United States
Environmental Protection
Agency
Pollution Prevention and
Toxics (7406)
EPA744-R-01-002
August 2001
www.epa.gov/greenchemistry
The Presidential
Green Chemistry Challenge
Awards Program
Summary of 2000 Award
Entries and Recipients
Printed on paper that contains at least 50% postconsumer fiber.
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The Presidential Green Chemistry
Challenge Awards Program
Contents
Summary of 2000 Award Entries and Recipients 1
Awards 3
Academic Award 3
Small Business Award 4
Alternative Synthetic Pathways Award 5
Alternative Solvents/Reaction Conditions Award 6
Designing Safer Chemicals Award 7
Entries From Academia 9
Entries From Small Businesses 21
Entries From Industry and Government 33
Index 55
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The Presidential Green Chemistry
Challenge Awards Program
Summary of 2000 Award Entries and Recipients
The Pollution Prevention Act of 1990 established a national policy to prevent or reduce
pollution at its source whenever feasible. Green chemistry, the design of chemical products
and processes that reduce or eliminate die use and generation of hazardous substances, is a
highly effective approach to pollution prevention because it applies innovative scientific solu-
tions to real-world environmental situations, all through voluntary partnership programs.
The Presidential Green Chemistry Challenge promotes pollution prevention and indus-
trial ecology through an EPA (U.S. Environmental Protection Agency) Design for die
Environment partnership with the chemistry community. Through high level recognition
and support, die Presidential Green Chemistry Challenge promotes innovative developments
in and uses of green chemistry for pollution prevention. The technologies recognized and
supported by die Presidential Green Chemistry Challenge direcdy reduce risks to human
health and the environment by reducing die hazards associated with the design, manufacture,
and use of chemicals.
Entries received for die 2000 Presidential Green Chemistry Challenge Awards were
judged by an independent panel of technical experts convened by die American Chemical
Society. The criteria for judging included health and environmental benefits, scientific inno-
vation, and industrial applicability. Five projects that best met the scope of the program and
die criteria for judging were selected for 2000 awards and were nationally recognized on
June 26, 2000.
This document provides summaries of die entries received for the 2000 Presidential
Green Chemistry Challenge Awards. The approaches described in diese summaries illustrate
how numerous individuals, groups, and organizations from academia, small businesses,
industry, and government are demonstrating a commitment to designing, developing, and
implementing green chemical methodologies diat are less hazardous to human health and die
environment. The approaches described in diese summaries also illustrate the technical and
economic feasibility of implementing green chemical mediodologies and are recognized for
dieir beneficial scientific, economic, and environmental impacts.
Note: The summaries provided in this document were obtained from the entries received for the 2000
Presidential Green Chemistry Challenge Awards. They were edited for space, stylistic consistency, and clarity,
but they were not written or officially endorsed by EPA. In many cases, these summaries represent only a frac-
tion of the information provided in the entries received and, as such, are intended to highlight the nominated
projects, not describe them fully. These summaries were not used in the judging process; judging was con-
ducted on all information contained in the entries received. Claims made in these summaries have not been
verified by EPA.
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Academic Award
Enzymes in Large-Scale Organic Synthesis
Organic synthesis has been one of the most successful of scientific disciplines and has con-
tributed significantly to the development of the pharmaceutical and chemical industries. New
synthetic reagents, catalysts, and processes have made possible die syndiesis of molecules with
varying degrees of complexity. The types of problems at which non-biological organic syn-
thesis has excelled, ranging from stoichiometric reactions to catalysis with acids, bases, and
metals, will continue to be very important. New synthetic and catalytic methods are, how-
ever, necessary to deal with the new classes of compounds that are becoming the key targets
of molecular research and development.
Compounds with polyfunctional groups, such as carbohydrates and related structures,
pose particular challenges to non-biological synthetic methods, but are natural targets for bio-
logical methods. In addition, biological methods are necessary to deal with increasing
constraints imposed by environmental concerns. Transition metals, heavy elements, and toxic
organic solvents are often used in non-biological processes. When these materials are used
with great care and efficiency, they may still be environmentally acceptable, but their han-
dling and disposal pose problems. The ability to use recombinant and engineered enzymes to
carry out environmentally acceptable synthetic transformations that are otherwise impossible
or impractical offers one of the best opportunities now available to chemistry and the phar-
maceutical industry.
Professor Chi-Huey Wong at the Scripps Research Institute has pioneered work on the
development of effective enzymes and the design of novel substrates and processes for large-
scale organic synthesis. The methods and strategies that Professor Wong has developed have
made possible synthetic transformations that are otherwise impossible or impractical, espe-
cially in areas vitally important in biology and medicine, and have pointed the way toward
new green methodologies for use in large-scale chemistry. A recent study by the Institute for
Scientific Information ranked Professor Wong in the top 15 of the most-cited chemists in the
world for the period 1994 to 1996. According to this study, he is also the most-cited chemist
worldwide working in the area of enzymes.
Some of the strategies and methods developed by Professor Wong are breakthrough
achievements that laid die framework for much of the current use of enzymes as catalysts in
large-scale organic synthesis. The techniques and reagents developed in this body of pioneer-
ing work are used widely today for research and development. The scope of contributions
ranges from relatively simple enzymatic processes (e.g. chiral resolutions and stereoselective
syntheses) to complex, multi-step enzymatic reactions (e.g. oligosaccharide synthesis). For
example, the irreversible enzymatic transesterification reaction using enol esters in environ-
mentally acceptable organic solvents invented by Wong represents the most widely used
method for enantioselective transformation of alcohols in pharmaceutical development. The
multi-enzyme system based on genetically engineered glycosyltransferases coupled with in
situ regeneration of sugar nucleotides developed by Professor Wong has revolutionized the
field of carbohydrate chemistry and enabled die large-scale synthesis of complex oligosaccha-
rides for clinical evaluation. All of diese new enzymatic reactions are carried out in
environmentally acceptable solvents, under mild reaction conditions, at ambient tempera-
ture, and with minimum protection of functional groups. The work of Professor Wong
represents a new field of green chemistry suitable for large-scale syndiesis that is impossible
or impractical to achieve by non-enzymatic means.
Professor
Chi-Huey Wong
The Scripps
Research
Institute
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RevTech, Inc.
Small Business Award
Envirogluv™: A Technology for Decorating Glass and
Ceramicware with Radiation Curable Environmentally
Compliant Inks
Billions of products are sold in glass containers in the United States every year. Most, if
not all, of these glass containers are labeled in some fashion. Typically, decorative indicia are
applied to glass using paper labels, decals, or a process known as applied ceramic labeling
(ACL). ACL involves first printing the glass with an ink composition that contains various
heavy metals such as lead, cadmium, and chromium, then bonding the ink to die glass by
baking in an oven known as a lehr at temperatures of 1,000 °F or more for several hours.
All of these processes have disadvantages. Paper labels are inexpensive but can be easily
removed if die container is exposed to water or abrasion. In addition, paper labels do not pro-
vide die aesthetics desired by decorators who want rich, expensive-looking containers. Decals
are expensive and difficult to apply at die high line speeds diat are required in the decoration
of most commercial containers. More importandy, decals are made from materials diat are
not biodegradable, which causes serious problems in die recycling of glass containers diat are
decorated by diis mediod. The use and disposal of die heavy metals required in ACL presents
serious environmental concerns. Moreover, the high-temperature lehr ovens required in ACL
decorating utilize substantial amounts of energy and raise safety issues widi respect to work-
ers and plant facilities that use this equipment. The inks used in ACL decorating also tend to
contain high levels of volatile organic compounds (VOCs) that can lead to undesirable emis-
sions.
Clearly there has been a need in the glass decorating industry for a decorated glass con-
tainer diat is aesthetically pleasing and durable and can be obtained in a cost-effective,
environmentally friendly, and energy-efficient manner. Envirogluv™ technology fills diat
need. Envirogluv™ is a glass decorating technology diat direcdy silk-screens radiation-cur-
able inks onto glass, then cures die ink almost instandy by exposure to ultraviolet light. The
result is a crisp, dean label diat is environmentally sound, widi a unit cost that is about half
of diat achieved widi traditional labeling.
Envirogluv™ technology offers many human health and environmental benefits. The ink
compositions used in the Envirogluv™ process do not contain any heavy metals and contain
little to no VOCs. All pigments used are biodegradable. The Envirogluv™ inks are cured
directly on the glass by exposure to UV radiation, eliminating the high-temperature baking
in a lehr oven associated widi die ACL process. This provides additional safety and environ-
mental benefits, such as reduced energy consumption and reduced chance of worker injury.
In addition, diere is less raw materials, use and the process does not generate any waste ink.
Furthermore, Envirogluv™ decorated glass containers eliminate die need for extra packag-
ing and are completely recyclable. Applications suitable for die Envirogluv™ process include
tableware, cosmetics containers, and plate glass.
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Alternative Synthetic Pathways Award
An Efficient Process for the Production ofCytovene®, A
Potent Antiviral Agent
The design, development, and implementation of environmentally friendly processes for
the large-scale production of pharmaceutical products is one of the most technically chal-
lenging aspects of business operations in die pharmaceutical industry. Roche Colorado
Corporation (RCC), in establishing management and operational systems for the continuous
improvement of environmental quality in its business activities, has, in essence, adopted die
Presidential Green Chemistry Challenge Program's basic principles of green chemistry: die
development of environmentally friendly processes for die manufacture of pharmaceutical
products. In particular, RCC has successfully applied diese principles to die manufacture of
Cytovene®, a potent antiviral agent used in die treatment of cytomegalovirus (CMV) retini-
tis infections in immunocompromised patients, including patients with AIDS, and also used
for the prevention of CMV disease in transplant recipients at risk for CMV.
In the early 1990s, Roche Colorado Corporation developed the first commercially viable
process for the production ofCytovene®. By 1993, chemists at RCC's Boulder Technology
Center designed a new and expedient process for die production ofCytovene®, which at the
time had an estimated commercial demand of approximately 50 metric tons per year.
Leveraging the basic principles of green chemistry and molecular conservation into the design
process, significant improvements were demonstrated in the second-generation Guanine
Triester (GTE) Process. Compared to the first-generation commercial manufacturing
process, the GTE Process reduced the number of chemical reagents and intermediates from
22 to 11, eliminated the (only) two hazardous solid waste streams, eliminated 11 different
chemicals from the hazardous liquid waste streams, and, efficiendy recycled and reused 4 of
the 5 ingredients not incorporated into the final product. Inherent widiin the process
improvements demonstrated was the complete elimination of the need for operating and
monitoring 3 different potentially hazardous chemical reactions. Overall, the GTE Process
provided an expedient mediod for die production ofCytovene®, demonstrating a procedure
diat provided an overall yield increase of more than 25% and a 100% increase in production
diroughput.
In summary, die new GTE Process for the commercial production of Cytovene® clearly
demonstrates die successful implementation of the general principles of green chemistry: the
development of environmentally friendly syndieses, including die development of alternative
syntheses utilizing nonhazardous and nontoxic feedstocks, reagents, and solvents; elimination
of waste at the source (liquid waste: 1.12 million kg/year and solid waste: 25,300 kg/year);
and, elimination of die production of toxic wastes and byproducts. The process establishes
new and innovative technology for a general and efficient method for the preparation of
Cytovene* and other potent antiviral agents and is registered with die FDA as the current
manufacturing process for the worlds supply ofCytovene®.
Roche
Colorado
Corporation
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Bayer
Corporation
and
Bayer AG
Alternative Solvents/Reaction
Conditions Award
Two-Component Waterborne Polyurethane Coatings
Two-component (2K) waterborne polyurethane coatings are an outstanding example of
the use of alternative reaction conditions for green chemistry. This technology is achieved by
replacing most or all of the volatile organic compounds (VOCs) and hazardous air pollutants
(HAPs) used in conventional 2K solventborne polyurethane coatings with water as the carri-
er, without significant reduction in performance of the resulting coatings. This may seem an
obvious substitution, but due to the particular chemistry of the reactive components of
polyurethane, it is not that straightforward.
Two-component solventborne polyurethane coatings have long been considered in many
application areas to be the benchmark for high-performance coatings systems. The attribut-
es that make these systems so attractive are fast cure under ambient or bake conditions,
high-gloss and mirror-like finishes, hardness or flexibility as desired, chemical and solvent
resistance, and excellent weathering. The traditional carrier, however, has been organic sol-
vent that, upon cure, is freed to the atmosphere as VOC and HAP material. Use of
high-solids systems and aqueous polyurethane dispersions ameliorate this problem, but do
not go far enough.
An obvious solution to the deficiencies of 2K solventborne polyurethanes and aqueous
polyurethane dispersions is a reactive 2K polyurethane system with water as the carrier. In
order to bring 2K waterborne polyurethane coatings to the U.S. market, new waterborne and
water-reducible resins had to be developed. To overcome some application difficulties, new
mixing/spraying equipment was also developed. For the technology to be commercially
viable, an undesired reaction of a polyisocyanate crosslinker with water had to be addressed,
as well as problems with the chemical and film appearance resulting from this side reaction.
The work done on the 2K waterborne polyurethanes over the past several years has resulted
in a technology that will provide several health and environmental benefits. VOCs will be
reduced by 50-90% and HAPs by 50-99%. The amount of chemical byproducts evolved
from films in interior applications will also be reduced, and rugged interior coatings with no
solvent smell will now be available.
Today, 2K waterborne polyurethane is being applied on industrial lines where good prop-
erties and fast cure rates are required for such varied products as metal containers and shelving,
sporting equipment, metal- and fiberglass-reinforced utility poles, agricultural equipment, and
paper products. In flooring coatings applications where the market driving force is elimination
of solvent odor, 2K waterborne polyurethane floor coatings provide a quick dry, high abrasion
resistance, and lack of solvent smell (<0.1 Ib/gal organic solvent). In wood applications, 2K
waterborne polyurethane coatings meet the high-performance wood finishes requirements for
kitchen cabinet, office, and laboratory furniture manufacturers while releasing minimal organ-
ic solvents in the workplace or to the atmosphere. In the United States, the greatest market
acceptance of 2K waterborne polyurethane is in the area of special-effect coatings in automo-
tive applications. These coatings provide the soft, luxurious look and feel of leather to hard
plastic ulterior automobile surfaces, such as instrument panels and air bag covers. Finally, in
military applications, 2K waterborne polyurethane coatings are being selected because they
meet the demanding military performance criteria that include flat coatings with camouflage
requirements, corrosion protection, chemical and chemical agent protection, flexibility, and
exterior durability, along with VOC reductions of approximately 50%.
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Designing Safer Chemicals Award
Sentricon* Termite Colony Elimination System, A New
Paradigm for Termite Control
The annual cost of termite treatments to the U.S. consumer is about $1.5 billion, and
each year as many as 1.5 million homeowners will experience a termite problem and seek a
control option. From the 1940s until 1995, the nearly universal treatment approach for sub-
terranean termite control involved the placement of large volumes of insecticide dilutions
into the soil surrounding a structure to create a chemical barrier through which termites
could not penetrate. Problems with this approach include difficulty in establishing an unin-
terrupted barrier in the vast array of soil and structural conditions, use of large volumes of
insecticide dilution, potential hazards associated with accidental misapplications, spills and
off-target applications, and worker exposure. These inherent problems associated with the use
of chemical barrier approaches for subterranean termite control created a need for a better
method. The search for a baiting alternative was the focus of a research program established
by Dr. Nan-Yao Su of the University of Florida who, in the 1980s, had identified the char-
acteristics needed for a successful termite bait toxicant.
The unique properties of hexaflumuron made it an excellent choice for use in controlling
subterranean termite colonies. The Sentricon* Termite Colony Elimination System, devel-
oped by Dow AgroSciences in collaboration with Dr. Su, was launched commercially in 1995
after receiving EPA registration as a reduced risk pesticide. Sentricon* represents truly novel
technology, employing an Integrated Pest Management approach using monitoring and tar-
geted delivery of a highly specific bait. Because it eliminates termite colonies threatening
structures using a targeted approach, Sentricon* delivers unmatched technical performance,
environmental compatibility, and reduced human risk. The properties of hexaflumuron as a
termite control agent are attractive from an environmental and human risk perspective, but
more importantly, the potential for adverse affects is dramatically reduced because it is pre-
sent only in very small quantities in stations with termite activity. The comparisons to barrier
methods show significant reduction in the use of hazardous materials and substantial reduc-
tion in potential impacts on human health and the environment.
The discovery of hexaflumuron's activity with its unique fit and applicability for use as a
termite bait was a key milestone for the structural pest control industry and Dow
AgroSciences. The development and commercial launch of Sentricon* changed the paradigm
for protecting structures from damage caused by subterranean termites. The development of
novel research methodologies, new delivery systems, and the establishment of an approach
that integrates monitoring and baiting typify the innovation that has been a hallmark of the
project. More than 300,000 structures across the United States arc now being safeguarded
through application of this revolutionary technology, and adoption is growing rapidly.
Dow
AgroSciences
' Trademark of Dow AgroSciences LLC
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8
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2000 Presidential Green Chemistry
Challenge—Entries From Academia
Affordable Composites from Renewable Sources
(ACRES)
In the past two years, the ACRES group has examined several hundred chemical pathways
to convert soy oil to high-performance plastics, adhesives, and composites and has developed
affordable soy resins that are compatible widi high-volume composite manufacturing
processes. New soy-based plastics and adhesive materials are being evaluated and tested by
end-users and converters for high-volume applications in agricultural equipment (tractors
and farming machines) and in the automotive (car and truck parts), civil (bridges and high-
way components), marine (pipes and offshore equipment), rail infrastructure (carriages, box
cars, and grain hoppers), and construction (formaldehyde-free particle board, ceilings, engi-
neered lumber) industries. Recent advances in genetic engineering, natural fiber
development, and composite science offer significant opportunities for new, improved mate-
rials from renewable resources widi enhanced support for global sustainability.
Benign Syntheses in Nearcritical Water
"Nearcritical water" (NCW) is water at elevated temperatures, typically at 250-300 °C,
but still well below the critical point. It is, of course, environmentally benign and far safer for
human health than typical organic solvents, but it also offers exceptional performance char-
acteristics. It offers wide-ranging advantages, ranging from human health to pollution
prevention and waste minimization. As water is heated to near its critical region, die fluid
becomes similar to acetone in density and dielectric constant and, as such, dissolves both salts
and organic chemicals, offering the possibility to run aqueous/organic reactions homoge-
neously. Also, as die temperature is increased, die dissociation constant for water, Kw, goes
up by several orders of magnitude, so that die water itself is both a natural base and acid and
can act to catalyze reactions. Since no base or acid catalysts need to be added, this avoids sub-
sequent neutralization and salt disposal.
