet per year.
The new synthesis for duloxctine was demonstrated on a pilot plant scale in 2002; Eli
Lilly is now developing its pilot plant process into an improved commercial process. The new
synthesis for atomoxetine is currently being used at an Eli Lilly production facility.
Invention and Commercialization of Environmentally
Friendly Acrylic Thermosets
Thermosetting binders are used ubiquitously in composite building and construction
materials such as fiberglass insulation, air filters, and engineered wood products. The most
common thermosetting resins are formaldehyde-based resins, which require expensive abate-
ment equipment as well as special handling and transport.
TSET™, the Rohm and Haas acrylic thermoset formulation, is a formaldehyde-free, cur-
able, aqueous solution of poly(acrylic acid), triethanolamine, and sodium hypophosphite.
Although hypophosphite catalysis of esterification was used earlier in permanent press fabric
applications, TSET™ chemistry is a significant departure from these early chemistries.
TSET™ is novel: from the very beginning, Rohm and Haas's objective was to synthesize an
alkyl phosphinic acid polymer backbone. Rohm and Haas obtained higher degrees of cross-
linking by combining steps that had never before been combined. These steps include: the
dual use of the esterification catalyst as a chain transfer agent in synthesizing the polymer
backbone; the mobility of the polyol within the curing resin (which becomes transport-lim-
ited at high degrees of cure); increased reactivity of primary alcohols such as triethanolamine
44
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(further activated by the p-tertiary amine) relative to the secondary alcohols of cellulosics; and
the higher cure temperatures available in heat-resistant noncellulosic substrates.
By combining these steps, Rohm and Haas has created a class of acrylic thcrmoscts that
are an ideal green chemistry alternative to the industrially ubiquitous phenol-formaldehyde
resins. With TSET™, the only byproduct of cure is water; there are no formaldehyde wastes,
emissions, or exposures. Acrylic thermosets are nonreactive, nonflammable, recyclable, and
benign at ambient conditions, simplifying handling, transport, storage, application, and
cleanup. TSET™ has been in commerce since 2002; several leading building products com-
panies are currently using it. By the end of 2004, TSET™ will have replaced approximately
100 million pounds of phenol-formaldehyde resins; by the end of 2010, TSET™ is poised
to eliminate over 400 million pounds of formaldehyde-based resins.
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 con-
cerns included a potential runaway bromination reaction, severe skin and eye irritation from
an intermediate product, and negative environmental effects of several organic solvents.
Previously, Bristol-Myers Squibb (BMS) had mitigated some of the negative EHS impacts of
the original synthesis, but the bromination in the first synthetic step remained a concern.
This bromination created a nonbiodegradable byproduct that required incineration and,
thereby, created a significant waste disposal problem.
To address that problem and further minimize EHS impacts, BMS has modified the
bromination and crystallization processes it uses in the synthesis and modified the recrystal-
lization 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 projected five-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.
Metal-, Phenol-, and Ash-Free Antiwear Hydraulic
Additive: Providing Performance Only Achieved
Previously with 'Zinc-Containing Additives
The use of heavy metals in lubricants presents environmental concerns, due primarily to
zinc contamination coming from hydraulic oils. The global antiwear hydraulic lubricant mar-
ket is approximately 980 million gallons. Roughly 95% of this global market is based on
lubricants containing zinc dialkyl dithiophosphatc (ZDDP) as the antiwear additive. Only
approximately 5% of this market is based on lubricants containing the less toxic, environ-
mentally friendly, ashless, antiwear additive technology. Of the lubricants using ashless
additive technology, the majority are based on conventional mineral oils with, globally, only
approximately 3% based on biodegradable fluids. The slow growth in the use of antiwear
hydraulic fluids based on ashless technology is due, in part, to problems in the field, where
performance equivalent to fluids based on ZDDPs had not been achieved previously. This is
especially true for biodegradable hydraulic fluids.
Bristol-Myers Squibb
Company
Alton Chemical
Corporation
45
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U.S. Army Engineer
Research and
Dewelopment Center
Rhodia Inc.
Afton has identified an additive technology that is not only ashless, but also phenol-free.
When used in mineral oils, Afton's product performs as well as, it not better than, ZDDP-
based fluids. This is the first ashless, mineral oil-based technology to be tested against new,
more severe requirements and approved by original equipment manufacturers (OEMs). Also,
this ashless additive technology, along with boosters in biodegradable oils, is the first to be
approved against new specifications designed for environmentally friendly fluids. Afton's
HiTEC 543 contains an amine salt of a sulfurized phosphite that provides antiwear protec-
tion over a wide temperature range in dry and wet conditions, a thiadiazole corrosion
inhibitor that provides comparability with yellow metals, a three-way phenol-free antioxidant
system, and a dispersant. Afton received its first commercial order for this new product in
April 2003.
Mold Prevention through the Novel Use of In Situ
Electrochemistry to Eliminate Water Seepage in Concrete
Structures
Electro-Osmotic Pulse (EOF) technology eliminates water seepage through concrete by
the novel use of in situ electrochemistry. It prevents mold growth and eliminates the use of
harmful volatile organic compounds (VOCs), such as from petroleum-based coatings used
for waterproofing. EOF has led to a revolution in waterproofing technology through the
application of electro-osmosis (forced movement of an aqueous solution containing a net
electric charge due to an external electric field) to control water transport through below-
grade concrete structures such as foundations, basements, and tunnels. Unlike many
conventional waterproofing methods, EOF reaction chemistry is inherently nontoxic and
releases no VOCs. EOF improves air quality in below-grade spaces by reducing the interior
concrete surface moisture below 55% relative humidity, such that mold cannot grow. Further,
it costs about 40% less to install than traditional waterproofing methods.
EOF combines the novel application of an asymmetric, dual-polarity pulse with long-life
ceramic-coated electrode materials. The anodes are inserted into the concrete wall on the
interior of the structure; cathodes arc placed either in the soil directly outside the structure or
in the structure itself, near the exterior. A direct current (DC) power supply produces a low-
voltage, dual-polarity pulse. This sets up an electric field between the electrodes, creating an
electro-osmotic pressure sufficient to overcome the external hydraulic pressure and to reverse
the flow of water seepage, actually causing moisture to move toward the outside of the base-
ment walls. During 2003 and 2004, the Army has installed EOF systems in the basements
of 382 family houses on military bases.
Natural, Guar-based Chemistry Reduces Drift and
Increases Retention of Crop Sprays
Supported by patented research, peer-reviewed publications, and market acceptance,
Rliodia's natural, guar-based chemistry is an innovative, effective, and environmentally sound
alternative that allows crop protection sprays to be applied more precisely to their targeted
areas, remain on targeted crops longer, and minimize waste and drift associated with tradi-
tional application aids. Rhodia's product, AgRHO™DR 2000, is a natural, plant-based
polymer; it contains new guar derivatives developed by Rhodia specifically for the market
needs of this product. The guar base of AgRHO™DR 2000 eliminates the need for solvent-
based formulations and is fully biodegradable, compatible with other spray ingredients, and
safe tor use and handling. Farmers now apply AgRHO™DR 2000 to more than 16 million
46
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acres of soybeans in the United States. This represents nearly 15 percent of the total sprayable
soybean acres, with significant potential for further market growth. Through its ongoing
research and pending patent applications, Rhodia expects that AgRHO™DR 2000 tech-
nology could be applied to other crops covering more than triple the current sprayable
acreage within the next five years.
A Novel Cleaning System Using Less Toxic, Safer
Chemicals
The nominated process cleans and sanitizes the polyethersulfone ultrafiltration (UF)
membranes used in the dairy industry. The current commercially available cleaning process
has been a three-cycle alkaline/acid/chlorinated alkaline system. Conventional alkaline clean-
ers typically consist of strong alkaline solutions of sodium and potassium hydroxide with a
small amount of nonionic surfactants. The acid cleaners typically consist of high levels of
phosphoric and nitric acids. The current sanitizer contains sodium hypochlorite at 200 ppm
in solution. The current procedure also requires large volumes of water to rinse and neutral-
ize the membrane.
JohnsonDiversey's technology uses peroxygen chemistry to develop more efficient clean-
ers and germicides with safer and more environmentally preferable chemicals. This new
technology consists of an aqueous solution of hydrogen peroxide, phosphorus-based acid,
phosphonate, and an anionic surfactant. This new technology yields safer cleaners by formu-
lating them at a more neutral pH. Hydrogen peroxide provides a good bleach alternative that
sanitizes more gently than chlorinated alkaline sanitizers. Overall, this technology cleans and
sanitizes effectively using less toxic chemicals than current alternatives; it is also safer with
respect to human health and environment. This technology has a great economic impact by
performing the cleaning and sanitization at lower temperatures. JohnsonDiverseys cost analy-
sis shows that it saves energy by up to 43%, reduces plant downtime by up to 18%, and
decreases water use by up to 33%. This technology also decreases wastewater generation and
improves the long-term stability of the UF membrane. During pilot plant studies,
JohnsonDiversey's peroxygen products demonstrated superior performance versus the current
competitive products. Compared to a typical system, JohnsonDiversey's new system would
save $700,000 per year, on average, in a dairy plant.
Oxygen-Enhanced Combustion for NOx Control
The abundance of coal and forecasts of high costs for alternative fossil fuels, such as nat-
ural gas, suggest that the use of coal to generate power will continue for some time. Coal-fired
utilities are also, however, major emitters of pollutants, such as nitrogen oxides (NOX).