Professors Eckert and Liotta at Georgia Tech have formulated an outstanding research
partnership. By a synergistic combination of chemistry and engineering, diey explore inter-
disciplinary areas of science and technology. The Eckert-Liotta Research Group has carried
out extensive studies over die past four years to demonstrate die novel chemistry available in
NCW and to show die wide span of synthetic applications and the economic and environ-
mental benefits of using this solvent, heretofore almost neglected. Working widi industrial
partners, they have demonstrated the value of NCW processes. This team has exploited the
properties of nearcritical water to demonstrate its potential for benign and novel synthetic
processes. Examples include Friedel-Crafts alkylations and acylations, aldol condensations,
Dieckmann condensations, Knoevenagel condensations, and ester and ether hydrolyses.
Professor Richard P.
Wool, Center for
Composite Materials,
University of Delaware
Professor Charles A.
Eckert, School of
Chemical Engineering,
and Professor Charles
L. Liotta. School of
Chemistry and
Biochemistry. Georgia
Institute of Technology
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Professor Eric J.
Beckman, Chemical
Engineering
Department. University
of Pittsburgh
Professor Chao-Jun Li,
Department of
Chemistry, Tulane
University
Catalysts for the Copolymerization of Carbon Dioxide
and Cyclic Ethers
Generating monomers and polymers from CO2 is a task that green plants accomplish
daily on a global scale, yet is one that remains difficult for polymer scientists. Nature has
developed an efficient system for extracting an abundant raw material (CCh) from dilute
solution and generating a variety of monomers and polymers from it. Professor Beckmans
group has created a series of sterically hindered aluminum catalysts (SHACs) that efficiendy
copolymerize carbon dioxide and cyclic ediers to form ether-carbonate copolymers. Unlike
previously reported catalysts for COa/oxirane copolymerization, SHACs allow complete con-
version at 10-50 °C in only hours, permit incorporation of a variety of cyclic ethers
(including ethylene and propylene oxides), generate copolymers with narrow molecular
weight distribution, and permit generation of products where the percentage carbonate can
range from zero to a completely alternating copolymer. The Beckman group has employed
simple alcohols as chain transfer agents during copolymerization; the molecular weight of die
copolymer dropped as predicted, yet the polymerization proceeded to 100% yield in the
same time as that without the transfer agent. Effective chain transfer in a living polymeriza-
tion is crucial, in that if one is to use die catalyst to generate low molecular weight polymers,
it is important that one catalyst fragment generate more dian one polymer chain, minimiz-
ing the amount of catalyst required. Further, dry-box procedures are not needed to employ
SHACs for copolymerizarion. This is significant from a practical perspective, as commercial
oxiranes are usually contaminated with up to 0.1% water, and exhaustive drying is not
feasible.
These catalysts allow the use of a renewable resource, COz, in die generation of aliphatic
polycarbonates, replacing phosgene. Further, the copolymers diemselves contribute to green
chemistry dirough their uses. The Beckman group observed that these ether-carbonate
copolymers are more "CCVphilic" than fluorinated polymers and, hence, can be used as low-
cost CCVphiles in processes employing COi as a solvent and as additives in all COa-blown
foam. Finally, edier-carbonate copolymers will hydrolyze enzymatically and, hence, can be
used in degradable polymers and soaps.
Chemical and Material Syntheses by Using Metal-
Mediated and Catalyzed Reactions in Water
To synchronize the advancement of science and technology widi die advancement of
green chemistry, radier dian sacrificing one or the other, is die key feature of the research car-
ried out by Tulane. A range of technologies has been developed diat uses water as solvent for
chemical, pharmaceutical, and material syndieses. The technologies developed not only offer
many benefits for human healdi and the environment, but also die use of water as solvent
plays an essential role in die success of this research. The use of large quantities of organic sol-
vents for industrial scale operations eventually leads to environmental problems. In fact,
volatile organic compounds are die principle pollutants of all organic compounds. On the
other hand, water is nontoxic, nonexplosive, nonflammable, as well as being die basis and
bearer of life in nature.
Numerous biochemical reactions affecting the living system have inevitably occurred in
aqueous medium. On die odier hand, most organic reactions and syndieses have been car-
ried out in organic solvents. At Tulane, Professor Chao-Jun U has developed various syndietic
methodologies by using water as solvent. By using these methodologies, he has syndiesized
biologically important natural products, novel electronic and optical materials, and nano-car-
10
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bon materials. In most cases, the studies nave the dual advantages of being aqueous and being
"atom economical". The use of water as die reaction solvent makes these reactions environ-
mentally friendly and is essential to die success of this research.
Chemlnformatics: Faster, Better, Cheaper, Greener
Chemical Analyses
A total of 10 million environmental samples were analyzed last year by 900 independent
testing labs, manufacturing companies, and government and university-owned laboratories.
Although no estimates exist for samples analyzed in support of drug discovery programs,
growth in the biomedical and life science markets is expected to dramatically increase the
number of samples analyzed by liquid chromatography/mass spectrometry (LC/MS).
Analyses made in support of state and federal regulatory programs and for research, develop-
ment, manufacturing, and quality control in these two markets alone use more than two
million gallons of solvent annually. The spent waste solvent must be discarded as hazardous
material at a cost of $51 million.
The primary objective of the proposed technology is to dramatically reduce solvent con-
sumption at the source, namely, during the sample preparation process and in the analysis
itself. The data analysis software, called Ion Fingerprint Detection™ (IFD), makes ultrafast
GC/MS and LC/MS possible. The patented peak deconvolution algorithms identify and
quantify target compounds in the presence of other target compounds and highly contami-
nated matrices without extensive sample cleanup. IFD should eliminate approximately 90%
of the solvent needed to prepare and analyze samples by GC/MS and as much as 50% for
LC/MS.
The proposed technology, Ion Fingerprint Detection™ (IFD) software, should reduce
solvent consumption in the two fields dealt with by approximately two million gallons annu-
ally and save $50 million in hazardous waste disposal costs. If forensic, petrochemical, drugs
of abuse, quality control, and other routine types of analyses are included, solvent consump-
tion and cost savings may be ten times the estimated numbers. Toward this end, Professor
Robbat has shown that IFD, when combined with large volume gas chromatography (GC)
inlets, provides quantitative analysis of EPA pollutants in minutes. The data produced have
been verified by state and federal regulators and used to determine contaminant risk to
ground water and to delineate the extent of contamination at twenty-five Superfund sites.
The proposed technology increases measurement precision, accuracy, and sensitivity, and
reduces the per-sample analysis costs.
Environmentally Benign Lithography for Semiconductor
Manufacturing
Current lithographic processes employed by the microelectronics industry have significant
environmental, safety, and health (ESH) impacts. For example, many microelectronics
foundries (fabs) require thousands of gallons of water and solvents for chip production, yet
are often located in arid climates. Both the application and development steps of the sacrifi-
cial resist layer generate large volumes of waste solutions. In the nominated work, solvendess
(dry) application of resist is accomplished by chemical vapor deposition (CVD), an alterna-
tive method to spin-coating films from solution. In an equally important pan of this process,
supercritical fluids (SCF), particularly SCF COa, are used as an alternative to conventional
solvents as the resist development medium. If the functionality of the resist and low dielec-
tric constant thin films are combined, the dielectric layer (an important component in many
Professor Albert
Robbat, Jr., Chemistry
Department, Tufts
University
Professor Karen K.
Gleason, Department
of Chemical
Engineering,
Massachusetts Institute
of Technology, and
Professor Christopher
K. Ober, Materials
Science and
Engineering, Cornell
University
11
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microelectronic devices) may be directly patterned. This would dramatically
simplify microelectronics fabrication by eliminating steps associated with application, pat-
terning, and stripping of the sacrificial resist layer.
Both 157-nm light and e-beam irradiation were investigated as a means to afford differ-
ential solubility of the exposed region to supercritical CCh. Both of these irradiation
techniques have sufficient resolution to achieve the nanoscale patterning desired for future
generations of integrated circuits. The micron-scale images were fully developed using SCF
COa. This result represents the first time that fluorocarbon CVD films have been direcdy
patterned on the micron scale. This is a proof of concept that low dielectric constant films
can be directly patterned without the use of resist or conventional solvents, affording the
opportunity to gready reduce processing complexity and waste relative to conventional
lithography.
Dr. Nancy W. Y. Ho,
Laboratory of
Renewable Resources
Engineering, Purdue
University
Professor James M.
Tanko, Department of
Chemistry, Virginia
Polytechnic Institute
and State University
Genetic Engineering of Saccharomyces Yeasts for
Effective Production ofEthanol and Other Green
Chemicals from Renewable Biomass
Ethanol is an effective, environmentally friendly, non-fossil transportation bioruel that
produces far less pollutants than gasoline. Furthermore, ethanol can be produced from plen-
tiful, domestically available, renewable cellulosic biomass. This reduces our nation's
dependency on imported oil, protects our energy security, and reduces our trade deficit.
Furthermore, cellulosic biomass is renewable, available at low cost, and extant in great abun-
dance all over the world, especially in the United States. Cellulosic biomass is, therefore, an
attractive feedstock for the production of ethanol-fuel and numerous other industrial prod-
ucts by fermentation. Although ethanol has been produced by die fermentation of
glucose-based feedstocks with Saccharomyces yeasts since die pre-industrial age, the conver-
sion of cellulosic biomass to ethanol presented a major challenge. This is because cellulosic
biomass contains two major sugars (glucose and xylose), and die Saccharomyces yeasts cannot
ferment xylose to edianol.
Dr. Ho has developed genetically engineered Saccharomyces yeasts that not only ferment
xylose but can also effectively coferment glucose and xylose to edianol. The genetically engi-
neered yeasts produce at least 30% more edianol from cellulosic biomass dian die
non-engineered parent yeasts. Dr. Ho's group has also recendy found diat dieir stable, meta-
bolically engineered yeasts can repeatedly coferment glucose and xylose (using pure sugars or
sugars from cellulosic biomass hydrolysates) to ethanol with high efficiencies for numerous
cycles requiring very litde nutrients. The technology outlined can easily be expanded to make
yeast for the production of other important industrial products, such as lactic acid and citric
acid, using glucose and xylose derived from cellulosic biomass as die feedstock
Green Chemistry through the Use of Supercritical Fluids
and Free Radicals
Professor Tanko explored the use of supercritical carbon dioxide (SC-COi) as a replace-
ment for many of the toxic and/or environmentally-direatening solvents used in chemical
synthesis. This research demonstrated that SC-COa is a viable, environmentally benign alter-
native to a variety of heahh or environmentally hazardous solvents and diat there are also
numerous advantages from a chemical perspective associated widi die use of SC-COa . The
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research led to the development of a new, environmentally friendly chemical process for
hydrocarbon functionalization and C-C bond formation.
SC-CO2 is especially attractive because its critical parameters (temperature and pressure)
are moderate, thereby permitting access to the supercritical state without a disproportionate
expenditure of energy. The newly developed hydrocarbon functionalization accomplishes (in
a single, high-yield step) a transformation which would normally require multiple steps and
the use of toxic reagents or strong acids and bases. This reaction should scale up readily for
large-scale (or industrial) applications.
In Vivo Synthesis of Lepidopteran Pheromone Precursors
in Saccharomyces cereviseae: An Economical Process for
the Production of Effective, Nontoxic, Environmentally
Safe Insect Control Products
Since die advent of DDT more dian 50 years ago, broad spectrum neurotoxic insecticides
have provided the principle means for the control of economically important insects in agri-
culture and public health programs. Whereas the use of synthetic insecticides initially resulted
in spectacular increases in crop yields and the suppression of some important human and ani-
mal disease vectors, the development of insecticide resistance in insect pest populations and
the environmental damage caused by insecticides were quickly recognized as serious draw-
backs to their use. Today, the environmental and human health effects associated with the
manufacture and use of insecticides for pest control are widely recognized, including their
acute toxicity to nontarget organisms (including human applicators), their persistence in the
biosphere, and major point-source pollution associated with their manufacture. Despite diese
effects, the scale of release of active ingredients in insecticide formulations into the global
environment is enormous; in the United States alone it is more than 400 million kg/year.
Pheromones have been used on a worldwide basis for the control of insect pests for more
than 15 years. Unlike conventional broad-spectrum insecticides, pheromones are nontoxic
and highly specific for the species they are intended to control. Unfortunately, their effec-
tiveness and selectivity depend upon high chemical and stereospecific purity, making them
expensive to synthesize. The latter factor has limited their commercial success versus conven-
tional insecticides. The major market for pheromone-based disruption products is in the
United States and amounts to less dian $50 million/year. In contrast, the worldwide insecti-
cide market is greater than $6 billion/year. The goal of the work of Dr. Knipple at Cornell
University is to develop a cheaper process for pheromone syndiesis. Toward this goal, he has
proposed to use genetic and molecular technology to clone and functionally express in vivo
genes encoding desaturase enzymes present in the pheromone glands of adult female moths,
which catalyze the formation of key unsaturated pheromone intermediates. Accomplishment
of the technical objectives of this work will contribute materially and methodologically to
development of an alternative biosynthetic process for commercial pheromone production.
Achievement of the latter goal will significantly improve the economic competitiveness of
existing pheromone products and could provide the basis for the expansion of this promis-
ing insect control technology into other markets.
Dr. Douglas C. Knipple,
Department of
Entomology, Cornell
University
13
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Professor Joan F.
Brennecke, Department
of Chemical
Engineering, University
of Notre Dame, and
Professor Eric J.
Beckman, Department
of Chemical and
Petroleum Engineering,
University of
Pittsburgh
Dr. Ajay K. Bose,
Department of
Chemistry and
Chemical Biology,
Stevens Institute of
Technology
Ionic Liquid/CO2 Biphasic Systems: New Media for
Green Processing
Room-temperature ionic liquids are considered to be environmentally benign reaction
media because they are low-viscosity liquids with no measurable vapor pressure. However, the
lack of sustainable techniques for the removal of products from the room-temperature ionic
liquids has limited their application. Professors Brennecke and Beckman have shown that
environmentally benign carbon dioxide, which has been used extensively, both commercial-
ly and in research for the extraction of heavy organic solutes, can be used to extract
nonvolatile organic compounds from room temperature ionic liquids (Blanchard et al.,
Nature, 1999,399, 28). They found that extraction of a material into carbon dioxide repre-
sents an attractive means for recovery of products from ionic liquids because (a) CO:
dissolves in the ionic liquid to facilitate extraction, and (b) die ionic liquid does not dissolve
appreciably in the CO:, so the product can be recovered in pure form.
The research groups of Professors Brennecke and Beckman have shown that ionic liquids
(using l-butyl-3-methylimidazolium hexafluorophosphate as a prototype) and CO: exhibit
extremely unusual, and very attractive, phase behavior. The solubility of CO: in ionic liquids
is substantial, reaching mole fractions as high as 0.6 at just 8 MPa. Yet the two phases do not
become completely miscible, so CO: can be used to extract compounds from the ionic liq-
uids. Most importantly, the composition of die CO:-rich phase is essentially pure CO:; that
is, there is no measurable cross-contamination of the CO: by the ionic liquid. Moreover, non-
volatile organic solutes (using naphthalene as a prototype) may be quantitatively extracted
from the ionic liquid with CO:, demonstrating the tremendous potential of ionic liquid/CO:
biphasic systems as environmentally benign solvents for combined reaction and separation
schemes.
Microwave-Induced Organic Reaction Enhancement
(MORE) Chemistry for Eco-Friendly Syntheses
Microwave-assisted organic synthesis is an emerging technology of great potential. Dr.
Ajay K. Bose at the Stevens Institute of Technology has contributed to this Held through the
development of nontraditional methods for using domestic microwave ovens for conducting
a wide variety of organic reactions that are fast, safe, and friendly to the environment. Dr.
Bose's group has shown that for a wide variety of reactions, microwave irradiation of reaction
mixtures in open glass vessels can lead to faster reaction rates, fewer byproducts, and higher
steric control. Because microwaves interact directly widi molecules with dipoles, there is lit-
tle need for a liquid medium to convey heat from the glass walls as in conventional heating.
The key features of Microwave-Induced Organic Reaction Enhancement (MORE) chemistry
techniques are die use of limited amounts of high-boiling solvents (or no solvents) — enough
to form the reaction into a slurry at room temperature — and efficient control of microwave
energy input to reach the desired reaction temperature widiout allowing the reaction mixture
to come close to its boiling point. Such reactions can be completed on several-hundred-grams
scale in a few minutes. Larger-scale synthesis should be possible by using commercial
microwave equipment used by the food industry.
The elimination or reduction of the use of organic solvents, and die purer products
formed, lead to reduced chemical waste (e.g., organic solvents for reactions and recrystalliza-
tion and chromatographic material for purification). To demonstrate 'atom economy (more
product for all the chemicals used) and the versatility of MORE chemistry techniques, Dr.
Bose's group has conducted multistep syntheses (including one-pot reactions for two or more
14
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steps) of advanced intermediates for lactam antibiotics, amino sugars, alkaloids, and other
biologically active compounds such as Taxol. They have also found that an efficient and eco-
friendly nitration mediod can be accomplished by irradiating with microwaves, have
observed mild acceleration of chemoenzymatic reactions under low-intensity microwave irra-
diation, and have devised a very eco-friendly oligopeptide synthesis that needs no
conventional peptide bond forming agents. In brief, MORE chemistry techniques can offer
very significant reductions in pollution at the source for small-scale as well as large-scale syn-
thesis, and thus make the development and production of life-saving drugs more eco-friendly.
On-Line Detection of Subsurface Pollutants by Thermal
Extraction Cone Penetrometry-ThermalDesorption Gas
Chromatography/Mass Spectrometry
The ability to rapidly assess or monitor the disposition of environmental contaminants at
purported or existing hazardous waste sites is an essential component of die nations envi-
ronmental restoration program. Last year, 900 independent environmental testing labs
analyzed five million samples in support of regulatory programs. Soil samples have to be col-
lected from surface to ground water and then shipped off-site for analysis with waiting
periods exceeding months. Soil samples, which represent approximately half the total num-
ber, are extracted with solvent then further separated using additional solvent to produce
chemical-specific fractions. Each fraction is then analyzed by an appropriate method. The
proposed technology is aimed at reducing or eliminating solvent usage during the sample col-
lection and sample analysis process by collecting and detecting organic pollutants at depth
without bringing the actual soil sample to the surface.
A thermal extraction cone penetrometry probe coupled to an ultrafast gas chromatogra-
phy/mass spectrometer (TECP-TDGC/MS) has been developed to collect and analyze
subsurface organic contaminants in situ. The TECP is capable of heating the soil to 300 °C,
which is sufficient to collect volatile and semivolatile organics bound to soil, in the presence
of soil-water content as high as 30%. Rather than using solvents to extract organics from soil,
the TECP uses heat, then traps the h6t vapor in a Peltier-cooled thermal desorption GC sam-
ple inlet for on-line analysis. In addition, the proposed technology reduces solvent usage
when decontaminating sample collection probes and utensils used to homogenize samples.
No other technology exists that is capable of thermally extracting organics as diverse as PCBs,
explosives, or PAHs under these conditions. When combined with the ION Fingerprint
Detection™ software, ultrafast TDGC/MS is capable of analyzing complex environmental
samples in less than 5 minutes.
Overcoming the Recalcitrance ofCellulosic Biomass and
Envisioning the Role of Biomass in a Sustainable World
This project addresses technical and visionary issues associated widi utilizing plant bio-
mass, the only foreseeable sustainable source of organic fuels, chemicals, and materials. The
project involves multiple topics related to consolidated processing, a widely applicable poten-
tial breakthrough in cellulose processing entailing production of cellulose enzymes, hydrolysis
of biomass components, and fermentation of resulting soluble carbohydrates in a single
process step. Additional project elements aimed at overcoming the recalcitrance of cellulose
biomass encompass aspects of applied enzymology and microbiology, kinetics and reactor
design for enzymatic hydrolysis of cellulose, pretreatment of biomass using compressed hot
water, and conversion of paper sludge. Process design and analysis work support the con-
Professor Albert
Robbat Jr., Chemistry
Department. Tufts
University
Dr. Lee R. Lynd, Thayer
School of Engineering,
Dartmouth College
15
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Professor Craig L. Hill,
Department of
Chemistry, Emory
University, and Dr. Ira
A. Weinstock, U. S.
Department of
Agriculture Forest
Service. Forest Products
Laboratory
tention that advanced biomass-based processes have the potential to be cost-competitive with
petroleum-based processes even at low oil prices. Accomplishments involving resource and
policy analysis include analysis that identifies and explores the potential of biomass-based
processes to have near-zero net CC>2 emissions, prioritizes among uses for the large but ulti-
mately limited biomass resource, and seeks to reconcile the vast range of estimates for the
magnitude of potential biomass availability for industrial uses.
Pollution-Free Conversion of Trees to Paper Using Air in
Place of Sulfur and Chlorine
A completely new approach to the delignification of wood or wood pulp — composites
of cellulose and lignin — for paper manufacture has been developed. This chemistry achieves
a goal no other technology developed thus far does, but one that is operable in nature — the
selective delignification of wood or wood pulp using only die readily available and nontoxic
agents air and water. Wood is comprised principally of two biopolymers: cellulose, which
imparts strength to trees and paper, and lignin, which imparts color, texture, and mechanical
properties to wood. The goal in the manufacture of high-quality paper is to remove the lignin
with as litde damage to the cellulose fibers as possible (high-quality paper is composed of
lignin-free cellulose fibers).
Nature carries out this chemically and technically challenging multistep process by using
a complex ensemble of selective metalloenzymes (glyoxal oxidase, ligninase, and Mn peroxi-
dase). The pulp and paper industry, since its inception many decades ago, has yet to achieve
what nature has. Chlorine compounds, not C>2, have been the dominant oxidants. While
decades of optimization have led to highly selective delignification (minimally damaged cel-
lulose), these man-made technologies produce waste streams that contain environmentally
deleterious phenolic compounds as well as non-biodegradable chloroaromatics. In conse-
quence, societal and legislative pressure in all developed countries is compelling pulp
manufacturers to phase out chlorine. The most attractive alternative oxidants, hydrogen per-
oxide (H2O2) or ozone (Os), are encumbered by inherent limitations. Hydrogen peroxide is
simply not effective. Ozone processes, while potentially effective, fall far short of the selectiv-
ity required for general commercial use or of the selectivity seen in nature.
The new catalytic biomimetic approach uses versatile, nontoxic, and inexpensive inor-
ganic dusters known as polyoxometalates (POM) in two steps. The first step involves
selective reaction of lignocellulose (wood or pulp) with the oxidized POM leaving high qual-
ity cellulose fibers. As the POM is reversibly reduced, the lignin is oxidized and solubilized.
In the second step, O2 is added and the same POM catalyzes the complete conversion (min-
eralization) of the dissolved lignin fragments to CO2 and t^O. The two steps sum to the
selective removal of lignin from wood, using only air and water, an ideal process that only
nature has achieved to date. This biomimetic and catalytic technology eliminates the envi-
ronmental problems associated with conventional chlorine-based processes while overcoming
the limitations inherent in other chlorine-free pulp bleaching strategies. It is green in at least
six ways, including the complete elimination of waste streams (a "closed process" is achieved).
The high selectivity entails less consumption of the natural renewable resource, wood. It is
energy-efficient and, as current analyses indicate, cost-effective.
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Pollution Prevention through Simultaneous Reduction of
Emissions and Commercial Utilization of Energy
Related Waste Streams
The U.S. electric power industry relies heavily on the use of coal as its main energy source,
where coal-fired units generate annually over 55% of the total electricity produced in the
United States. However, the U.S. power utility industry faces environmental challenges due
to emissions of pollutants such as NOx and die associated increase in byproduct waste
streams. The installation of low-NOx burners has efficiendy decreased NOx emission levels
by lowering die temperature of combustion, but this results in reduced combustion efficien-
cy and an increase in die concentration of uncombusted coal in die fly ash. This increased
concentration of unburned carbon restricts die use of fly ash in the cement industry; conse-
quendy, die carbon-rich ash is placed in holding ponds or landfilled.
Dr. Maroto-Valer has addressed this problem by combining the installation of low-NOx
burners in coal combustion furnaces with strategies that manage the associated increase of
byproduct streams, mainly fly ash and unburned carbon. Two novel, cost-effective routes for
die commercial utilization of unburned carbon present in fly ash have been established. In
the first route, steam activation of the unburned carbon generates activated carbons suitable
for water purification applications. In the second route, the unburned carbon serves as a supe-
rior replacement for petroleum coke in the manufacture of carbon artifacts used in
applications ranging from brushes for electrical machines to anodes for aluminum smelting.
This program offers a sustainable source of energy for the next century by simultaneously
reducing emissions and byproduct waste streams.
Production of Hydrogen Peroxide Directly from
Hydrogen and Oxygen in CO2
Hydrogen peroxide is an environmentally benign oxidant that has replaced chlorinated
reagents in paper processing, is used in drinking water treatment, and is increasingly sug-
gested as a green oxidant in chemical processing. Hydrogen peroxide is generally considered
to be a green oxidant, as it is relatively non-toxic and breaks down in the environment to non-
toxic byproducts. Despite its "green" characteristics, H2O2 is not produced in a particularly
green manner. The current method for production, the sequential hydrogenation and oxida-
tion of an alkyl anthraquinone, has been in use for over 50 years, produces significant
volumes of waste, and consumes sizeable quantities of energy during the purification and
concentration of the product. Because H2Oa is produced in organic solvent, then recovered
by stripping into water, the solvent contaminates die aqueous product, creating a situation
that requires downstream remediation before die product can be sold. The rates of bodi the
hydrogenation and oxidation steps of the synthesis are limited by transport between the gas
and liquid phases, and by the low solubility of hydrogen and oxygen in liquids. Multiple
phases present in the reactors also prevent strict control over anrhraquinone residence time,
leading to generation of a byproduct waste stream. There has been great interest over the past
three decades in the direct synthesis of HaOa from Oa and H:, yet processes developed to date
have been unable to resolve the safety vs. productivity dilemma to the point where scale up
has been advisable.
Professor Beckman has synthesized a series of highly CO2-soluble palladium catalysts and
has subsequendy generated HiO2 from O2 and H2 in a biphasic mixture of CO2 and water.
The use of CO2 as a solvent permits the use of reasonable concentrations of H2 and O2 with-
out danger of explosion, and homogeneous catalysis eliminates difrusional limitations to the
Dr. M. Mercedes
Maroto-Valer, The
Energy Institute, The
Pennsylvania State
University
Professor Eric J.
Beckman, Chemical
Engineering
Department, University
of Pittsburgh
17
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Dr. Thomas Mitzel,
Department of
Chemistry, Trinity
College
Professor Harold S.
Freeman, Department
of Textile Engineering
Chemistry and Science,
North Carolina State
University
reaction. The H2C>2 produced is rapidly stripped into water, minimizing the degradation of
the product by the catalyst commonly observed in heterogeneous systems. This process con-
figuration eliminates waste streams owing to anthraquinone degradation and die use of
organic solvent and also eliminates die need for distillation, reducing energy requirements
substantially. In summary, production of HiOi direcdy from Ha and Oz in CO: reduces
waste, eliminates the use of the organic solvent, and eliminates diree energy-intensive units:
the oxidation reactors, die stripping column, and the distillation train. This process will pro-
duce a cleaner product, while using less energy, at a significandy lower cost than die
andiraquinone route.
Stereoselective Synthesis of Epoxy Alkynes: Use of
a-Chlorosulfides to Control Syn/Anti Selectivity in
Indium Promoted C-C Bond Formation in an Aqueous
Medium
In response to increasing demands for die chemical industry to implement more envi-
ronmentally friendly practices, chemists have begun to probe the development of organic
transformations in an aqueous medium. The use of water as a solvent in these transforma-
tions is attractive for a number of reasons: 1) water is die cheapest solvent on earth, making
it economically favorable; 2) synthetic efficiency may be increased by eliminating die need
for traditional protecting groups; 3) reaction conditions are simplified, because an inert
atmosphere and anhydrous solvents are not needed; and 4) pollution caused by use and dis-
posal of traditional organic solvents is eliminated. Indium metal has proven effective in
promoting C-C bond formation in aqueous media, forming chelates diat allow good stereo-
control in die formation of coupling products.
Professor Mitzel has employed indium in water to selectively synthesize epoxy alkynes
from a-chlorosulfides. Because epoxyalkyne functional groups are prevalent in a variety of
natural products, stereoselective syntheses of diese molecules have potential industrial appli-
cations. Utilizing indium metal allows this reaction to be carried out in water, a benign
solvent that is more readily recycled than traditional organic solvents, thereby decreasing
organic emissions while increasing safety.
Synthetic Dyes Based on Toxicological Considerations
This nomination pertains to the design of nontoxic alternatives to currendy used metal-
complexed dyes containing metals designated as priority pollutants. Specifically,
iron-complexed dyes were synthesized as substitutes for metal-complexed dyes currendy used
in situations requiring colorants possessing very high photostability and resistance to removal
under wet conditions. The dyes investigated were iron (Fe) complexes of ligands and provid-
ed the foundation for a pollution prevention approach to environmental problems associated
widi the manufacture and use of organic dyes based on chromium (Cr) and cobalt (Co). As
a starting point for this study, die Freeman group synthesized and evaluated Fe-complexed
analogs of commercial azo and formazan dyes containing Cr and Co. Fe (II) sulfate was
employed as the metallizing agent because it has exhibited low aquatic toxicity in studies.
This investigation led to the discovery of nontoxic alternatives to high-volume chromi-
um-based commercial black dyes, without compromising the desirable photostability of the
latter. In addition, red and blue 1:2 Fe-complexed dyes (1 iron atom per 2 dye molecules)
were discovered, an achievement heretofore unreported and presumed unachievable. An
18
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explanation for the dull colors that have traditionally characterized Fe-complexed dyes was
also developed, providing a basis for further achievements in this area.
Tandem Enzymatic-Electrochemical Methods for Green
Manufacturing: Efficient Synthesis of Pharmaceuticals
from Halogenated Aromatic Waste
The prevention of pollution at its source is addressed by die replacement of currently used
methods of oxidation and reduction (i.e., all based on metal reagents) with enzymatic and
electrochemical techniques (i.e., all performed in water, alcohols, or other environmentally
accepted solvents). The combination of enzymatic transformations with electrochemistry,
along with efficient designs, yields unprecedented brevity in the attainment of important
Pharmaceuticals from metabolites of the arene cis-diol type. Halogenated aromatic com-
pounds, viewed in many cases as harmful to the environment, are enzymatically converted to
useful synthons and effectively removed from the hazardous waste pool, with added eco-
nomic benefits of strategic conversion that would not be available through outright
incineration of such compounds. It must be emphasized that the enzymatic conversion of the
toxic aromatic materials takes place in the very first step of the synthetic pathway and that all
subsequent intermediates are harmless. The residual mass from enzymatic or electrochemical
processes is judged suitable for disposal to municipal sewers, thus further reducing the
amount of actual waste. The synthesis of a homochiral cyclitol from halobenzene by several
steps involving essentially no reagents serves as the illustration of the technology. Given that
the length of a synthesis plays a direct role in the attendant accumulated waste mass for the
process, it follows that short and efficient syntheses lead to lesser accumulation of waste and
thus reduce pollution at the source.
The Use of Soluble Polymers to Recover Catalysts and to
Control Catalytic Reactions
New strategies for the use and recovery of homogeneous catalysts and for carrying out
chemical processes are of increasing interest because of problems associated with the use of
organic solvents and the costs associated with purification and the removal and disposal of
byproducts. This nomination recognizes the work by Bergbreiter's group at Texas A&M,
which uses polymeric ligands and new separation strategies to facilitate homogeneous catal-
ysis. This technology uses the well-known properties of polymers to recover and separate
catalysts and ligands for reuse. By employing relatively simple polymer chemistry, a wide vari-
ety of known homogeneous catalysts can be attached to such polymers without significant
alteration of their reactivity or selectivity. Separation and recovery strategies that use solid/liq-
uid separation of precipitate polymers or liquid/liquid separations of polymer
solutions/product solutions have both been demonstrated. The utility of simple linear poly-
mers in the formation of aqueous and fluorous phase soluble catalysts has also been
demonstrated by this work. Finally, this technology has also demonstrated a unique approach
to regulate and control reactions using soluble polymer-bound "smart" ligands that precipi-
tate on heating.
Professor Thomas
Hudlicky, Department
of Chemistry,
University of Florida
Professor David E.
Bergbreiter,
Department of
Chemistry, Texas A&M
University
19
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20
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2000 Presidential Green Chemistry
Challenge—Entries From Small
Business
Biodegradable Thermoplastic Material (Mater-Bi™)
Mater-Bi™ is a completely biodegradable and compostable resin that has the physical
and mechanical properties of conventional plastics. Mater-Bi™ is designed to be used in the
manufacture of a wide range of disposable products such as trash bags, shopping bags, food
serviceware, and packagings. Mater-Bi™ is a product technology that offers enormous
advantages for dealing with die problems of solid waste disposal. Disposal of conventional
plastic products, which constitute the largest share of disposable products, has a significant
negative impact on die environment. Typically, disposal products are landfilled and rapidly
diminish landfill capacity. Being compostable, disposable products made of Mater-Bi™ are
fully recyclable.
Biodegradable food serviceware, for example, presents a significant opportunity for reduc-
ing die volume of die solid waste stream. In 1994, nearly 39 billion pieces of disposable
cudery (knives, forks, and spoons) were used in die United States. More dian 113 billion dis-
posable cups and nearly 29 billion disposable plates were used. Biodegradable products are
being developed for medical products, textiles, and odier new and significant applications.
Such products can be transformed into much needed composts and soil amendments for
agricultural and horticultural use. Mater-Bi™ resin used for films and sheets is made of
starch and a polymer, polycaprolactone. Biodegradation time is between 20 and 45 days in
composting conditions. Mater-Bi™ resin used for dimensionally stable injection molded
items is made from completely natural products, including cotton seeds and cornstarch.
Biodegradation time is between 75 and 120 days in normal composting conditions.
Cadmium Replacement in. Mechanical Coating
Madison Chemical Company manufactures specialty chemical compounds used in
numerous applications throughout general industry and in die metal manufacturing indus-
try. In die mechanical plating industry, platers use powdered metal rotated in a barrel widi
impact media to mechanically plate parts. Frequendy, cadmium is die metal of choice in
mechanical plating applications because it adheres to die substrate metal to form a corrosion-
resistant coating while giving die coated part a lustrous finish. Cadmium is also highly toxic,
a proven carcinogen, and listed under Section 313 of SARA. Chemists at Madison Chemical
developed a method of replacing large concentrations of cadmium widi trace amounts of
nickel in zinc mechanical plating. Zinc and nickel exhibit far less toxicity than cadmium, and
the product shows greater corrosion resistance than the cadmium compounds generally used.
This formula change, MULTIPLATE N-2000, received two U.S. Patents.
Mechanical Coatings, a Madison Chemical customer, was able to reduce their usage of
cadmium by 100 pounds per week using the MULTIPLATE N-2000 process. In addition to
that reduction, Mechanical Coatings also eliminated one complete waste stream, and a sec-
ond waste stream containing mainly zinc is now recyclable. Mechanical Coatings also
completely eliminated its hazardous waste, saving at least $12,000 per year in disposal costs.
MULTIPLATE N-2000 has also made compliance with local, state and federal environmen-
tal laws much easier.
BIOCORP, Inc.
Madison Chemical
Company
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CerOx Corporation
ClearMate, Inc.
The CerOx Process: A Non-Thermal Alternative for
Hazardous Waste Destruction
The release and subsequent presence of persistent, bioaccumulative, and toxic (PBT)
materials in the environment have recently come to the forefront of the public consciousness.
The adverse health effects of PBTs, such as dioxins, have been well documented and have led
to the placement of very strict limits on the releases of these materials to die environment by
industrial processes, particularly from waste disposal by incineration. The chemistry and
physics of die thermal processes, particularly with incineration, are such diat die production
of dioxin-type materials is obligatory given the process conditions. Materials pass dirough the
high temperature zone without being completely combusted and continue to "burn" at lower
temperatures. It is here diat die dioxin-type materials are syndiesized.
The CerOx Process is a cerium-catalyzed chemical process for die destruction of organic
hazardous materials under mild reaction conditions, atmospheric pressure, and temperatures
less than 100 °C. The CerOx Technology is an alternative to incineration diat does not pro-
duce the products of incomplete combustion diat have plagued high temperature destruction
mediods. The process uses the high oxidizing power of Ce(IV) in a closed liquid solution to
destroy die organic compounds. Upon reaction, die Ce(IV) is reduced to a nonreactive
Ce(III) diat, in turn, is recycled to die active Ce(FV) oxidation state via an electrochemical
oxidation. The cerium ion is a true (electro)catalyst and is not consumed in die reaction.