Praxair's Oxygen-Enhanced Combustion (OEC) technology for NOX control is a unique
combination of reduced NOX emissions and enhanced combustion. In OEC, a small portion
of the combustion air in a staged combustion system is replaced with oxygen, increasing the
local temperature under fuel-rich conditions. These higher flame temperatures enhance reac-
tions, converting NOX to N2 in the flame zone. In various trials from laboratory-scale
furnaces to a nominal 125-megawatt power plant, oxygen-enhanced staged combustion
reduced NOX emissions by as much as 60% without the added operational problems com-
monly associated with staged combustion. An OEC system operated for most of the 2003
and 2004 ozone seasons at the Northwest Utilities 125-megawatt Mt. Tom Station, achiev-
ing NOX emissions of less than 0.15 pounds per million Btu.
JohnsonDiwersey, Inc.
Praxair, Inc.
47
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Pacific Northwest
National Laboratory
By minimizing NOX formation in the combustion zone, OEC reduces or eliminates the
need for post-combustion cleanup technologies that require ammonia, such as selective cat-
alytic reduction (SCR). By minimizing the need for SCR systems, Praxair's OEC technology
also minimizes the production, transportation, and storage of ammonia. Because ammonia
is hazardous, minimizing its use increases the safety of both plant personnel and the public.
Replacing ammonia with oxygen also reduces atmospheric emissions of ammonia, thereby
reducing the associated impacts on respiratory health. Further, because ammonia production
requires natural gas, minimizing ammonia also helps preserve this important natural
resource. Based on some broad assumptions for 600 coal-fired plants in 22 states, OEC tech-
nology could eliminate the use of over 500 million pounds of ammonia per year and
atmospheric emissions of over 30 million pounds of ammonia in flue gas per year.
Self-Assembled Monolayers on Mesoporous Silica
Technology: A Green Alternative Synthesis of a Novel
Adsorbent for Mercury Source Reduction
Until now, there had been no effective technology for removing mercury from ground-
water down to 2 parts per billion, as required by the maximum contamination limit for
drinking water set by the U.S. Food and Drug Administration (FDA) and the U.S. EPA.
Thiol self-assembled monolayers on mesoporous silica (thiol-SAMMS) can absorb mercury
from low-volume waste streams, but the original synthesis of thiol-SAMMS created its own
environmental problems. SAMMS used to be functionalized in toluene. The resulting waste
stream consisted of water, methanol, toluene and traces of mercaptan. It was impractical to
separate this mixture; therefore, the mixture was usually disposed of as hazardous waste.
In response to this problem, scientists at the Pacific Northwest National Laboratory
(PNNL) have created and patented a green chemical process to synthesize SAMMS more effi-
ciently. PNNL scientists use supercritical carbon dioxide (scCO2), a green solvent that allows
complete silane deposition and yields a higher quality product. With this new process, PNNL
can conduct SAMMS deposition faster and more efficiently. A reaction that normally took
several hours in rcfluxing toluene (110 °C) is complete in only a few minutes in scCO?.; the
reaction now produces a defect-free silane monolayer with no residual silane left in solution.
The only byproduct is the alcohol from the hydrolysis of the alkoxysilane. The CO2 and the
alcohol are readily separated; each is then captured and recycled. The SAMMS emerges from
the reactor clean, dry, and ready to use. This new synthesis produces higher-quality SAMMS
at one-third of the original cost, with virtually no waste. PNNL is working with an oil and
gas filtration equipment company to conduct pilot-scale tests of mercury removal from water
produced during off-shore oil drilling. PNNL expects to commercialize the SAMMS tech-
nology through licensing agreements within the next two years.
Pfizer Global
and Development
Separation ofRacemic Tetmlone
Sertraline is the active ingredient in Zoloft*', used to treat depression. Pfizer has empha-
sized green chemistry objectives in the separation of racemic tetralone, the starting material
for the Sertraline process. Consequently, the Sertraline process is more environmentally
friendly, solvent use is more efficient, process atom economy is better, waste streams are
reduced, and worker safety is enhanced.
Pfizer uses a relatively new technology, multicolumn chromatography (MCC), to separate
its current racemic raw material, 4(/?,5)-tetralone. Pfizer has also demonstrated that the phar-
maceutically undesired enantiomer, 4/?-tetralone, which constitutes 50% of the process
48
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input, can be racemized, reprocessed, and separated as 4S-tetralone by MCC. Thus, the
racemic starting material can be used in the downstream processing more efficiently, greatly
reducing the 4/?-tetralone waste stream, which is toxic to aquatic organisms. Other benefits
of starting with 45-tetralone include: more than doubling the overall yield, reducing by one-
half the volumes of cthanol (saving 800,000 gallons per year), monomethylamine (saving
65-2 metric tons per year), and catalyst (saving 4.1 metric tons per year), eliminating a clas-
sical resolution step (saving 160 metric tons of D-(-)-mandelic acid per year), eliminating the
undesired Sertraline mandelate waste stream (nearly 500 metric tons per year), eliminating
50% caustic (saving 150 metric tons per year) in the process and the subsequent waste steams
associated with the mandelate salt break, and eliminating a methanol recrystallization step
(saving 600,000 gallons per year). The new process could potentially reduce the raw materi-
al requirement of 4(/?,5)-tetralone by 180 metric tons annually. In summary, Pfizer has
dramatically improved its process by using raw materials and energy more efficiently and by
reducing and eliminating waste streams. Pfizer is currently using MCC separation as part of
its synthesis of Sertraline and plans to begin recycling 4/?-tetralonc as soon as it receives
approval from the U.S. Food and Drug Administration (FDA).