Virtually all organic materials can be processed and destroyed by the CerOx Process,
including PCBs, dioxins, pesticides, chlorocarbon wastes, and chemical weapons agents. The
organic materials are converted to carbon dioxide and water; die odier reaction products are
chlorine from chlorocarbons, sulfate from organosulfur compounds, phosphate from
organophosphates, and nitric acid from amines. Comparison of die process conditions and
economics of the CerOx Process to standard incineration indicates diat diis new nondiermal
technology is economically competitive with existing technologies and, in many cases, is
more economical dian die incinerator alternative.
ClearMate
Process chemicals used in die electroplating industry are subject to a number of harmful
contaminants that ultimately decrease die usable capacity of a process solution. Once a badi
is no longer usable it must be waste-treated, usually in die form of an expensive batch dump.
In particular, die clear chromate badi is most susceptible to harmful contaminants and its life
can vary in length from one week to one mondi based on heavy to moderate use, respective-
ly. The major contaminant of die clear chromate solution is iron, which is introduced to the
system when raw metal parts are submerged during processing or dropped and left at die bot-
tom of a chromate tank.
Clearmate developed a process for recovering a spent clear chromate solution and dien
developed an additive diat prevented premature iron contamination in die first place. The
ClearMate chemical additive is an innovative, yet simple, chemical combination diat drasti-
cally extends die longevity and quality of die clear chromate conversion solution for the metal
finishing industry. It can extend die lifetime of conventional clear chromate solutions by a
factor of 12. The additive protects raw metals from die acidic nature of die chromate solu-
tion. On initial contact widi raw metal substrates, iron begins to dissolve into solution as an
ion. The additive contains highly charged cationic polyelectrolytes diat surround and impede
any attack on die substrate by die acidic chromate solution. Extending die badi life by a fac-
tor of 12 has the potential to reduce the 70 million gallons of clear chromate waste produced
annually in die United States to 6 million gallons.
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Crystal Simple Green®
Hydrocarbon and petroleum solvents are the current "workhorses" for industrial cleaning
and degreasing. Current practice is to utilize solvent recovery systems to minimize solvent
waste streams from such cleaning/degreasing operations. This process has four negative
aspects with regard to human health and the environment: (a) solvent recovery requires con-
sumption of energy; (b) air emission of solvent fugitives cannot be eliminated; (c) recovery of
solvent from the solvent and dirt/grease mixture concentrates the dirt/grease into a poten-
tially toxic sludge; and (d) spent solvent must eventually be handled as hazardous waste.
Crystal Simple Green®, dirough its unique formulation and mode of action, allows users
to clean and degrease without using die hydrocarbon and petroleum-based solvents or sol-
vent systems diat are die backbone of current technology in diis area. Crystal Simple Green®
is approximately 85% water. Thus, use of Crystal Simple Green® in place of solvents in clean-
ing/degreasing reduces die demand for diese solvents in diis application. The total organics
content of Crystal Simple Green® is only about 12%, diereby reducing the need for organic
feedstocks and conserving valuable petrochemical resources.
The product utilizes proprietary technology to effectively clean/degrease substrates that
are heavily loaded widi industrial oils, greases and hydrogenated animal fats. Crystal Simple
Green® contains only biodegradable, water-soluble ingredients, reduces air emissions due to
its low VOC content, and eliminates die formation of concentrated cleaning/degreasing
waste sludges and spent hazardous solvent waste. Crystal Simple Green® offers a safer and less
toxic alternative to solvent cleaners/degreasers currendy used in industry.
Development of a Practical Model and Process to
Systematically Reduce the Environmental Impact of
Chemicals Utilized by the Textile and Related Industries
It was discovered in die early 1980s diat discharges from textile dyeing and finishing oper-
ations were adversely impacting publicly owned waste treatment facilities. The results of early
toxicity reduction evaluations pinpointed toxic and poorly degraded textile chemicals and
surfactants as culprits. It was decided diat elimination of toxic agents prior to formulation
was an important long-term objective to provide for a sustainable textile industry in die
United States. To achieve products "Designed for die Environment", a means to inexpen-
sively screen chemicals and raw materials and communicate results internally and externally
to consumers and regulators was needed.
Burlington Chemical discovered diat die results from diree OECD tests (OECD 30ID,
202, and 209) could be related in an expert computer system (AQUATOX®) to design tex-
tile chemicals widi gready reduced environmental impacts. This discovery led to the
development of a waste/toxicity reducdon program, Burco® Care, based on diis information.
Burco® Care has resulted in die producdon of low-impact wet processing chemicals. It
spawned a system of comparing textile chemicals for environmental impact diat can be uti-
lized in purchasing decisions by textile manufacturers and has been found suitable by U.S.
textile market leaders. Burco® Care is a giant leap away from simple regulatory compliance
to the creation of a systems-based thinking approach to building value by reduction of risk
and improvement of die environment. It is estimated that millions of dollars of waste treat-
ment costs are saved annually by customers who are improving the chemistry of their
processes utilizing diis tool.
Sunshine Makers, Inc.
Burlington Chemical
Company, Inc.
23
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U.S. Polychemical
Corporation
H and H Associates, Inc.
Environmental
Technology and
Education Center
Dispersit™: A Waterbased Oil Dispersant for Oil Spills
in Salt and Fresh Water
Oil spills are a well-documented environmental and economic catastrophe. They present
a long-term threat to populations of marine life, birds, aquatic mammals, and plants. The
economic loss due to spills can be similarly devastating. Clean up costs can be enormous, and
the long-term costs of a major spill in a populated or resort area could be incalculable.
Petroleum-based dispersants have proven more effective than booms and skimmers in clean-
ing up oil spills, but they pose health hazards and do not work in low salinity.
Dispersit™ is an effective and non-toxic oil spill dispersant that is a unique blend of
water, surfactants, and a coupling cosolvent. The product combines oil-soluble and water-sol-
uble surfactants with a cosolvent for coupling a mixture of die oil-soluble surfactant and oil
spill with the water-soluble surfactant. Water is included in the combination to help advance
the interaction between the surfactants and cosolvent and to reduce the viscosity of the dis-
persant to allow it to be pumped under pressure. Dispersit™ is more effective than
petroleum-based dispersants, less toxic to marine life, safer to apply, and works well in fresh,
brackish, and salt water.
DUAL-ICE®: A Non-Toxic, Non-Caustic Instant Cold
Compress
Instant cold compresses have been employed by bodi industry and the general public for
decades. Instant cold compresses employed for trauma or heat stress are mainly a combina-
tion of water and ammonium nitrate encased in a thin polyplastic bag. Ammonium nitrate
is classified as a hazardous substance by the EPA and is recognized as potentially explosive and
detrimental to the environment. In addition, the genetically low-stress packaging applied by
most commercial manufacturers of items employing this chemical places the consumer at
unnecessary risk. In response to a need by the U.S. Marine Corps, which was prohibited from
deploying current instant cold compresses for numerous factors, H and H Associates devel-
oped DUAL-ICE®, an environmentally safe alternative to ammonium nitrate cold packs.
Following proof-of-principal testing, H and H engineers deduced that a combination of
ammonium chloride, urea, and water would act to provide the necessary endothermic reac-
tion. The product is fully non-toxic, non-caustic, non-hazardous, and heavily packaged for
rough handling. DUAL-ICE® demonstrates a high cooling potential, maintains a shelf life of
at least one year, and is air- and ground-shippable. Furthermore, the postendothermic reac-
tion chemical byproduct is such that, after the initial use as an instant cold compress,
DUAL-ICE® is fully reusable as a refreezable cold pack that remains flexible and conforms to
an injured appendage or area.
High Energy Efficiency, Environmentally Friendly
Refrigerants
For several decades chlorofluorocarbons (CFCs) were die most widely used refrigerant flu-
ids because of their nonflammability, low toxicity, low cost, and reasonably high
performance. Because CFCs have been implicated in stratospheric ozone depletion, their pro-
duction worldwide was stopped at the end of 1995 under the provisions of the Montreal
Protocol as amended in Copenhagen in 1992. The phaseout of CFCs and HCFCs and
increasing concern about greenhouse gases create the urgent need for nontoxic, nonflamma-
ble, environmentally safe refrigerants with high capacity and energy efficiency.
24
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Dr. Jonathan Nimitz and his co-inventor, Lance Lankford, have discovered and patented
a family of improved refrigerants based on blends containing trifluoromethyl iodide (Cp3l).
CF3I has attractive physical properties, zero ozone depletion potential (OOP), low global
warming potential (GWP), relatively low toxicity, and is a combustion inhibitor. CPJ. can be
combined with high-capacity, energy-efficient, environmentally friendly, but flammable
refrigerant compounds to obtain excellent refrigerant blends that remain nonflammable. The
result is an energy-efficient, environmentally friendly, safe refrigerant.
The inventors and Dole Food Company have formed a new company, Ikon, Inc., to sup-
port testing and commercialization of the refrigerants. The first formulation developed,
Ikon® A, has extremely low GWP and can be used in R-12 or R-134a systems. Ikon® A has
been demonstrated for over 3 years in Dole Food Company refrigerated transports, with
excellent results. Ikon® A was also tested in a new R-134a domestic refrigerator, with results
of 19% higher energy efficiency and 15% greater volumetric cooling capacity versus R-134a.
Ikon® B was developed as a less expensive version of Ikon® A; it has been tested and demon-
strated in refrigerated transport units, a 5-ton water chiller (sponsored by NASA Kennedy
Space Center), and a new R-134a domestic refrigerator (sponsored by EPA).
A 20% market penetration of Ikon® B by 2010 will result in a decrease in carbon diox-
ide emissions of approximately 4 million tons per year. There would also be annual
reductions of approximately 12 thousand tons paniculate, 16 thousand tons nitrogen oxides,
and 24 thousand tons sulfur oxides. The installation cost for Ikon refrigerants will be repaid
within 3 years in most applications. At 20% market penetration by 2010, $0.08 per kWhr
and 15% lower energy use, estimated energy cost savings by 2010 are $400 million per year.
The human health and environmental benefits of the Ikon refrigerants will be significant.
Their use will result in improvements in human health, improvements in air and water qual-
ity, and reductions in skin cancer and ecological and crop damage from UV radiation.
The MICARE Liquid CO2 Dry Cleaning Process
The commercial dry cleaning industry faces a tremendous burden of environmental lia-
bility due to reliance on chlorinated and organic solvents. Over 72 million pounds of
perchloroethylene was sold to the industry in 1998. This material ultimately ends up in the
environment or in consumer clothes, impacting the health of communities and consumers.
No one has previously been able to integrate an environmentally friendly technology with an
effective cleaning process that alleviates this burden to our personal and environmental
health.
The application of CCh to the dry cleaning industry has been suggested since 1977.
However, commercial realization of this goal has been hindered by two main factors: the
unavailability of an appropriate process and high-pressure equipment and the inability of
unmodified CO2 to provide effective cleaning. Micell has overcome equipment barriers by
designing a dry cleaning process and manufacturing equipment that use liquid CC*2 just
below ambient temperature (-18-22 °C) and vapor pressure (-50 bar). As for the second fac-
tor, Micell has translated the fundamental discoveries of CO: surfactants to create detergent
packages appropriate for use in liquid CC»2 at saturated vapor pressure. The end result is a
system that deans clothes effectively, substantially reduces garment damage due to linting
from heat, substantially reduces dye and finish loss from aggressive organic solvents, and is
friendly to the environment. The successful combination of these elements has led to the
launch of the first national chain of dry cleaning stores to offer liquid CC«2 garment care to
the consumer.
Micell Technologies
25
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TechMatch, Inc.
KM Limited, Inc.
N-Methylmorpholine-N-oxide (NMMO): A Novel,
Nontoxic Solvent for Cellulose for Source Reduction in
the Production of Textile Fibers
For decades, scientists had been searching for an environmentally friendly means of form-
ing a cellulosic fiber. The standard procedure for producing cellulosic fibers had been die
viscose process, invented in 1894. There were no neutral organic solvents for dissolving cel-
lulose until 1965 when Dee Lynn Johnson, working in die laboratories of Eastman Kodak,
discovered that N-methylmorpholine-N-oxide (NMMO) is a solvent for cellulose. In addi-
tion, he demonstrated that die cellulose solution can be filtered and die cellulose filaments
regenerated by precipitation into water. Furthermore, die NMMO could be recovered by
evaporating die water and reused. This new solvent has now been commercialized by
Huntsman Petrochemical Corporation, and several fiber manufacturers have developed com-
mercial processes for producing the fibers. Fibers made by use of NMMO are called lyocell
fibers, meaning cellulose spun from solution. The previous viscose process produces rayon
fibers, but it requires a chemical reaction between carbon disulfide and cellulose in die pres-
ence of a strong base to produce a xandiate complex. Carbon disulfide is highly flammable
and toxic to humans as well as being a greenhouse gas. Further, to produce fibers, die xan-
diate must be regenerated by extrusion into an acid coagulating badi where it decomposes
and produces polluting byproducts diat are discharged into water.
The PIX Module Software: Combining Life Cycle
Assessment with Activity-Based Costing to Reduce
Global Environmental Impact and Sustain Industrial
Profitability
The LCAPDC module is die first commercially available software package that simultane-
ously allows die user to perform bodi Activity Based Costing and Life Cycle Assessment
(LCA). By using an industrial engineering approach employing drivers and driver values, die
model and relational database provide a unique combination of two strategies diat comple-
ment and enhance die implementation of an Environmental Management Strategy (EMS).
This approach has strong appeal to those involved in any manufacturing sector — die point
source for more dian 50% of "undesirable effluents" affecting our global climate.
The conventional approach to LCA studies has been the application of "simple" mass and
energy balances to manufacturing facilities. This approach is useful in providing guides for
cost reduction and large-scale beneficial changes, but it requires difficult definitions of system
boundaries, time-consuming data collection, and limits final inventory calculations. In con-
trast, die LCAPDC module provides a stand-alone software application diat can analyze
processes on a product basis, determine'environmental load centers, and allow for develop-
ment of a comprehensive database. The software package is a multifunctional tool in diat it
provides for inexpensive, rapid, and simple, strategic or environmental LCA comparisons of
any product, process, or service.
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Polymers and Plastics from Lignin Biomass
The most easily available as well as renewable supply of carbon is biomass: the trees,
shrubs, and foliage around us. Meeting society's needs from trees requires that new chemistry
and technology be invented to convert plant mass into industrial supplies, consumer goods,
and the drugs we use. Cellulose, the major component of wood plants, is already well-used
to make paper and chemicals. Lignin, the other one-fifth to one-third of the plant, is often
landfilled or burned as a byproduct at the rate of 20 million tons per year. This means that,
on average, one quarter of every tree harvested is wasted. Through 15 years of research, the
Center for Forest Products has developed methods to convert lignin and wood into the poly-
mers, plastics, and engineering materials that society will need in the future.
The methods involve reacting lignin with a polymer building block in the presence of a
salt and peroxide bleaching agent to generate a new graft copolymer. This simple and fairly
general reaction allows a byproduct of the paper industry to be converted into water treat-
ment chemicals for purifying water, dewatering agents for compacting sewage sludge,
chemicals for insulation and furniture foams, biodegradable and consumer plastics, binders
for wood-plastic composites, and reinforcing fillers for tire rubber. In addition, this modified
lignin can replace up to 37 million tons of monomers such as acrylamide, styrene, vinyl chlo-
ride, and acrylomidomethylpropane, all of which are flammable, toxic, explosive, or
carcinogenic. By developing a chemical method to alter lignin, future generations can obtain
the supplies and materials they need while harvesting fewer trees, wasting less of each tree,
and depending less on toxic and carcinogenic compounds.
Primer for Antifouling Paint
This technology and material is a primer to be used in conjunction with the bottom paint
(antifouling paint) that is found on the bottoms of all ocean-going boats. Every year, thou-
sands of ocean-going boats receive a coating of antifouling paint that typically must be
removed and reapplied annually. Current technology mandates that the paint be sanded off.
The resultant powder is dangerous, as it can be blown into the water and inhaled by the peo-
ple sanding the bottom of the boat. Copper oxide is commonly used as an antifoulant, but
it is toxic to all forms of life, including humans. Every year, 1.5 million pounds of copper
oxide paint dust are dumped into the ocean in the United States alone because of boat bot-
tom sanding.
A method and material have been developed that allow antifouling paint to be removed
quickly, in large sheets, without sanding. The primer uses a sophisticated wax/water emul-
sion. Once the water from die emulsion has evaporated, the antifouling paint is applied. The
boat is used, as usual. When the boat is to be hauled and the antifouling paint is to be reap-
plied, die old antifouling paint is removed widi hot water at a temperature just above the
melting point of the wax. The spent antifouling paint is easily collected in drums and either
recycled or properly disposed of in a hazardous waste disposal site.
Center for Forest
Products Research, Inc.
BAT Technologies, Inc.
27
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CHEMECOL, LLC
Nextec Applications,
Inc.
PVC Alternative Technology
CHEMECOLs technology can promote and expand the elimination of chlorine and
phthalates, two components of polyvinyl chloride (PVC) products, which are among the syn-
thetic chemicals that environmental activists and medical researchers claim are health risks.
Several organizations are seeking to phase out the use of PVC. The European Commission,
citing health risks to small children, formally decided to ban phthalates from PVC toys, and
concerns about die hazards of PVC are growing in the United States.
CHEMECOUs patented technology allows the incorporation of a liquid monomer widi
a metallocene polymer to form an interpenetrating network polymer system offering pro-
cessing similar to PVC with the unique property characteristics of a metallocene polyolefin.
The technology can be processed on conventional PVC manufacturing equipment, which
will save manufacturers added capital expenditure. In addition to improved quality, new
product features, and ease of processing, there are also environmental improvements with the
new technology. Specifically, die liquid monomer acts and behaves like a plasticizer without
being a plasticizer, preventing migration of phthalates that may be unsafe for biological sys-
tems.
An additional benefit of the technology is that no dioxins are produced during incinera-
tion, which is a common problem associated with PVC and is a particular concern for the
medical industry. Even more advantageous from an environmental and cost consideration
aspect is the ability to recycle products made as a result of using the technology. These com-
modity products may also be customized to contain enhanced product features such as
increased flame retardancy, an important factor in products used for construction. As such,
CHEMECOIi technology provides the capability for development of environmentally
friendly products, widi enhanced product features as compared to PVC, at a system cost that
is competitive widi PVC.
Solventless Process for Improving Fabric Performance
Properties
In the areas of apparel and protective gear there has always been an ongoing thrust to
achieve improved fabric performance properties. Properties of interest range from the quan-
tifiable, like water resistance/repellency, fire resistance, and adhesion performance, to the
subjective, such as comfort. One of the main ways of achieving improved properties is
dirough surface modification. Difficulties encountered with surface modification have
included durability as well as economically feasible and environmentally friendly processing.
In textile technology, surface modifications are applied via immersion, coating, or lamina-
tion. Immersions, coatings, and laminates can be applied as 100% solids, solvent dissolved
solids, or aqueous emulsions.
The Nextec process delivers performance benefits to manufacturers of rubber-treated fab-
rics through a process that utilizes no solvents, has no volatile organic compounds (VOCs),
utilizes essentially nontoxic starting materials, and yields inert residuals diat have passed
biocompatability testing. The unique patented technology that is practiced by Nextec Appli-
cations, Inc. replaces processes in which rubbers are dissolved in toxic aromatic or chlorocar-
bon solvents and are coated or spread on fabrics. Nextec's process allows precise placement of
thin polymeric films around fibers and crossover points and allows filling in or leaving open
interstitial spaces within fabrics. The choice of polymer, substrate, and placement of polymer
allows for improvement of properties such as breathable barrier performance, controlled
porosity, resistance to fluids, and adhesion/release behavior. This technology has found appli-
cations in such industries as aerospace, automotive, apparel, and medical.
28
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Solvox Special 5501, an Antiagglomerate and Stickles
Neutralizer for the Paper Industry
The scope of papermaking over the last twenty years has changed dramatically, in large
part because of the use of secondary fibers as a source of furnish. Economics have made sec-
ondary fiber a mainstay for a variety of paper producers because it is an inexpensive source of
fiber and is readily available. Furthermore, legislation has mandated the use of secondary
fibers whenever possible to conserve valuable natural resources. With these forces in play,
there have been numerous challenges that have presented themselves not only to the paper
industry but also to its chemical suppliers. One of these challenges, "sticky" control, has pro-
vided Solvox Manufacturing Company with an opportunity to position itself as the
problem-solver to customers world wide.
"Stickies" refer to any insoluble resin that has tacky properties and adversely affects paper-
making. Commonly used items such as Post-it® notes, address labels, and envelopes
contribute to the problem of sticky control. Pressure sensitive adhesives alone cost the paper
recycling industry an estimated $700 million per year. Recently, Solvox has formulated a spe-
cial chemical additive, Solvox Special 5501, that enables the paper industry to make quality
paper with recycled furnish equal in quality to that made with virgin fiber. This additive is
an antiagglomerate that can be considered a stickies neutralizer. Solvox Special 5501 coats the
sticky to make it dimensionally stable, thereby allowing it to be removed by mechanical
means, while preventing reagglomeration of the stickies. When compared with additives cur-
rendy in use, Solvox Special 5501 reduces VOC emissions, eliminates cosdy downtime, and
produces a higher quality end paper product.
This additive is important to the paper industry and the environment for several reasons.
First, this one additive does the job of three or more chemicals. But more importandy, this
chemical has a very low VOC level (approximately 0.50% by weight) compared to the chem-
icals that it replaces (some over 50% by weight). Additionally, it eliminates cosdy downtime,
thereby decreasing the total cost of making paper. Finally, it is now possible to make an end
paper product of high recycled content that is equal in quality to that of virgin fiber. This will
lower the amount of waste paper entering our landfills. Ultimately, this will reduce the use of
trees and preserve this planet for generations to come.
Sugars from Lignocellulosic Materials for the Production
of Bio-Based Fuels and Chemicals
The disadvantages of relying on fossil fuels are well known. Environmental problems
linked to fossil fuel usage include acid rain, global warming, and air and water pollution.
Production and use of carbohydrate-based chemicals can overcome many of these environ-
mental issues. Yet, widespread production and use of biobased chemicals have not occurred.
The return to the carbohydrate economy is stymied in an environment of artificially low
petroleum prices, an uneven playing field tilted toward the use of fossil fuels, and a lack of
technology to competitively produce products from biomass.
Arkenol, Inc. has developed an environmentally sound and cost competitive technology
for the carbohydrate industry. While completely analogous to the petrochemical industry,
Arkenols technology uses innocuous and renewable feedstocks. The Arkenol process utilizes
concentrated sulfuric acid to break down the cellulosic structure in lignocellulosic feedstocks
and then, with water, to complete the new formation of individual C6 and C5 sugars for fur-
ther processing into chemicals and fuels. The lignin is processed for soil amendment or solid
fuel. Silica, uniquely present in rice straw, can be recovered and converted to high value pre-
Solvox Manufacturing
Company
Arkenol Holdings, L.L.C.
29
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Anderson Chemical
Company
cipitated silicas and zeolites. Trace amounts of sulfuric acid in the sugar solution are convert-
ed into gypsum for soil amendment or ammonium sulfate for fertilizer. The sugars can be
converted into alcohols and carbon dioxide, acids, ethers, solvents, or surfactants either by
direct chemical conversion, fermentation, or a combination of both. With over 200 different
chemicals and an even greater number of downstream chemical product combinations that
can be derived from biomass, die market opportunities are considerable.
Arkenol is pursuing several opportunities worldwide to convert feedstocks such as rice
straw, sugar cane bagasse, and municipal solid waste into ethanol and other chemicals. An
advanced project in Sacramento County, California, will use Arkenols technology to divert
approximately 132,000 tons per year of rice straw from open-field burning to produce up to
12 million gallons per year of ethanol and coproducts. While eliminating burning on some
60,000 acres of rice fields, the Sacramento project will provide a much needed disposal alter-
native for rice growers faced widi the legislative mandate to phase out open-field burning. In
addition, by diverting the rice straw from open-field burning, the Sacramento project creates
significant improvements in the regions air quality. Avoidance of open-burning of about
140,000 tons per year of rice straw results in annual net emissions reductions of 280 tons of
NOx, 173 tons of PMio, 130 tons of VOCs, 138 tons of SO2, and 4,988 tons of CO.
The successful implementation of ArkenoPs technology will lead to decentralized and
competitive economic production of fuel ethanol and other biobased chemicals (ethanol is
produced from the Arkenol process at a cost of $0.66 per gallon, compared to $1.29 per gal-
lon from the industry standard process). Arkenols ability to use a wide variety of feedstocks
will enable placement of production facilities (or "biorefineries") near the market for the
products. Large scale conversion of waste materials into fuels and chemicals is a novel solu-
tion to waste management, pollution prevention, and economic development.
Total Impact Program (TIP®): An Environmentally
Preferable Program for Laundry
Anderson Chemical Company's Total Impact Program* employs chemistry with a more
positive environmental profile for human health and the environment than that used in con-
ventional laundry systems. Historically, institutional markets (hospitality, hospitals, nursing
homes, and others) have maintained a program of high alkaline breaker in conjunction with
an alkaline wash badi, sodium hypochlorite bleaching, acid souring to reverse die alkaline
breaker, and softening with poorly biodegradable softeners. Temperatures have been kept
high (150 °F to 160 °F) for performance, and high volumes of water for dilution and addi-
tional neutralization badis have claimed large volumes of energy for heating these water
baths.
The Total Impact Program (TIP*) targets three main impact areas: user safety and health,
environmental impact for pollution prevention via source reduction, and efficiency through
resource consumption reduction by decreasing processed pound costs. It was the intent of the
TIP* to reduce the toxicity of die washroom chemicals to achieve benefits in the areas of
human safety and healdi and subsequent effluent improvement as well. TIP* chemistry is
designed so that the NFPA raring is never higher than 1-0-0 for Health, Flammability, and
Reactivity. Alkaline breakers, acid sours, sodium hypochlorite, and alkylphenol ethoxylates
are not used in TIP®. This provides the facility and personnel using the TIP® a large degree
of safety.
30
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The TIP* incorporates a neutral pH detergent enhanced widi enzymes and surfactants,
oxygen bleach, and biodegradable softeners. Decreased water use and temperatures provide
energy and water savings. Shorter machine running times are a function of fewer baths need-
ed for alkalinity building and souring down steps. Water savings of 33% and energy savings
of 27% are typical for the TIP® when compared to conventional programs. Effluent savings
run at 33% as well. Fabric savings and linen replacement costs typically are in the range of
17-20% for the institutional markets worked with to date. As such, die change from con-
ventional laundry programs to the environmentally preferable TIP* provides a real
environmental management solution.
Waste Oil Source Reduction through Extended Oil
Service Life
According to National Petroleum Refiners Association estimates, 1.1 billion gallons of oil
were used in passenger vehicles and 916 million gallons were used in diesel engine vehicles in
the United States in 1996. Much of the motor oil changed by passenger vehicle owners is
improperly introduced into the environment. The management of used oil is a major envi-
ronmental issue because of its hazardous nature. Used oil contains toxins such as lead,
benzene, cadmium, chromium, and odier heavy metals. These contaminants can cause illness
in plants and animals and can contaminate drinking water. Waste oil has been granted spe-
cial regulatory status, exempting its management from conventional hazardous waste rules in
an attempt to encourage its beneficial use as a source of energy. Overall, this has had some
success in die management of used oil in the business sector. Used oil generated by house-
holds, however, is currendy disposed of improperly at an alarming rate nationally—220
million gallons per year as estimated by die U.S. Department of Energy.
In 1972, AMSOIL, Inc. introduced die first 100% syndietic motor oil to meet American
Petroleum Institute service requirements, passing performance testing for gasoline-fueled
consumer passenger vehicles. AMSOIL, Inc. has since developed syndietic oil formulas diat
extend oil service life up to 11 times diat of conventional petroleum lubricants in consumer
and commercial automobile and truck service and diat work much longer when used widi
an oil analysis program. AMSOIL, Inc. also manufactures extended life, premium-grade
lubrication and related products for commercial and industrial applications, including
hydraulics, compressors, gears, and diesel-engine power plants. The scope of AMSOIL lubri-
cating products' ability to provide uncompromising engine and machine wear protection,
while reducing die volume of waste oil generation at the source, benefits die consumer, die
commercial goods and services provider, and die upstream industrial entity. Syndietic oil
basestocks are comprised of well-defined particular molecule types diat can be designed for
specific performance characteristics. One distinct advantage over crude petroleum is diat diey
can be tailored to fit die requirements of die application. The uniform molecular structure of
syndietic oil base-stocks reduces die lubricant volatility (aromatic boil off) in extreme heat,
which in turn reduces oil consumption. Widi long drain syndietics, die average American
can use 75% less oil, reducing die volume and the potential for accidental environmental
contamination.
AMSOIL. Inc.
31
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lonEdge Corporation
Zero-Waste Dry Plating of Cadmium
Electroplated cadmium is widely used in die defense and aerospace industries for die cor-
rosion protection of steel. Cadmium, however, is a known toxic material. In addition, die
electroplating process generates large quantities of toxic sludge and effluents. A typical, medi-
um-sized electroplating shop, for example, discharges well over 100,000 gallons of effluents
daily and disposes of 15 to 20 tons of hazardous sludge per week.
As an alternative to this conventional process, lonEdge Corporation has developed and
commercialized a novel "zero-waste" dry plating technology. The dry plating does not use liq-
uid chemicals and recycles solid materials in situ, resulting in elimination of waste. In this dry
plating technique, a vapor-bath concept has been used in vacuum as opposed to the liquid
badi of electroplating. This vapor bath allows for multidirectional and economical plating of
cadmium only in the intended parts, resulting in a green technology. In addition, the amount
of water used, filtered, and deionized on the line is reduced by at least one order of magni-
tude, and the energy consumption in die dry plating process is only 35% of diat in
electroplating. Estimated water treatment and disposal cost savings on the dry plating line are
greater than $ 1,000 per day, and the capital costs in setting up the line are substantially lower.
At lonEdge Corporation's facility in Fort Collins, Colorado, a complete dry plating line has
been set up for production. The plating line consists of only four processes and a quality
inspection as opposed to more than a dozen baths and related operations in electroplating.
This plating line has been certified by a major aerospace parts supplier, and two dry plating
machines are in service for plating cadmium on aerospace components.
32
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2000 Presidential Green Chemistry
Challenge—Entries from Industry
and Government
ADVAFLEX™ Organic Stabilizer
ADVAFLEX™ Organic Stabilizers (ADVAFLEX) are novel organic polyvinyl chloride
(PVC) heat stabilizers primarily geared toward flexible PVC applications. While PVC is a ver-
satile polymer with many useful properties, it cannot be processed without the addition of
heat stabilizers. Conventional flexible PVC stabilizer technology relies on complex mixtures
consisting of as many as 10 components, with primary active ingredients that include lead,
cadmium, and barium compounds with metal contents in the range of 8 to 10%. Most of
the components originate from nonrenewable resources, and many are health and environ-
mental hazards.
ADVAFLEX™ is an entirely new concept in PVC stabilizer technology diat offers
numerous advantages over conventional stabilizers. First and foremost, diese are two-com-
ponent systems containing new organosulfur chemistry and low levels of metal activators,
such as zinc. The performance advantages include excellent thermal performance, competi-
tive costs, good secondary performance attributes, compatibility with coadditives chemistries,
and simplicity of PVC formation. The environmental and health benefits include: very low
metal content (as low as 0.4%); low odor and volatility; and die absence of barium, cadmi-
um, lead, phosphorous, alkylphenol, and other aromatic chemicals that are used in
conventional technology.
ADVAFLEX™ has undergone a thorough toxicity screening that demonstrates that the
product is essentially nontoxic and not mutagenic, carcinogenic, or environmentally haz-
ardous. The metal activators in ADVAFLEX™ formulations are generally required at
catalytic levels, and the preferred metal, zinc, is a required element of the human diet.
ADVAFLEX™ technology is a commercially attractive alternative that improves on all
aspects of the conventional technology, especially with respect to human and environmental
safety.
Morton International,
Inc.
Ashless Friction Modifier IAntioxidant for Lubricants
Cars consume roughly half the oil used in the United States and account for about one
quarter of die greenhouse gases generated. There are at least two important benefits to
improving passenger car fuel economy: conserving natural petroleum resources and improv-
ing the environment through reduced volatile emissions. While automobile manufacturers
work on improving vehicle fuel economy dirough upgrading engine efficiency and utilizing
lighter weight materials in automobile construction, products that can improve the perfor-
mance of cars already on the road could have a more immediate impact. Development of
engine oils that improve engine efficiency are in this category.
Engine oil is a mixture of petroleum base stock and additives that protect die metal sur-
faces, expand the useful temperature range of the lubricant, and extend the useful life of the
oil. Additives in a typical engine oil include detergents to keep the metal surfaces deposit-free;
dispersants to keep the insoluble particles suspended in the oil; viscosity modifiers, which sta-
bilize lubricant thickness at various temperatures; antiwear agents, which reduce
metal-to-metal contact; metal deactivators, which reduce friction between metal parts in
motion; and antioxidants, which reduce oxidation and breakdown, preserving the lubricants
properties over its lifetime.
Ciba Specialty
Chemicals Corporation
33
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DuPont Crop Protection
Developing a combination friction modifier/antioxidant reduces the number of additives
that a lubricant requires. More importandy, it has the capability to extend the durability of
the friction modifier, leading to improved lubricants. This in turn can positively influence gas
mileage and reduce environmental emissions. Irgalube F10 is a unique ashless, multifunc-
tional, combination friction modifier and antioxidant. Chemically it is a high molecular
weight phenolic antioxidant with hydroxyl functionalities providing friction modifying prop-
erties. It has been designed to replace glycerol monooleate, a friction modifier that tends to
promote oxidation at higher temperatures, and molybdenum didiiocarbamates (MoDTC),
which are metal-containing and can form undesirable, metal-containing inorganic particu-
lates upon combustion.
Irgalube F10 is made via the reaction of coconut oil, glycerol, and a phenolic antioxidant
and, as such, is the only commercially available, metal-free, multifunctional friction
modifier/antioxidant in the world. Irgalube F10 passed the ASTM fuel economy test proce-
dure, registering a fuel economy improvement of 1 to 1.5% over the standard test oil. A
fuel-efficiency improvement of 1% could have an annual impact of reducing carbon monox-
ide by 1.2 billion pounds, NOx emissions by 240 million pounds, and paniculate matter
emissions by 17 million pounds (based on National Air Quality and Emissions Trends
Reports, 1996).
Biocatalytic Production of 5-Cyanovaleramide
The first step in the manufacture of DuPont's new herbicide azafenidin (Milestone*), the
base component of a total weed control program, is die catalytic hydration of adiponitrile to
5-cyanovaleramide (5-CVAM). Using a traditional catalyst, manganese dioxide, the process
suffers from several problems: (1) the manganese dioxide recovered from a single hydration
reaction is inactive and not reusable, (2) it would be difficult and expensive to recover and
reactivate the catalyst, (3) significant amounts of adipamide are produced, and (4) a difficult
solvent extraction using toluene is required for the separation of 5-cyanovaleramide from
unreacted adiponitrile. In addition, rapid catalyst deactivation when using manganese diox-
ide requires the use of large amounts of this catalyst, resulting in the production of 1.25 kg
catalyst waste/kg 5-CVAM.
As an alternative to traditional chemical catalysis, a biocatalytic process was developed for
die highly regioselective hydration of adiponitrile. 5-Cyanovaleramide is produced in aque-
ous solution under mild conditions, with 96% selectivity at 97% conversion, and at
concentrations comparable to standard chemical processes (19 wt%). The biocatalyst,
Pseudomonas chloromphis B23 cells immobilized in alginate beads, is a naturally-occurring,
Biosafety Level 1 bacterium containing a nitrile hydratase enzyme. This biocatalytic process
reduces catalyst waste production by 99.5% and no longer requires the use of toluene for
product purification. To date, 77 metric tons of 5-cyanovaleramide have been manufactured
by this method, eliminating the production of 97 metric tons of metal oxide catalyst waste.
At full commercialization, it is predicted that several hundred metric tons/year of catalyst
waste will be avoided.