Substitution with Carbon Dioxide Eliminates A Major
Use ofSulfuric Acid
Crane & Company, Inc. produces specialty papers with highly technical specifications,
mostly from cotton and other natural and synthetic fibers. Company products include 100%
cotton social stationery, commercial printing papers, reprographic papers, synthetic fiber
nonwovens, and currency and security papers. To reuse preconsumer products that either do
not meet specifications or have been reclaimed from finishing operations (referred to as
'"broke"), Crane must process the paper into a slurry form. Because many of its papers have
a high degree of permanent wet strength, Crane must use an alkaline substance and high tem-
peratures to make the slurries. In its traditional papermaking method, Crane then adjusted
the pH of the slurried broke with sulfuric acid before adding the broke to the papermaking
stock.
Crane's Research and Development Department initiated a toxics use reduction project
aimed at replacing the sulfuric acid with a less toxic chemical. The research was successful,
and Crane is now using its improved process to repulp off-specification papers. The compa-
ny has replaced sulfuric acid with an innovative liquid carbon dioxide system. It has also
reduced the amount of sodium hypochlorite it uses by specifying cleaner raw materials. It
controls the temperature and pH of the process more closely as well. Crane reduced its use
of sulfuric acid by approximately 697,000 pounds and sodium hypochlorite by 576,000
pounds between 1999 and 2000, a combined reduction of about 46%. Overall, these
improvements have reduced the costs of pulp production by 3%.
Tin- and Copper-Compatible Conductive Adhesive for
Lead-Free Electronic Circuit Assembly
Tin/lead eutectic solder is currently the most common product used to attach electronic
components on circuit boards. Lead, however, is a known toxin. Because lead can leach into
the environment, Europe recently passed legislation mandating recycling of consumer elec-
tronics containing lead by 2006. 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 components terminated with palladium/silver, silver, and
Crane & Company, Inc.
Emerson & Cuming
49
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Highland Supply
Corporation
The Dow Chemical
Company
gold (noble metals) 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 and patented chemistry allows it to achieve stable contact
resistance and stable adhesion under damp-heat and high-temperature aging conditions with
tin, tin/lead, and copper finishes. Compatibility with these finishes was not possible in the
past. This compatibility was achieved by preventing galvanic corrosion on these less 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 envi-
ronmental conditions and leads to stable performance over time. About 30 electronic circuit
assembly companies currently purchase the Emerson & Cuming adhesive. Over the last three
years, this product has effectively eliminated the use of 2.3 metric tons of tin/lead eutectic
solder; in five years, it should replace 100 metric tons of solder a year.
Using Chemistry and Engineering Technology to Reduce
Volatile Organic Compound (VOC) Emissions and
Eliminate Hazardous Process Waste in the Printing
Industry
Highland Supply Corporation (HSC) manufactures decorative packaging for the floral
industry using flexographic and rotogravure printing presses as part of its production process-
es. Until 1988, HSC used only solvent-based inks that contained 50% or more VOCs by
weight. During 1988, however, the executive management of HSC accelerated its efforts to
develop a viable water-based ink system and issued a corporate policy directing the reduction
of VOC emissions and hazardous air pollutants (HAPs), which are harmful to human health
and the environment. HSC researched installing air pollution control equipment, but chose
to replace its solvent-based ink system with a cleaner water-based system. Commercially avail-
able water-based inks contained approximately 20% VOCs by weight, however, and had
lower print quality. HSC elected to develop its own water-based ink system to reduce VOC
content further and to increase print quality.
Within the last five years, HSC has refined its technology: now its water-based ink system
contains less than 0.70% VOCs by weight. HSC continues aggressive research to lower this
percentage. By switching from solvent-based to water-based printing inks in all of its facili-
ties, HSC has reduced VOC emissions and eliminated HAPs and hazardous process waste.
Water-based inks also cost about 40% less than solvent-based inks to print the same area. Its
Highland, Illinois plant released 198.5 tons of VOCs in 1989, but releases less than two tons
per year today. In 1989, HSC spent over $100,000 to dispose of hazardous process waste
from that plant; today there are no such wastes, so it spends nothing. The company now recy-
cles all of its water-based inks by reformulating excess inks into useful ones. HSC thoroughly
reviews product information and controls all items that enter its facilities based on strict envi-
ronmental, health, and safety criteria.