The novel, biocatalytic hydration of an aliphatic dinitrile to die corresponding
monoamide with high regioselecrivity at high conversion and at concentrations equivalent to
standard chemical processes is an environmentally friendly route that is generally applicable
to a large and broad-based segment of die chemical industry. In addition, this biocatalytic
process is easy to perform in standard chemical equipment at standard production rates and
it is readily transferred to other facilities because of the simple reaction conditions and com-
mon equipment required. In the present case, die biocatalytic process is the low-cost option
34
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for 5-CVAM production; DuPont expects to realize a cost savings of more than
$2,000,000/year at full commercialization, relative to the cost of using an alternate chemical
process.
BioPreparation™ of Cotton Textiles: A Cost Effective,
Environmentally Compatible Preparation Process
In textiles, one of the most potentially damaging activities to the environment originates
from traditional processes used to prepare cotton fiber, yarn, and fabric. Fabric preparation
consists of a series of various treatments and rinsing steps critical to obtaining good results in
subsequent textile finishing processes. These water-intensive wet processing steps generate
large volumes of wastes. Scouring, for example, is a cleaning process that removes impurities
from cotton substrates during textile processing. Conventional scouring processes use large
quantities of sodium hydroxide, high temperatures, and acid neutralization steps to remove
impurities, thereby generating large amounts of salts, acids, and alkali. In view of the 40 bil-
lion pounds of cotton fiber that are prepared annually on an international level, it becomes
clear that the preparation process contributes environmentally harsh chemicals to the efflu-
ent, with the major offender being sodium hydroxide and its salts.
BioPreparation™ is an enzymatic process for treating cotton textiles that meets the per-
formance characteristics of alkaline scour systems while reducing chemical and effluent load.
This pectate lyase process degrades pectin to release the entangled waxes and other compo-
nents from the surface. Successful full-size industrial mill trials in preparing yarn and knitted
textiles confirmed the processing advantages of the technology. These advantages, relative to
chemical preparative routes, include ease of operation (no modification of existing equip-
ment) and selective degradation of components that enhance properties with minimal weight
loss (maintaining the quality/integrity of the cotton fiber). In addition, a substantial reduc-
tion in biological oxygen demand (BOD), chemical oxygen demand (COD), and total
dissolved solids was documented during these trials. The trials with knit, for example, gave
20% and 50% reduction in BOD and COD, respectively, when a two-step alkaline treat-
ment was replaced with a one-step enzymatic preparation and dyeing process.
Furthermore, the BioPreparation™ technology also significandy reduces water, time, and
energy consumption. Shortened water rinses, for example, give 33 to 50% water savings.
Considering a recent statistical survey that determined that 162 knitting mills used 89 mil-
lion mVyear of water in processing goods from scouring to finishing, the BioPreparation™
approach would save from 27 to 45 million m3/year of water. These BOD, COD, and water
reductions would allow a mill to save 30% in waste and water costs. In conclusion, this bio-
compatible process provides an economical and environmentally friendly alternative to
alkaline scour systems, or any combinations thereof, currendy used in the textile industry
today.
The Chemical Kinetics Simulator Program
Computer simulators offer a powerful means of minimizing waste generated through
physical experimentation during process development and optimization, a waste stream not
usually addressed in green chemistry programs. The potential impact of simulations will not
be realized, however, unless tliey are widely accessible in an organization. The Chemical
Kinetics Simulator (CKS) Program, developed at die IBM Almaden Research Center to meet
diis need, is a general purpose, easy-to-use package diat allows outcomes of reactions to be
predicted for a large variety of gas, solution, and solid phase systems in static and flowing
Novo Nordisk BioChem
of North America, Inc.
IBM Research Division
-------
Argonne National
Laboratory
Air Products and
Chemicals, Inc.
reactors. Its basic computational method is well-founded in theory and has been
significantly enhanced through new algorithms that have been awarded U.S. patents. CKS
has been in use at IBM for three years for process research and development. Since May 1996,
the package has been available globally for a no-cost license through the World Wide Web
and is used in many other industries for process research and development because of its
exceptional ease-of-use and functionality. It also has been frequendy licensed by environ-
mental researchers in universities, corporate and government laboratories, and environmental
regulatory agencies to develop models and evaluate hazards.
Clean-Diesel Breakthrough: Simultaneous Decrease in
Emissions of Both Particulates and Oxides of Nitrogen
during Combustion
One of today's most challenging environmental problems is air pollution by oxides of
nitrogen (NOx) and participates, created largely by diesel engines, particularly in urban areas.
NOx and paniculate emissions from diesel engines are a major source of urban air pollution.
Paniculate matter contains organic compounds that may potentially cause cancer or muta-
tions. Nitrogen oxides contribute to the formation of acid rain, ground-level ozone, and
smog. Although the availability of oxygen enrichment in diesel engines has long been known
to reduce paniculate levels, it has not been a feasible technology because it increased NOx
levels. By using only a modest increase in the oxygen levels in engine intake air and by opti-
mizing fuel conditions, Argonne National Laboratory (ANL) has broken through the
technical barriers to create an oxygen enrichment technology that simultaneously reduces
both particulates and NOx.
The breakthrough came when ANL tested a new combination of three changes to engine
operating conditions: 1) increased oxygen content in the engine air supply; 2) retarded tim-
ing of fuel injections; and 3) increased fuel flow. ANL tests were the first to adjust all three
parameters. Previous strategies had changed only one or two of these conditions. This break-
through technology is made practical by the development of a compact advanced polymer
membrane that is a passive design and can be retrofitted to existing engines. The mass-pro-
duction cost is expected to be modest ($75 to $160), compared with paniculate traps ($200
plus 2 cents per gallon to operate) and NOx treatment catalytic converters ($300 plus peri-
odic maintenance).
This is the first oxygen enrichment technology to simultaneously reduce both NOx (by
15%) and particulates (by 60%). It is an all-in-one, in-cylinder treatment that solves the
emissions problems at the source, does not drain engine power (in fact, increases gross power
by 18%), and improves fuel efficiency (2 to 10% improvement in brake-specific fuel con-
sumption across the entire load range in a locomotive notch schedule). This breakthrough
technology will be important to diesel-engine manufacturers, who are faced with helping
their customers meet tougher regulatory standards beginning in model year 2002.
DEOXO-FLUOR™ Reagent
The importance of organofluorine compounds in the pharmaceutical and agricultural
industries has stimulated the discovery and development of simple, safe, and efficient meth-
ods for introducing fluorine in organic molecules. Deoxofluorination, the conversion of
carbon-oxygen to carbon-fluorine bonds, is one such method for the selective introduction
of fluorine in organic molecules. This transformation has traditionally been accomplished
with dialkylaminosulfur trifluorides, such as DAST [(diethylamino)sulfur trifluoride,
36
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], but only for laboratory-scale" reactions. Due to the well-known catastrophic
decomposition (explosion or detonation) of DAST on heating to greater than 90 °C, it is not
used for large scale industrial applications.
Air Products and Chemicals, Inc. embarked on a scientific and technological program to
provide deoxofluorination reagents and processes diat would be safe for large scale industrial
use. This led to the discovery and development of the DEOXO-FLUOR™ reagent, [bis(2-
medioxyediyl)aminosulfur trifluoride]. Various thermal analysis data from DSC, ARC,
Radex, and Setaram calorimetry clearly show the superior thermal stability of the DEOXO-
FLUOR™ reagent over DAST. This greater thermal "robustness" of the reagent over DAST
is satisfactorily rationalized on the basis of ab initio quantum mechanics calculations that
show an interaction between one of the edier oxygens and sulfur, resulting in a shielding of
die SFs group by the ether side chain, thus making the reagent less prone to decomposition
by bimolecular disproportionation reactions, as putatively occurs with DAST. The DEOXO-
FLUOR™ reagent is effective for the conversions of alcohols to alkyl fluorides, of aldehydes
and ketones to die corresponding gem-difluorides, and of carboxylic acids to their trifluo-
romethyl derivatives with, in some cases, superior performance compared to DAST.
Designing an Environmentally Friendly Copper
Corrosion Inhibitor for Cooling Water Systems
Copper alloys are widely used in industrial cooling systems because of their good heat
transfer qualities. However, unless they are protected by an inhibitor, copper alloys will cor-
rode in cooling systems. This corrosion produces extremely toxic copper compounds that are
dien released into the environment. Azole materials are the best available copper corrosion
inhibitors and, in general, they protect copper very well. Tolyltriazole (TTA) is by far the
most frequently used azole and is considered to be the industry standard. However, azole
materials have a serious drawback in that they are not compatible with oxidizing halogens,
such as chlorine and bromine. Oxidizing halogens are the most common materials used to
control microbiological (MB) growth in cooling water systems. TTA reacts with chlorine,
producing a chlorinated species that is not protective to copper. When corrosion protection
is lost, TTA feed rates are usually increased in an attempt to overcome the reaction with chlo-
rine and maintain a high enough residual to protect the copper surface. Very high TTA
dosages are frequendy applied to improve performance, often with limited success.
BetzDearborn has developed a new Halogen-Resistant Azole (HRA) that does not react
with chlorine and protects copper when chlorine is present. The substitution of this new
material for TTA provides substantial environmental benefits. These were demonstrated in a
field test at a nuclear power plant diat was utilizing chlorine for MB control. HRA was com-
pared to TTA with respect to copper corrosion rates and discharge toxicities. Upon
examination of the discharge, it was clear that copper-containing compounds, formed as a
result of copper corrosion, were the most significant causes of toxicity to aquatic species.
The use of HRA resulted in a five-fold decrease in the amount of copper released to the
environment, compared to TTA. Since HRA does not react with oxidizing biocides, consid-
erably less chlorine or bromine is required for prevention of MB activity. A reduction in
chlorine usage of 10 to 20% was observed at the above nuclear power plant, and reductions
of 35 to 40% have been observed at odier industrial sites. Lower chlorine usage means lower
amounts of chlorine- or bromine-containing compounds ultimately being released in dis-
charge waters. In addition, substantially lower concentrations of HRA are required for copper
alloy protection compared to TTA. At the nuclear power plant trial, the five-fold reduction
in the copper discharged was obtained with 2.0 ppm HRA compared to 3.0 ppm TTA.
BetzDearborn
37
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Furthermore, a mass balance showed that only 9% of the TTA was recovered (compared to
90% of the HRA). The TTA loss was due to the reaction with chlorine and the formation of
a chlorinated azole. Thus, the use of HRA resulted in a net reduction in the amounts and
types of azole and halogenated azole compounds that were released into the environment.
Finally, direct measurement of LC50 acute toxicities for fathead minnows, done on site in the
plant effluent at the nuclear facility, showed a reduction in toxicity when TTA was replaced
by HRA.
Nalco Chemical
Company
Designing an Environmentally Sensible Chlorine
Alternative
Industrial water treatment is necessary for energy conservation and to ensure a sustainable
global supply of fresh water. Far more chlorine is used to control microbial fouling in indus-
trial water treatment as compared to any other chemical. An environmentally sensible
chlorine alternative is needed because die gas is hazardous, the liquid is not stable, chlorine
is too volatile, free residuals do not efficiendy control fouling biofilms, combined residuals
are not very effective, reactivity with scale and corrosion inhibitors is counter-productive, and
disinfection byproducts are toxic. Chloramines are not effective antimicrobials and are espe-
cially toxic to aquatic wildlife.
STABREX was purposefully designed to imitate the stabilized bromine antimicrobials
produced naturally in die mammalian immune system. STABREX is the first biomimetic
industrial biocide. It is chemically analogous to die antimicrobial product of die oxidadve res-
piratory burst in eosinophils, a type of mammalian white blood cell. These cells consume
oxygen in a cellular process recendy proven to produce stabilized bromine antimicrobials. In
eosinophils, HOBr is produced by die enzymatically-catalyzed oxidation of bromide with
HaOa . The HOBr then immediately reacts widi 2-aminoedianesulfonic acid (taurine). The
product of this natural stabilization reaction is a potent antimicrobial, N-bromo-
aminoedianesulfonic acid; it is the design model for STABREX.
The design and performance benefits of STABREX Microorganism Control Chemical
have been proven in two hundred billion gallons of successfully treated industrial water since
commercial introduction in May 1997. This water, mosdy in cooling systems, would have
otherwise been treated with thirty million pounds of chlorine or its equivalent. Compared to
chlorine, the new product is more than 10-fold less toxic, generates 50% fewer disinfection
byproducts, is much more effective in controlling microbial biofilms, is many orders of mag-
nitude less volatile, is much simpler to handle and feed, is 50% less reactive with other water
treatment chemicals, and degrades an order of magnitude less in storage or transport.
STABREX is manufactured in six locations on five continents. Seventy percent of produc-
tion is used in the United States; 30% is applied internationally throughout Asia, Europe,
Africa, Latin America, and Australia.
The Lubrizol
Corporation
Durable AMPS® Antimist Polymers for Aqueous
Metalworking Fluids
The generation and accumulation of metalworking fluid (MWF) mists in the plant envi-
ronment during metalworking production gives rise to worker health and safety concerns. It
is estimated that about 1.2 million workers are potentially exposed to MWFs annually. In
response to increasing worker health concerns from MWF mists, the United Auto Workers
Union has petitioned the Occupational Safety and Health Administration to lower the per-
missible exposure limit (PEL) of oil mists in the workplace from the current PEL of 5 to 0.5
38
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mg/m3. The current mist control methods being used for exposure control have drawbacks.
For instance, engineering mist controls based on machine enclosures and mist collection are
exorbitantly expensive to install and maintain. A second type of chemical mist control
method, based on high molecular weight polymers as antimist (AM) additives for aqueous
MWFs, has found limited acceptability because AM polymers lose their performance due to
shear degradation, requiring frequent additions to maintain performance.
The development of durable AMPS® polymers at Lubrizol solves this problem. These
polymers suppress mist formation at the source by stabilizing MWF against breaking up into
small droplets that get suspended in the plant environment as mist. The reduction in mist
minimizes worker exposure to MWF chemicals and other pollutants present in the mist, cre-
ating a safer worker environment. Because they are shear stable, the AMPS® polymers provide
long-lasting mist reduction. The application and performance of the AMPS® polymers were
evaluated during field trials at small machine shops and large Ford manufacturing plants. In
a small machine shop field test, a one-time addition of 1,000 ppm AMPS® polymer resulted
in a stable 60% mist reduction. During large-scale plant trials at Ford Motor Company, a
one-time addition of 1,000 ppm AMPS® polymer resulted in stable 40 to 60% mist reduc-
tion over two months in the plant environment. The worker response to reduced mist levels
during these trials was extremely positive. It was felt that after the polymer addition, there
was a distinct improvement in plant air quality, general improvement in working conditions,
and less slippery floors from oil mist deposits.
AMPS® polymers provide a low-cost method of suppressing mist generation and con-
trolling exposure because they provide long-lasting mist suppression at low (ppm)
concentrations. These polymers are less labor-intensive to implement in the field because they
disperse easily in the MWF and do not require frequent addition. They are manufactured as
aqueous solutions and do not contain any volatile organic compounds. Extensive sensory,
inhalation, and dermal toxicity tests have shown that AMPS® polymers exhibit a profile of
minimal toxicity under conditions of use. Waste water treatment evaluations have shown that
they do not affect the waste treatability of aqueous MWFs.
Electronic and Photonic Polymers from Biocatalysts
As technologies continue to become more sophisticated in this fast-paced information
age, the need for new and advanced electronic and photonic materials becomes a critical
requirement for future leaps in performance, size, and speed. Simultaneously, however, with
this drive for new advanced materials is the growing concern over the negative impact that
these new technologies will have on the environment. Conventional conducting polymers are
synthesized, for example, from reactions that involve strong chemical oxidants and the use of
toxic solvents for solubilization and processing. Earlier studies had shown that enzymes were
an exciting, environmentally friendly alternative to the synthesis of many of these polymers.
However, the mechanisms involved in these reactions only led to highly branched and often
insoluble polymers that had very poor electrical conductivities and optical activity.
While investigating new ways to overcome these limitations with the enzymatic approach,
it was found that simple addition of a charged molecular species (polyelectrolyte or surfac-
tant) to the reaction medium provides a type of biocompatible nanoreactor that not only
optimizes enzymatic function and monomer coupling, but also provides water solubility of
the final complex. The final polymers have enhanced electrical and optical properties and are
processable, and the entire process is environmentally compatible.
A number of templated polyanilines and polyphenols have been produced and character-
ized using this process. Enzymatic polymerization of anilinic and/or phenolic monomers is
U.S. Army Soldier and
Biological Chemical
Command (SBCCOM)
39
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Radtech International,
North America
carried out in the presence of ionic templates to yield high-molecular-weight and water-sol-
uble complexes of the polymer and the template used. This approach is particularly attractive
because it is completely benign and simple (one step) and uses very mild aqueous conditions.
In addition, the process is general, as numerous ionic templates and derivatized monomers
may be interchanged to build in desired functionalization. This process has the potential to
revolutionize the use of electronic and photonic polymers because toxic catalysts or solvents
are no longer required for the synthesis or processing of these polymers into useable forms.
The technological applications for these enzymatically synthesized polymers are signifi-
cant and diverse. Polyaniline is already well known as a promising material for electrochromic
displays, electromagnetic interference (EMI) shielding, corrosion protection, electrostatic dis-
sipation, and sensing. There is also great potential for these materials in photonic devices and
batteries. Polyphenols are currently being investigated in polymeric batteries that could be
coupled to photovoltaic devices containing conducting polymers and light absorbing dyes to
create environmentally friendly energy harvesting and storage devices. It was recently found
that the mild and benign conditions of this biocaralytic approach even allow for the use of
DNA as a template to form a conducting DNA/polyaniline complex. This material could
have enormous opportunities in medical diagnostic devices, probes, and bioconductors. This
technology offers both potential economic and environmental benefits to industry and soci-
ety due to the commercial potential of the products made and the environmentally benign
methods used to produce them.
Eliminating Air Pollution (VOC and HAP) at the
Source through the Use of Ultraviolet and Electron
Beam Polymerization
Air pollution remains a major environmental concern in the United States. Ground-level
ozone, a major pollutant formed by die reaction of nitrogen oxides with volatile organic com-
pounds (VOC), affects more people than all other pollutants combined. Most of the VOC
emissions in the United States result from the practice of using volatile solvents in the man-
ufacture and use of coatings, inks, adhesive:, and similar products where polymers are
dissolved or dispersed in solvents. After application, the products are exposed to heat in cur-
ing or drying ovens to drive off die solvents. Attempts to reduce die VOC generated by
source reduction approaches have resulted in high solids and water-based materials. These
advances reduced VOC emissions for a while, but as die economy has soared and production
increased, VOC emissions again climbed to undesirable levels.