VORANOL* VORACTIV* Polyolsfor
Polyurethane Foams
Polyurethane is the material of choice for cushioning materials in automotive seating,
mattresses, and furniture. Its performance is unrivaled by competitive materials. Global pro-
duction of flexible polyurethane foam is over 2 million metric tons (4.4 billion pounds) each
year. Foam producers blend a polyether polyol, an isocyanate, water, a surfactant, and a fugi-
50
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tive tertiary amine catalyst together in a mix-head to form a reacting mixture that generates
the foam. Most foams use either bis(dimethylaminoethyl)ether or trietliyletiediamine as the
fugitive amine catalyst. These amines are undesirable for a number of reasons. First, they may
be hazardous to the skin or eyes and, hence, require careful handling. Second, workers could
be exposed to them during handling and processing of polyurethane chemicals. And third,
they are released slowly from the foam during use and, hence, can provide odor and degrade
indoor air quality.
VORANOL VORACTIV polyols embed the amine catalyst covalcntly into the polyol
structure, eliminating amine catalyst emissions both during the foaming process and from the
finished product. This technology results in performance that exceeds current industry stan-
dards, provides greater yields, and makes smoother, more consistent foam block shapes,
reducing waste from trimming. Dow Chemical has been selling its VORANOL VORAC-
TIV polyols in the U.S. since 2002; in 2004, its global sales exceeded $25 million.
Wash 'n Walk™ Floor Care System
Ecolab has introduced a revolutionary floor care system that removes kitchen grease from
foodscrvicc floors. This system uses a novel no-rinse procedure, leaving enzymes on the floor
to digest and break down the grease deposits that accumulate over time. Formulated to clean
kitchen floors, Wash 'n Walk™ incorporates a patent-pending blend of surfactants, water
conditioners (including Trilon M), lipase, and spore-forming, fatty-acid-degrading microbes
that break down the hard-to-degrade fatty acid components of floor grease. This chemistry
provides immediate cleaning, comparable to industrial-strength floor cleaners, as well as long-
term deep cleaning by removing imbedded organics left in pores, cracks, corners, and
crevices. Its key benefits include: (1) clean floors; (2) clean grout, reducing the potential for
growth of odor-producing bacteria; (3) a significant increase in the coefficient of friction (i.e.,
increased slip resistance) of kitchen quarry tile floors, reducing worker accidents. In addition
to institutional and industrial floors, the environmentally friendly formula of Wash 'n
Walk™ cleans flooring and grout in household kitchens.
Ecolab introduced Wash 'n Walk™ in January 2004; by November 1, 2004, over 30,000
customer sites were already using this product. Ecolab has introduced this product in Canada
and will expand to global sales in 2005. Globally, Ecolab estimates that there are over one
million potential institutional and industrial users for this technology.
WOODSTALK™ Strawboard
Dow Chemical and Dow BioProducts have implemented a revolutionary process for
manufacturing fiberboards using 100% waste straw as the fiber raw material. After harvest-
ing wheat grain, the remaining stalks are typically burned in the fields or plowed into the
topsoil. Historically, field burning has been the preferred method of disposal; however, CO
and CO;; emissions from open-air field burning can be significant, especially in the wheat belt
areas of Kansas, Iowa, and Manitoba. Smoke from these burning fields decreases visibility and
poses health concerns.
In the WOODSTALK™ process, Dow BioProducts takes straw that would have been
burned as waste in the fields and manufactures it into fiberboard composite panels. WOOD-
STALK™ fiberboard competes head-to-head with traditional fiberboard made from wood
particles (i.e., particleboard, medium-density fiberboard, and plywood). WOODSTALK™
fiberboard uses polymeric methylene diphenyl diisocyanate (pMDI) instead of formalde-
hyde-based resins and, therefore, emits substantially less aldehyde than do traditional
Ecolab
Dow BioProducts Ltd.
51
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Ryst-OIeym
Corporation
wood-based composite panels. Overall, the WOODSTALK™ process uses waste from a
renewable resource, reduces CO and CO-2 emissions associated with the wheat harvest, and
substantially reduces the aldehyde emissions from wood-based composite panels that are a
growing concern with indoor air quality. Each year, Dow BioProducts uses over 255 million
pounds of waste straw that would have generated 175,000 tons of CO2 had it been burned.
Dow BioProducts does this today while being competitive with traditional indoor wood-
based fiberboard products.
Zero-VOC, Zero-HAP, No-Odor Industrial Coatings
Sierra Performance Coatings by Rust-Oleum have eliminated the traditional use of sol-
vents to manufacture and apply industrial coatings. Through a number of patented and trade
secret processes, Sierra has developed a way to combine uniquely designed resins and resin
systems into a line of industrial coatings that has zero volatile organic compounds (VOCs),
zero hazardous air pollutants (HAPs), and no odor. As a commercial product line, these coat-
ings reduce VOC and HAP emissions, which translates into broad-based benefits for
end-users (paint applicators, workers, and building occupants) and the environment.
Sierra Performance products range from single-component (IK) acrylic and acrylic-urc-
thanes to two-component (2K) epoxies and acrylic-epoxies. The IK compositions are unique
resin systems that achieve application and finished properties by manipulating particle size,
molecular weight distribution, and chemical composition without solvents. These composi-
tions, combined with other traditional paint and coatings raw materials, activate upon the
evaporation of water. The principal component of the 2K products is a proprietary, advanced-
molecular-weight epoxy polymer with a unique molecular weight distribution that produces
high-performance coatings that cure quickly without requiring solvents to reduce viscosity or
aid coalescence.
Rust-Oleum's development of alternative processes and material compositions has made
possible new designs for watcrbornc resins, coatings, and paint products that meet the
demanding performance requirements of institutions and industry, without any airborne
environmental emissions or worker safety issues. Since Rust-Oleum introduced the Sierra
Performance product line in 2004, the company has sold 90,500 gallons of coatings. The
switch to Sierra coatings has reduced VOC emissions, conservatively, by 200,000 pounds.
52
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winners are with *.
3M Division Laboratory
Development of a Water-Based Adhesive, Primer, and Release Coating
for Post-it® Super Sticky Notes 37-38
Afton Chemical Corporation
Metal-, Phenol-, and Ash-Free Antiwear Hydraulic Additive: Providing
Performance Only Achieved Previously with Zinc-Containing Additives 45-46
Air Polymers, L.P.
Airflex® EF811 Vinyl Acetate Ethylene (VAE) Emulsion Polymer: A Binder for
Environmentally Friendly, High-Performance, Cost-Effective Architectural Coatings 33
Corporation
Advanced Marine Technologies (AMT): Reducing Nitrates in Buzzards Bay by
Producing Organic Gem® Fertilizer from New Bedford's Fish Processing Wastes
(A Sustainable Greater New Bedford Project) 17
* Archer Company
Archer RC"™: A Nonvolatile, Reactive Coalescent for the Reduction ofVOCs in
Latex Paints 8
NovaLipid™: Low Trans Fats and Oils Produced by Enzymatic Interesterification
ofVegetable Oils Using Lifozyme(e> 5
Atmospheric Glow Technologies, Inc.
Sterilization of Medical Devices with Atmospheric Plasma 28-29
*BASF
A UV-Curable, One-Component, Low-VOC Refinish Primer: Driving
Eco-Ejficiency Improvements 7
Eric J., Chemical
Uniwersity of
N-Vinyl Formamide: The "Greening" of a Green Replacement for Acrylamide . ........ 13
K., of Chemistry Chemical
Biology, of Technology
Unconventional High-Efficiency Green Synthesis 16
Company
Irbesartan (Avapro®) Greenness Project 45
Broin Project X"™: A Method for Producing Ethanol Using Raw Starch 34-35
Bunge North America
Enzymatic Degumming of Soybean Oil with PLAj Enzyme 40
Carolina Inc.
A Dry and Environmentally Superior Process for the Recovery of Phosphoric
Acid from Phosphate Ore 19
Changing World Technologies, Inc.
Renewable Feedstock to Marketable Products 27
Chemical Inc.
Green Product and Munitions Compliance Analytical Systems 21-22
53
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Cholli, L., Center for
University of Lowell
Biocatalytically Synthesized High-Performance Novel Antioxidants for Materials 9
deary Chemical Company
ROACH TERMINAL™ Insect Control: A Nontoxic Alternative that Prevents the
Development of Pest Cockroach Populations 28
Sustainable Earth'* Cleaning Products Designed for Health and the Environment 30
Codexis, Inc.
A Clean and Economic Eiocatalytic Process for the Key Chiral Intermediate
for Atorvastatin Using Three Evolved Enzymes 17-18
& Company, Inc.
Substitution with Carbon Dioxide Eliminates a Major Use ofSulfuric Acid 4.9
Cytec Incorporated
Cylinderized Phosphine as a Safer, More Environmentally Friendly
Alternative to Traditional Fumigants for Stored Products 35-36
DeSimone, ML, of Chemistry,
University of Carolina at Hill
of Chemical Engineering, Carolina
University
Surfactant-Free Supercritical Carbon Dioxide Fluoroolefin Polymerization Technology. . . 16
GF-120™ NFNaturafyte™ Fruit Fly Bait 42
BioProdycts Ltd.
WOODSTALK™ Strawboard. 51-52
Chemical Company, The
VORANOL* VORACTIV* Polyols for Flexible Polyurethane Foams 50-51
DyPont Company
Eioderived Solvents, Surfactants, Fuel Additives, and Monomers 34
Dyraflame, Inc.