The only way to achieve permanent control of VOCs without impeding economic
growth is to remove all VOC generators (solvents) at die source. Use of powder coatings is
one approach that has been successful for metallic products that can withstand the high cure
temperatures required. For heat-sensitive substrates, such as paper, plastic, and wood, die
answer has been found in technology depending on the use of low-level radiation energy (i.e.,
ultraviolet light (UV) or electron beams (EB)) to polymerize coatings, inks, adhesives, etc.
without heat.
Radtech International has developed a UV/EB procedure that eliminates solvents com-
pletely. The UV/EB technology uses low-molecular-weight oligomers dissolved in monomers
of similar activity. These liquid resins can be used as clear finishes or formulated with pig-
ments and other conventional additives. When applied and cured with UV or EB, the liquid
materials are convened 100% to solids with virtually no emissions. As a consequence of this
environmental achievement, combined with other advantages such as high speed curing,
greater efficiency, no end-of-pipe requirement, space savings in oven elimination, excellent
40
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performance properties, etc., the use of UV and EB has been increasing rapidly over the past
five years.
This technology is currently in use in a wide variety of industries and is growing at a 10
to 12% annual rate. The Coors Company, which makes over four billion beer cans a year,
switched their production entirely to UV curing. They reduced their emissions in the man-
ufacture of each billion cans from 28.9 tons/year for a water-based enamel to 1.677 tons/year
for a UV-cured acrylic (free radical) enamel and dience to 0.224 ton/year for a UV-cured
epoxy (cationic) enamel. In short, they reduced their emissions by 94% using the acrylate and
over 99% using die epoxy, without the use of add-on pollutant collection and destroying
equipment. Other industries using UV/EB technology include (with 1999 estimated usage)
fiber optics (2,400 tons), wood products (12,500 tons), plastic products (5,200 tons), graph-
ic arts (36,000 tons), electronics (4,000 tons), and adhesives (1,500 tons).
Environmentally Benign Antibacterial Agents
Many effective antibacterial agents for consumer and health care applications on textiles
and fibrous substrates are no longer available on the market or are restricted due to their dele-
terious environmental effects in streams and watersheds. Chlorinated phenols and
chlorinated bisphenols are coming under scrutiny because their structure is similar to that of
polychlorinated biphenyls (PCBs), and they could potentially lead to the formation of the
very toxic substance dioxin. Tributyltin and related trialkyl tin oxides are also being restrict-
ed or closely monitored because of their adverse effects of polluting water sources. Thus, there
is a need for new, environmentally benign antibacterial agents to replace ones such as those
described above. Moreover, it would be useful if the new agents had chemistries compatible
with bleaching processes in the fiber and paper industries that increasingly utilize the envi-
ronmentally acceptable agent hydrogen peroxide in place of environmentally deleterious
bleaching agents, such as hypochlorite and other chlorinating agents.
Such agents have been synthesized and patented. These new environmentally benign
antibacterial agents, containing only magnesium and peroxide, are affixed as aqueous disper-
sions to textiles to impart antibacterial activity to natural, synthetic, and blended fibers by
conventional pad-cure processes (10 to 17% active ingredients cured at 2 to 4 minutes at 120
to 150 °C.). Modified textiles contain bound peroxide (0.1 to 1.7% by weight) that is active
against bacteria with contents as low as 0.10% active oxygen. These agents have been shown
to have excellent resistance to representative gram-positive and gram-negative bacteria.
Fixation of aqueous dispersions of these agents to a wide variety of fiber types and fab-
ric constructions has been demonstrated, as well as the long-term durability of these agents
to laundering to retain antibacterial activity. These agents have also been applied to a vari-
ety of cotton and wood-pulp cellulosic nonwovens. Thus, these agents have the additional
benefit of being more suitable for renewable fibers, such as cotton and cellulosic fibers
derived from wood pulp, than the nonrenewable synthetic fibers (such as polyester and
polypropylene). Moreover, because cellulosic fibers are bleached with hydrogen peroxide,
these agents have compatible chemistry with prior purification processes. The agents them-
selves may also be used in other applications (e.g., skin disorders, toothpastes, virus
inactivation) yet to be evaluated.
U.S. Department of
Agriculture,
Agricultural Research
Service, Southern
Regional Research
Center
41
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U.S. Department of
Agriculture, National
Center for Agricultural
Utilization Research
U.S. Department of
Agriculture, National
Center for Agricultural
Utilization Research
Environmentally Benign Synthesis of Monoglyceride
Mixtures Coupled with Enrichment by Supercritical
Fluid Fractionation
Supercritical fluid extraction (SFE), supercritical fluid fractionation (SFF), and, more
recently, synthesis under supercritical conditions have attracted considerable attention as pos-
sible alternatives to existing processes that employ organic solvents or catalysts requiring
postreacrion disposal. These methods utilizing carbon dioxide (CCh) have received the pre-
ponderance of attention due to CC^'s compatibility widi the environment (i.e., toxicity,
flammability). To date, however, no one has demonstrated how COz can be utilized in a series
of processes embodying synthesis, extraction, and/or fractionation, thereby creating an entire
process or plant that practices green chemistry from start to finish.
Studies conducted at the National Center for Agricultural Utilization Research have pro-
duced two alternative syntheses for producing monoglyceride-containing mixtures (via
gylcerolysis) that employ COi, either as a catalyst or transport medium coupled with a lipase
biocatalyst, to produce mixtures of varying monoglyceride content. Further, the same carbon
dioxide medium can then be used in a sequential fashion to effect an enrichment of the syn-
diesized glyceride mixtures to yield products having a monoglyceride content in excess of
90 weight percent that have high value as emulsifiers, lubrication aids, and food additives.
Using carbon dioxide under pressure, metal-based catalysts can be eliminated from the tra-
ditional batch stirred-reactor glycerolysis to yield a product that is lighter in color, less
odoriferous, and has a monoglyceride content between 35 to 45 weight percent, depending
on the botanical oil source.
Alternatively, the National Center for Agricultural Utilization Research has demonstrated
and patented a synthesis that uses CC>2 in the supercritical state to dissolve vegetable-based
oils prior to transport over a supported enzyme catalyst to yield designer glyceride mixtures
having a variable monoglyceride content between 50 to 90 weight percent. Finally, by cou-
pling one of die two CCvbased synthesis processes widi a thermal gradient fractionation
column, it is possible to utilize a totally environmentally benign process for production and
enrichment of high value oleochemicals from natural resources.
Environmentally Benign Two-Step Synthesis of Fatty
Alcohol Mixtures Using Supercritical Carbon Dioxide
(SC-COJ and SC-CO2/Hydrogen Mixtures
Fatty alcohols and dieir derivatives are important in many industrial processes where diey
are used as raw materials for surfactants and lubricants. The annual production of fatty alco-
hols is over one million metric tons. Commercially, fatty alcohols are produced by one of
three processes: the Ziegler process, the 6xo process, or by a high pressure hydrogenation of
fatty acids or esters. The last process is die only one that uses renewable, natural fats/oils,
whereas the first two processes utilize petrochemical feedstocks. This last method involves the
transesterificarion of the candidate oil/fat substrate with alkaline earth catalysts in a batch
reactor followed by hydrogenation of the resultant fatty acid methyl esters, also in a batch
autoclave with copper chromite catalysts. This synthetic route suffers from the use of envi-
ronmentally objectionable catalysts that must be filtered from the products; long reaction
times due to inefficient contact between hydrogen, the catalyst surface, and the methyl esters;
and slow production cycles due to the need to empty batch reactors and recharge them.
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In an improved process, the above reactions have been implemented in environmentally
friendly supercritical carbon dioxide (SC-CO2), using an enzyme catalyst in the transesterifi-
cation step followed by hydrogenation with a chromium-free catalyst. Further, the reactions
are run under supercritical conditions sequentially in two connected flow reactors, thereby
speeding up the turnaround time attendant with a continuous process. The hydrogenation
step can be achieved in 4 to 9 seconds due to the superior mass transport properties exhibit-
ed by H2 in SC-COa. Methanol produced as a byproduct in this reaction can be recycled back
to the first reaction (tranesterification) for use as a reactant. Using soybean oil as a substrate,
yields greater than 96% can be achieved using the candidate lipase for as many as 20 pro-
duction runs.
The resultant products, methylated fatty acids, are readily soluble in SC-CO2 and can be
transported to the second reactor, where 10 to 25 mole % hydrogen is added to the pressur-
ized COa stream. The high pressure/temperature hydrogenation to produce the saturated
alcohol mixtures employs a commercially available, chromium-free catalyst, T-4489. A con-
sequence of using renewable soybean oil as the initial starting substrate is the production of
a saturated fatty alcohol mixture that consists of 90% steryl alcohol. The described process is
the first example of conducting a sequential two-step synthesis entirely in SC-CCh, resulting
in a totally green synthesis with environmentally safe catalysts.
Filter Leak Test Using Ozone-Benign Substances
Air purification filters operate by adsorbing impurities from flowing contaminated
streams onto high-surface-area microporous materials, such as activated carbon. For such a
filter to operate properly, it must be packaged so that leak channels are eliminated. Testing to
ensure proper adsorbent material filling of manufactured fibers is routine and has tradition-
ally been performed using substances such as chlorotrifluoromethane (CFC-11) and
dichlorodifluoromethane (CFC-12). It is now well known that small chlorocarbons, chlori-
nated fluorocarbons (CFCs), and certain bromine-containing, fire-extinguishing materials
(halons) are detrimental to the environment because of their extreme environmental stabili-
ty in the lower atmosphere and their ability to release chlorine and bromine atoms upon
vacuum ultraviolet irradiation in the stratosphere. Chlorine and bromine atoms produced in
the stratosphere destroy ozone catalytically, thereby compromising the UV-protection that
the stratospheric ozone provides.
With the advent of the Montreal Protocol eliminating production of ozone-depleting sub-
stances, the search for substitute materials for common items including air-conditioning and
fire extinguisher fluids has to be intensive. Work at the U.S. Army Edgewood Research,
Development, and Engineering Center was directed at finding filter leak test materials that
were not destructive to earths stratospheric ozone layer and were capable of rapidly identify-
ing filter assembly problems. Materials investigated included several hydrogenated
fluorocarbons (HFCs) of differing volatility. HFCs do not contain chlorine or bromine,
which have been implicated as potent stratospheric ozone destroyers. Two HFCs were iden-
tified as substitute filter leak test vapors: 1,1,1,2,2,3,4,5,5,5-decafluoropentane
(HFC-4310mee) for in-service filters and 1,1,1,2-tetrafluoroethane (HFC-134a) for new fil-
ters. These materials have been adopted by the U.S. Army to test the integrity of filters used
to provide respiratory protection against chemical warfare agents.
U.S. Army Soldier and
Biological Chemical
Command, Edgewood
Chemical Biological
Center
43
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3M
Mallinckrodt Baker, Inc.
Evergreen Nylon
Recycling LLC
Hydrofluoroethers (HFEs) — The Right Balance of
Properties
Research on hydrofluoroethers (HFEs) started in 1994, and the first commercial com-
pound came to the marketplace in 1996. The design of the hydrofluoroethers provides a
balance of properties that make them excellent substitutes for ozone-depleting compounds.
3M formed a technical team in the early 1990s to find a substitute for ozone-depleting
substances (ODSs, i.e., CFCs and HCFCs). In addition to addressing die issue of ozone
depletion, the team also set criteria for candidate molecules on die basis of flammability, tox-
icity, photochemical reactivity (potential for smog formation), and global warming potential.
The 3M team investigated the performance, health, and environmental attributes of more
than 100 compounds before the invention of HFEs. HFEs did not require the team to com-
promise on any of its desired qualities for an ODS replacement. HFEs do not deplete die
ozone layer, do not contribute to photochemical smog, are very low in toxicity, are nonflam-
mable, and have very low global warming potentials.
The first commercial product for the HFE program was HFE-7100. HFE-7100
(C^OCHs) was brought to die market in 1996 and was followed by HFE-7200
(C^OCHaCHs) in 1997. Both of these compounds are approved for use under EPA's
Significant New Alternatives Policy Program (SNAP) for solvent cleaning, aerosol, and heat
transfer applications. EPA also declared these materials as VOC exempt on August 25, 1997.
The acute and subchronic toxicity of HFE-7100 has been thoroughly investigated. An eval-
uation of these data by the American Industrial Hygiene Association Workplace
Environment Exposure Limit Committee yielded an exposure guideline of 750 ppm. The
exceptional low toxicity of HFEs make them unique in a marketplace that has traditionally
had to compromise on die toxicity of available alternatives.
Hydrogen Sulfide Elimination
Mallinckrodt Baker has developed a method that eliminates hydrogen sulfide from die
substances not precipitated by HaS test. The existing method uses hazardous hydrogen sul-
fide, takes about 5 hours to perform, and is precise only for combined alkali results. The new
method is safer (does not use hazardous reagents), takes only 30 minutes to perform, and is
accurate for individual element determinations.
Innovative Green Chemistry for Sustainable
Manufacture of Caprolactam
Honeywell and DSM chemicals have both manufactured caprolactam and nylon 6 for
decades. Demand for nylon has continued to grow at a steady pace, and born companies have
continually improved dieir productivity to meet the increasing demand. In me mid-1990s,
Honeywell and DSM reached a point where demand outstripped dieir ability to supply from
dieir traditional plants. Expansion of capacity was necessary. The most financially attractive
and environmentally beneficial alternative was the Evergreen technology.
The Evergreen technology is a unique, proprietary green chemistry process for die depoly-
merization of nylon 6 and purification of die resulting caprolactam. It uses an alternative and
sustainable feedstock in the form of nylon 6 waste carpet and eliminates the use and genera-
tion of toxic materials as compared to traditional caprolactam manufacturing. The waste
carpet is converted into first-quality caprolactam diat is then used, without limitation, in crit-
44
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ical and aesthetic applications including carpet fibers, engineering plastics, and films. The
coproduct is used for its raw material and fuel value in the manufacture of cement.
Evergreen is the world's first large-scale, sustainable nylon recycling process. It eliminates
the annual use of 700,000 barrels of crude oil, 83 million pounds of benzene, 120 million
pounds of cumene, and 86 million pounds of phenol as the source feedstock for caprolactam.
Additionally, numerous direct environmental benefits are gained. Over 200 million pounds
of waste carpet (nearly 20% of nylon 6 waste carpet in the United States) are diverted from
landfills each year. All 200 million pounds of carpet (including backing materials) are recy-
cled into valuable end products; hence, die Evergreen process produces no solid waste. There
is zero use, generation, or emission of toxic materials in the Evergreen process. Air emissions
are significantly reduced (by 89%) compared to traditional caprolactam manufacturing, and
the feedstock for the process is indefinitely renewable because nylon 6 can be recycled by
Evergreen over and over again without ever degrading product quality.
Manufacturing Qualification of an All Dry Via Deveil
Plasma Process
The semiconductor industry is known for its heavy use of toxic and hazardous com-
pounds. The industry has taken a very responsible position in protecting workers from these
hazards; however, protective equipment, alarm systems, and special materials handling equip-
ment are all expensive items. If the use of diese hazardous materials can be substantially
eliminated, then the costs associated widi worker protection will also be reduced.
The process of plasma dry etching through silicon oxide layers creates submicron-sized
vias for interlevel metal contacts on silicon wafers patterned widi photoresist. The process also
leaves die wafer surface contaminated widi polymer residues, which must be removed. These
residues are called "veils" because of dieir appearance in die scanning electron microscope.
Conventionally, residue removal has been accomplished using special solvents and acids, and
although these materials are very costly, hazardous, and an environmental disposal burden,
die use of sulfuric acid/hydrogen peroxide mixtures for wafer cleaning and resist removal has
gone on for more than 30 years.
Collaborators at ULVAC Technologies, Inc. have developed a replacement technology
diat uses dry plasma chemical processes for treating the polymeric residues, which renders
diem 100% soluble in deionized water, along with die associated processing equipment for
using this capability in manufacturing. Togedier, Motorola Corporation and ULVAC
Technologies, Inc. have performed a comprehensive program evaluating die equipment and
processes in the manufacturing environment and have developed appropriate methods for
employing die technology in the production environment to render it useful and available to
die entire worldwide industry. Process repeatability and reliability, integrity of devices man-
ufactured in terms of electrical performance, yields, and operating lifetimes have been
demonstrated to meet or exceed the levels of the conventional acid-solvent technology.
Adoption of this technology by the semiconductor industry is anticipated to have a signifi-
cant impact on reducing the environmental burden associated with this industry, as well as
offering major manufacturing cost savings.
Motorola Corporation
and ULVAC
Technologies, Inc.
45
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ECOGAS Corporation
Mobil Oil Corporation
46
McCommas Bluff Landfill Gas Processing Facility
The McCommas Bluff Landfill Gas Processing Facility utilizes landfill gas, a renewable
feedstock, to produce energy. Landfill gas, containing primarily mediane, carbon dioxide,
and volatile organic compounds, is produced by the anaerobic decomposition of solid waste
material located in municipal landfills. The facility is located in Dallas, Texas, adjacent to the
McCommas Bluff Sanitary Landfill. Landfill gas is collected from interconnected wells locat-
ed within the landfill itself. The gas is processed to remove liquids, volatile organic
compounds, and carbon dioxide. The McCommas Bluff facility employs a technology called
Vacuum Pressure Swing Adsorption, or VPSA, to produce pipeline-quality gas that contains
greater than 97% methane. VPSA operates on the premise that certain gases are more readi-
ly adsorbed at certain pressures than others. This application works especially well for the
separation of carbon dioxide from mediane. Carbon dioxide is adsorbed on molecular sieve
material widiin a pressure vessel, while mediane passes through die vessel unaffected.
Desorption of carbon dioxide then occurs by applying a vacuum to the vessel, effectively grab-
bing die carbon dioxide from the molecular sieve. Not only does die facility use a renewable
feedstock in a unique process, but it also reduces greenhouse gas and volatile organic com-
pound emissions, provides odor control, and prevents mediane migration from die landfill.
Membrane Separation in Solvent Lube Dewaxing
Mobil Oil Corporation and W R. Grace have developed a pioneering technology diat sig-
nificandy reduces the impact of solvent refining of lubricants on the environment. The
membrane-based process provides greater lubricant selectivity and reduces waste generation,
while simultaneously decreasing emissions of volatile organic compounds and greenhouse gases.