Duraflame® All-Natural Manufactured Firelog 39
Ecolab
Formula 1 ™ Laundry System 41-42
Wash 'n Walk'™ Floor Care System 51
Eli Lilly Company
An Improved Approach to the Preparation ofDuloxetine and Atomoxetine 44
Emerson & Cuming
Tin- and Copper-Compatible Conductive Adhesive for Lead-Free Electronic
Circuit Assembly 49-50
Fyngi Perfect!, LLC
Mycopesticides and Mycoattractants 23
Garcia-Garibay, Miguel A., Department of Chemistry
Biochemistry, Uniwersity of California, Los Angeles
Solvent-Free, Crystal-to-Crystal Photochemical Reactions: The Synthesis of
Adjacent Stereogenic Quaternary Centers .................................... 15
GlaxoSmithKline
Discovery and Development of a Green Process for Radafaxine. ................. 38-39
54
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GreenEarth Cleaning, L.L.C.
GreenEarth Cleaning': Dry Cleaning With Silicone Solvent 21
o J o
Harris
Evapo-Rust'™: Nonhazardous Rust Removal By Selective Chelation 20-21
Supply Corporation
Using Chemistry and Engineering Technology to Reduce Volatile Organic
Compound (VOC) Emissions and Eliminate Hazardous Process Waste in
the Printing Industry 50
Innovative Formylation Company
Ecological Paint 19-20
Chemical Products, Inc.
PICKLEX11: An Environmentally Safe Metal Surface Preparation and
Pretreatment Chemical. 25-26
JohnsonDiversey, Inc.
A Novel Cleaning System Using Less Toxic, Safer Chemicals 47
Krische, J., of Chemistry
Biochemistry, University of at
Hydrogen-Mediated Carbon-Carbon Bond Formation: Catalytic
Cross-Coupling with Complete Atom Economy 12
LATA Groyp, Inc., The
New Green Technology for Eliminating Hydrogen Sulfide in Aqueous Systems,
Especially Petroleum Industry Systems. .,.,.,.,..,.,.,.,.,.,,.,., 24
Inc.
Equinox* Technology: A Greener Approach to Microbiological Control .............. 41
MacRitchie, Finlay, Department of Grain Science
Indystry, University
The Application of Ultrasound (Sonication) to Catalyze Reactions in
Some Industrial Processes. 9
of Chemistry,
Carnegie University
Development of Environmentally Benign Low- VOC Manufacturing Processes
for Functional Materials: Towards Elimination of Transition Metals from
Materials Made by Atom Transfer Radical Polymerization (ATRP) 10
Technology, Inc.
Data-Collection Technology that Minimizes Environmental Impact
through Intelligent Design 18
*HVIerck & Co.
A Redesigned, Efficient Synthesis of Aprepitant, the Active Ingredient in
Emend*: A New Therapy for Chemotherapy-Induced Emesis 6
*HVIetaboIiJc, Inc.
Producing Nature's Plastics Using Biotechnology................................. 4
IVIETSS Corporation
Environmentally Friendly Aircraft Deicing Fluid 20
Inc.
Technology of Safe, Biodegradable, Non-Polluting Products as Alternatives
to Toxic Microbicidal Chemicals 30-31
55
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MIOX Corporation
On-Site Generation of Mixed Oxidants Using Sodium Chloride Brine as a
Safe Alternative for Chlorine Gas Disinfection 25
MLI
Renewable-Resource-Eased, Environmentally Benign DeicinglAnti-Icing (D/A) Agents . . . 27
SE, Inc.
Levan: A Renewable Raw Material for Several Industries ........................ 22
IVIYCELX Technologies Corp.
MYCELX Technology: Synthesis and Use of a Curable Viscoelastic Polymeric
Surface-Active Agent in the Removal of Organic Pollutants from Aqueous and
Airborne Influent Streams 23
Company
3D Trasar Bio Control 33
D., Of
Uniwersity
Effective, Economical, and Relatively Benign Totally Organic Wood
Preservatives to Replace the Current Copper-Rich Systems ........................ 11
Nike Global Footwear
Development of Nike Brand Footwear Outsole Rubber as an Environmentally
Preferred Material 37
Corporation
Development of Green and Practical Processes Utilizing Dialkyl Carbonates
as Alkylating Reagents 36-37
*No¥Ozymes America, Inc.
NovaLipid™: Low Trans Fats and Oils Produced by Enzymatic Interesterification
of Vegetable Oils Using Lipozyme® 5
Pacific
Self-Assembled Monolayers on Mesoporous Silica Technology: A Green
Alternative Synthesis of a Novel Adsorbent for Mercury Source Reduction 48
Pantheon Chemical
PreKote® Surface Pretreatment: Replacing Hexavalent Chrome with an
Environmentally Safe Solution 26
Discovery and Development of an Environmentally Benign Commercial
Route to Sildenafil Citrate 38
Green Chemistry in the Redesign of the Celecoxib Process 42-43
Green Chemistry in the Redesign of the Pregabalin Process ....................... 43
Green Process for the Synthesis of Quinapril Hydrochloride, A 43-44
Separation ofRacemic Tetralone 48-49
Polnox
Biocatalytically Synthesized High-Performance Novel Antioxidants for Materials ....... 17
Praxair, Inc.
Oxygen-Enhanced Combustion for NOX Control 47-48
T.V. of Chemistry,
The Ohio University
Feedstocks for Catalytic Asymmetric Synthesis: New Route to (S)-lbuprofen
and Other 2-Arylpropionic Acids from Ethylene and Styrene Derivatives .......... 11-12
56
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Recovery Inc.
Process for Treatment of Hog Waste and Production of Saleable Products from
This Waste. 26-27
Rhodia Inc.
Natural, Guar-based Chemistry Reduces Drift and Increases Retention of
Crop Sprays 46-47
*Rogers, D., The University of
A Platform Strategy Using Ionic Liquids to Dissolve and Process Cellulose for
Advanced New Materials. 3
Company
Invention and Commercialization of Environmentally Friendly
Acrylic Thermosets 44-45
Rust-Oleum Corporation
Zero-VOC, Zero-HAP, No-Odor Industrial Coatings 52
Rynex Ltd.
RYNEX® Dry Cleaning Solution 28
River
BioTiger™: Biocatalyst for Accelerated Cleanup of the Environment. ............... 34
SC Johnson
Chemistry-Based Design Process to Create Environmentally Benign
Consumer Products: The Greenlist™ Process 35
Tor P., of
University
Effective, Economical, and Relatively Benign Totally Organic Wood
Preservatives to Replace the Current Copper-Rich Systems 11
Severtson, L, of Prodycts,
University of
Research, Development, and Commercialization of Environmentally Benign
Thermoplastic Pressure-Sensitive Adhesive Label Products 7.5
Solutia Inc.
Deejuest PB—Carboxymethyl Inulin: A Versatile Scale Inhibitor Made
from Chicory Roots 36
Fertilizer
A New Polymer Coating for Increasing Efficiency of Phosphorous Use and
Reducing Environmental Impact. 24-25
Stoller Enterprises, Inc.
Stoller ROOT FEED for Crop Production: Reduction in Fertilizer Pollution,
More Efficacy of Pesticides, Increased Yield, Increased Quality, and Increased
Crop Plant Disease and Insect Tolerance 29
Stoller STIMULATE: A Natural Product for Improving Crop Plant Performance
and Enhancing Pest Resistance 29-30
Tester, W., Chemical
of Technology
Replacing Organic Solvents and Homogeneous Catalysts with Water
and Carbon Dioxide 14
57
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U.S. Army Engineer Research and Development Center
Environmentally Friendly Water Treatments for Control of Corrosion, Scale,
and Bioactivity in Heating and Cooling Systems 40
Mold Prevention through the Novel Use of In Situ Electrochemistry to
Eliminate Water Seepage in Concrete Structures 46
U.S. Army, U.S. Army Edgewood Chemical Biological Center
Enzyme-Based Technology for Decontamination of Toxic Organophosphorus
Compounds 41
U.S. Department of Agriculture (USDA) Agricultural
Research Service
GF-l20™ NF Naturalyte™ Fruit Fly Bait 42
Value Recovery, Inc.
Economic Destruction of Methyl Bromide from Air Streams Using Nonhazardous
Aqueous Solution 39
Van Ooij, Wim J., Department of Chemical and Materials
Engineering, University of Cincinnati
A One-Step, Anti-Corrosion, VOC-Free, Primer System to Replace Chromate
Pretreatment and Pigments 13
Vasileiadis, Sawas
Direct Step Olefin-to-Polyolefin Process with Toxic Solvent Elimination 10-11
Ventana Research Corporation
Development of High-Performance Environmentally Benign Lapping Fluids
for Hard Disk Drive Manufacturing Applications 18-19
Warner, John C, School of Health and the Environment
and Director, Green Chemistry Program, University of
Massachusetts Lowell
Bioinspired Thymine-Based Photopolymers: A Green Chemistry Platform for
Innovation, Research, Education, and Outreach 9-10
WaterSavr Global Solutions, Inc.
WaterSavr™ Evaporation Control 31
Westech Aerosol Corporation
WT-HSC13: A High-Strength, Low-VOC Aerosol Adhesive 31-32
W.F. Taylor Co., Inc.
Meta-Tec™ Low-VOC, One-Component, Cross-Linking Adhesive:
Innovative Science—Applied Technology 22
Wool, Richard P., Department of Chemical Engineering,
University of Delaware and Affordable Composites from
Renewable Resources Center for Composite Materials
Materials from Renewable Resources 12-13
Zhang, Xumu, Department of Chemistry, The Pennsylvania
State University
Practical Asymmetric Catalytic Hydrogenation 14
Zivatech
New Biomass Catalytic Reforming Process for Solid Oxide Fuel Cell
Power Generation 23-24
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