The use of membranes to facilitate the solvent dewaxing of lubricants represents the first
significant, environmentally focused improvement in this technology in over 40 years. In
conventional lube dewaxing, a lube oil/solvent mixture is generated as part of die process.
The solvent is removed from this mixture by distillation to isolate the lube oil product. The
solvents are then cooled and refrigerated to die desired process temperature before being recy-
cled to die process. The improved process uses a proprietary polymeric membrane material
developed by W. R. Grace to separate up to 50% of die dewaxing solvents from die lube
oil/solvent mixture. Consequendy, the spirally wound membranes significandy reduce ener-
gy consumption by minimizing the need for energy-intensive distillation, cooling, and
refrigeration.
As a result, a single commercial facility could reduce fuel oil consumption by
36,000 bbl/yr. This equates to a reduction in greenhouse gas emissions of about
20,000 tons/yr for each plant in which the technology is installed. The same plant would
reduce cooling water use by nearly 4 million gal/day, or about 15 billion gal/yr. The use of
membranes allows more solvent to-be recirculated in the dewaxing operation, which in
turn leads to higher lubricant yields and a reduction in the amount of undesirable byprod-
ucts generated in the process. The higher process yields reduce by about 5% the volume of
crude oil required to produce a given volume of lube oil. For a world-scale plant, this
equates to a savings of about 2 million barrels of crude oil per year. Finally, the loss of
dewaxing solvents, which are volatile organic materials, into the environment could be
decreased by 50 to 200 tons/yr per plant depending on the age and mechanical condition
of die dewaxing equipment. This results from a reflection in the number of pieces of equip-
ment required to refine a given volume of lube oil.
This technology was first implemented commercially at Mobil's Beaumont, Texas, refin-
ery. It can easily be retrofitted into existing plants or incorporated into new plant designs and
is currendy available for license.
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Minimizing Environmental Emissions by Using
Different Solvents in Manufacturing Processes
Solvent selection is an important aspect of chemical process development. Two well-
known effects of solvents are their influence on the desired reaction kinetics and their
potential to minimize die effects of hazardous undesired reactions dirough dilution and heat
absorption as solvent is vaporized.
Recent testing of energetic chemicals has demonstrated that the chemistry and kinetics of
their undesired decomposition reactions are also significandy altered by solvents. Eastman
Kodak has successfully applied this knowledge to the process safety element of process devel-
opment by systematically evaluating potential solvents for their effectiveness in minimizing
the potential environmental impacts of accidental process upsets. For example, the batch size
of an existing process had been very restricted because of the potential severity of a thermal
runaway. Research on chemistry/solvent-specific decomposition data was utilized to select
candidate replacement solvents that would minimize environmental hazards. A cooperative
effort by safety engineers and development chemists ensued, resulting in a final process that
entirely eliminated die possibility of loss of containment due to a diermal runaway. The end
result of this work is that a new tool is available to help chemists and chemical engineers
develop inherendy safer chemical processes.
Historically, changing a process to mitigate a potential hazard has been accomplished
through drastic changes in process conditions, process chemistry, or through equipment
modifications, all of which require significant capital and resources. It is demonstrated by
example that the application of recent investigations into the effects of solvents on the
decomposition kinetics of energetic chemicals can be leveraged to substantially decrease the
potential environmental impact of thermal runaways in production-scale equipment. The
technology described has the potential for broad application in chemical manufacturing
processes that make or use thermally unstable materials.
A New Environmentally Friendly Corrosion Inhibitor
Corrosion is estimated to cost the United States well over $300 billion per year. The
industrial water treatment market for corrosion inhibitors is 50 million pounds per year,
growing at 5 to 7% annually, with more than 500,000 individual use sites in this industry
category. Exposure to corrosion inhibitors is thus a major concern. Conventional corrosion
inhibitors used in industrial cooling systems are either hazardous to the environment or have
other drawbacks, such as instability in the presence of oxidizing biocides, limiting their
applicability.
A new, all-organic corrosion inhibitor, Bricorr* 288, a phosphonocarboxylate mixture,
has been discovered and patented. Bricorr* 288 is a highly effective corrosion inhibitor with
wide applicability to industrial cooling systems. Bricorr* 288 is an aqueous solution, does not
contain VOCs (Volatile Organic Compounds), is halogen free (bromine, chlorine, etc.), is
heavy metal free (zinc, chromate, etc.), and does not contribute to dioxin or AOX
(Absorbable Organic Halide) formation. Bricorr* 288 has an environmental profile permit-
ting, in many instances, discharge of treated water direcdy into rivers without any adverse
effects. In many cases, the recommended treatment level is at least an order of magnitude
below diat which would be toxic to fish. Bricorr* 288 is extremely water-soluble and, there-
fore, will not bioaccumulate. Bricorr* 288 has excellent handling characteristics due to its low
mammalian toxicity, helping to improve safety. Additionally, die manufacturing process for
Bricorr* 288 is environmentally benign in that it is solvent-free and does not result in dis-
charges to water or air, nor does it produce any byproducts requiring disposal.
Eastman Kodak
Company
Albright & Wilson
Americas, Inc.
47
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Ciba Specialty
Chemicals Corporation
CDTech
New Organic Corrosion Inhibitors Help Replace Toxic
Heavy Metals and Reduce Solvent Emissions
The coatings industry in the United States has had to focus its efforts to develop products
that are compliant with an ever-expanding set of Federal, state, and local regulations, all
designed to reduce or eliminate materials that pose a threat to either human health and safe-
ty or more broadly, environmental safety. The Irgacor family of organic corrosion inhibitors
was designed and developed specifically to replace the standard anticorrosive pigments that
are based on heavy metals such as lead, chromium, zinc, strontium, and barium. These heavy
metals are classified as being harmful to humans and/or the environment. In addition to die
toxicity generally associated with diem, heavy metal-based anticorrosive pigments are not
particularly effective in low volatile organic content (VOC) waterborne coatings due to
incompatibility.
Irgacor organic corrosion inhibitors are free of heavy metals. They offer effective replace-
ments for heavy-meral-based products and can produce commercially viable waterborne and
high solids solvent-based coatings. Replacement of all conventional corrosion inhibitors by
diese organic corrosion inhibitors could result in a potential overall annual source reduction
of heavy-metal-based inhibitors of approximately 11.0 million pounds (4.2 million pounds
chromate, 3.9 million pounds zinc/nonchromate, and 3.0 million pounds barium borates
and silicates). Irgacor corrosion inhibitors are typically used at levels (based on total solids) of
1.5% to 4% compared to 10% to 20% or more for anticorrosive pigments. The volume of
Irgacor necessary to replace the 11.0 million pounds, therefore, will be only 2.0 million
pounds. In addition, if Irgacor can further stimulate the replacement of solvent-based systems
widi waterborne coatings in the maintenance, auto finish, and marine markets by 20%, the
annual volume of VOCs being emitted to the atmosphere would be reduced by 6.7 million
pounds (from 8.0 million pounds to 1.3 million pounds). Irgacor organic corrosion
inhibitors provide both long-term anticorrosive properties as well as excellent protection
against flash rust. This provides die coatings industry with effective materials to further the
development of waterborne coatings as replacements for solvent-based, higher VOC
products.
A New Process for Producing Dimethyl Carbonate
Over the past several decades, the chemical industry has been interested in finding eco-
nomic alternatives to phosgene as a chemical intermediate to introduce carbonate
functionality into molecules (e.g., in the production of polycarbonates and polyurerhanes).
These products have multibillion pounds per year markets. The goal was to eliminate die use
of a very hazardous material and the need to dispose of chloride-containing waste streams. It
has long been known that dimethyl carbonate (DMC) could be used for this purpose, but it
was not until relatively recently that a technology was available to produce DMC at a cost
that could justify its use in new polycarbonate plants. This technology is based on the reac-
tion of merhanol, carbon monoxide, and oxygen in the presence of a copper chloride catalyst.
The cost of production, however, is still too high to encourage the replacement of phosgene
in existing polycarbonate plants.
A practical process for DMC production was never developed because available catalysts
were not sufficiently active, byproduct formation was too high, and product recovery was
complicated and expensive. These problems were solved by employing a novel catalyst sys-
tem and innovative reaction and separation technologies. The patented catalyst system is a
homogeneous complex of dibutyltin dimethoxide in triglyme (triethylene glycol dimethyl
ether). Triglyme has low volatility under the reaction conditions and is a nonhazardous low
48
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volatility solvent that is readily contained in the reaction zone. A further discovery was that
DMC selectivity is enhanced by rapidly removing die DMC from the reaction zone. Near-
stoichiometric yield of DMC was demonstrated using medianol as the stripping vapor in
laboratory-scale experiments. The new process efficiendy produces DMC and ammonia from
medianol and urea while affording significant environmental and economic advantages. The
potential for accidental release of phosgene is eliminated along widi the salt waste stream.
Furthermore, integrating die DMC plant with a urea plant allows efficient recycling of the
ammonia to urea production, widi a net effect of producing DMC from methanol and CC^.
Oxidizer Scrubber Project
NASA, in conjunction widi its previous Engineering Support Contract contractor, INET,
and die current contractor, Dynacs Engineering Co., Inc., has developed an innovative
process diat converts hypergolic oxidizer waste to a fertilizer used by Kennedy Space Center
(KSC). The Toxic Vapor Detection (TVD) Laboratory of die KSC has demonstrated that die
efficiency of die oxidizer scrubbers can be increased, a hazardous waste stream can be avoid-
ed, die operating cost of die process can be lowered, and fertilizer purchases can be reduced.
Hypergolic propellants are used in spacecrafts such as die Space Shutde, Titan IV, Delta
II, and odier vehicles and payloads launched at KSC and Cape Canaveral Air Station
(CCAS). Fueling and deservicing spacecrafts constitute die bulk of operations in which envi-
ronmental emissions of NOx occur. Monoediylhydrazine, nitrogen tetroxide, and hydrazine
are die main propellants of concern. The scrubber liquor waste generated by die oxidizer
scrubbers (approximately 311,000 pounds per year) is die second largest waste stream at
KSC. The waste disposal for this oxidizer scrubber liquor is approximately $0.227 per pound,
or $70,600 per year.
Widi die new process change, die scrubber liquor waste stream at KSC and CCAS will
be converted to a high-grade fertilizer, which will be applied to citrus groves. The process
reacts nitrogen tetroxide widi 1% hydrogen peroxide and potassium hydroxide to produce
potassium nitrate, which is a main ingredient in commercial fertilizers. This process avoids
die generation of hazardous wastes, which occurs when sodium hydroxide is used as die
scrubber liquor. In addition, die new scrubber liquor is more efficient in catching nitrogen
tetroxide than when sodium hydroxide is used. For example, when the new and existing
scrubber liquors were compared under the same test conditions, the efficiencies were
improved from 72.6 to 98.7% for the old scrubber liquor to 98.3 to 99.99% for the new
scrubber liquor. Therefore, the emissions from the scrubber were 10 to 200 times lower for
the new scrubber liquor than die emissions from the sodium hydroxide scrubber liquor. This
new chemical change has eliminated the second largest hazardous waste stream at KSC and
developed a new scrubber liquor, which is approved for application as fertilizer to the lawns
and citrus groves at KSC. The cost savings with this new system amount to approximately
$80,000 per year.
Oxygenation of Hydrocarbons by Photocatalysis: A
Green Alternative
The chemical industry is a significant component of the domestic economy, generating
well over $250 billion in sales and a trade surplus exceeding $15 billion in each of the last
five years. The industry is also a major source of industrial waste and is the dominant source
of hazardous waste in the United States. The costs of handling, treating, and disposing of
wastes generated annually in the United States have reached 2.2% of gross domestic product
Dynacs Engineering
Company, Inc. and
Kennedy Space Center
U.S. Environmental
Protection Agency,
Office of Research and
Development, National
Risk Management
Research Laboratory
49
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U.S. Environmental
Protection Agency,
Office of Research and
Development, National
Risk Management
Research Laboratory
and continue to rise. The chemical manufacturing industry generates more than 1.5 billion
tons of hazardous waste and 9 billion tons of nonhazardous waste annually. Organic chemi-
cals constitute the largest source of the toxic releases. Many of these releases can be minimized
by improving the conventional housekeeping methods and pollution prevention techniques.
However, cleaner production methods can be achieved by adopting green synthetic methods.
In recent years, there has been considerable work aimed at utilizing semiconductor pho-
tocatalysts for a variety of applications. High-value oxygenated organic compounds have been
successfully synthesized from linear and cyclic hydrocarbons by a low-temperature photocat-
alytic oxidation using the semiconducting material titanium dioxide (TiOa). Various
hydrocarbons were partially oxidized in both aqueous and gaseous phase reactors using ultra-
violet light and titanium dioxide under mild conditions. The conversions and selectivities
obtained for the partial oxidation of hydrocarbons have been comparable to those achieved
with the conventional method. For example, vapor phase photocatalytic oxidation of toluene
with air, using a continuous reactor at 160 °C and 27 mW/cm2 irradiation, resulted in a 12%
conversion per pass to benzaldehyde and benzoic acid, with 95% selectivity to benzaldehyde.
The gas phase photocatalytic reactors eliminated the separation step involved with liquid sol-
vents and catalyst slurry mixtures and minimized the adsorption of products to the catalyst.
Initial life-cycle analysis studies have shown that this technology has the potential to
reduce water contaminants and eliminate the use of toxic metal catalysts and solvents. Light-
induced catalysis expands the possibilities of using molecular oxygen in partial oxidation
reactions that are now being conducted with far more expensive polluting oxidants. This
technology also promises the potential of visible light-induced chemistry for commercially
important syntheses. Furthermore, the high selectivity and mild conditions achieved with
photochemical routes will be especially attractive for the manufacturing of fine chemicals.
Paris II Solvent Design Software
There is a need to replace solvents currently used in industry whose continued use pre-
sents health difficulties, such as worker health concerns, and environmental impacts, such as
toxicity. The replacement of these objectionable solvents, however, is a difficult task. In part,
this is because solvent parameters and different compositions for mixtures need to be con-
sidered. The list of solvent parameters, such as density, viscosity, and surface tension, can be
quite large. Trying to accomplish this replacement by hand is an interminable task. It is also
desirable and more economical to replace the solvent but not the process or the equipment
where the solvent is used. At the U.S. EPA's National Risk Management Research Laboratory,
an effort has been underway to address this problem by developing a computer program that
will allow users to design more benign replacement solvents and solvent mixtures.
A new Program for Assisting the Replacement of Industrial Solvents entitled PARIS II for
the Windows* operating system has been developed. The program is capable of solvent
design. The solvent design capability allows the user to match or to enhance desirable solvent
properties while simultaneously suppressing undesirable ones, such as toxicity. This is
achieved by designing mixtures of pure solvents and manipulating the composition. The
composition is manipulated by a solvent search algorithm aided by a library of routines with
the latest fluid property prediction techniques. The program contains a database of 1600 pure
solvents with solvent properties. The solvent properties adequately characterize both the sta-
tic and the dynamic behavior of pure solvents and solvent mixtures. The solvent properties
include comprehensive measures of toxicity and the means to estimate volatile organic emis-
sions, among other features. PARIS II is able to design replacement solvents that meet the
50
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technical requirements of any solvent now in use while having better environmental perfor-
mance (lower VOC's, less toxicity, lower environmental impacts), irrespective of the intended
application of the solvent. PARIS II has demonstrated die design of technically effective
replacement solvents for many environmental requirements.
Pollution-Free Conversion of Trees to Paper Using Air in
Place of Sulfur and Chlorine
NOTE: This project is a partnership between the U.S. Department of Agriculture and
Professor Craig Hill of Emory University. This entry was submitted by each party of die pro-
ject and, therefore, was judged in both die academic and industry categories. The project
summary appears in the academic entries section on page 16.
Process to Produce Biodegradable Polylactic Acid Polymers
Polylactic acid (PLA), a highly versatile biodegradable polyester derived from 100%
renewable resources, offers great promise as a replacement for petrochemical-based plastics in
a wide range of commodity applications. While the environmental benefits of PLA, dubbed
die "sleeping giant" of biodegradable polymers, have long been appreciated, its commercial
viability has been limited by high production costs, often leading to resin prices greater dian
$2/lb. Until now PLA has enjoyed little success in replacing petroleum-based plastics in com-
modity applications.
Cargill Dow Polymers LLC (CDP) has developed a novel, solvent-free process for the pro-
duction of lactide and polylactic acid. This environmentally friendly process is the first to allow
the economical manufacture of a biodegradable and renewable-resource-based polymer diat
can effectively compete widi petrochemical-based, commodity plastics on a cost/performance
basis. The patented, multi-step process starts widi L-lactic acid, a fermentation product
derived from 100% renewable resources. Aqueous lactic acid undergoes a condensation poly-
merization to produce low-molecular-weight PLA pre-polymer. Next, the pre-polymer is
depolymerized by an intramolecular cydization reaction into a mixture of L- and meso-lactide
diastereomers. The lactide isomers are then isolated with high purity using vacuum distillation.
Finally, PLA high polymer is continuously produced via a ring-opening polymerization of neat
lactide using very low levels of tin catalyst. Two major advantages of this new synthetic process
are that 1) the use of cosdy and environmentally unfriendly solvents is completely eliminated,
and 2) all side streams can be recycled internally within the process.
Millions of pounds of PLA have been produced by this process in the CDP semiworks using
lactic acid derived from both corn and sugar beets. Increasing market demand has prompted
Cargill Dow Polymers LLC to plan the construction of a 250 MM Ib/yr facility in 2001. The
combination of versatile production capability and low-cost economics uniquely positions
EcoPLA™ resins to be competitive with petrochemical-based plastics in a wide variety of appli-
cations—demonstrating that green chemistry can indeed make good business sense.
U.S. Department of
Agriculture Forest
Service
Cargill Dow Polymers
LLC
51
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PPG Industries, Inc.
Eka Chemicals, Inc.
Replacement of Asbestos in the Diaphragm Cell Process
for Manufacture of Chlorine and Caustic Soda
Approximately 75% of the chlorine and caustic soda (NaOH) produced in the United
States (54 million Ibs/day of chlorine and 58 million Ibs/day of caustic soda) is made by the
electrolysis of salt brine in diaphragm electrolysis cells. In these cells, salt dissolved in water is
supplied as anolyte to an electrolysis cell consisting of an anode, a cathode, and a
"diaphragm." Historically, asbestos is the material used as the diaphragm to maintain die crit-
ical separation of bodi die gas phase and liquid phase products.
PPG has developed die Tephram® nonasbestos diaphragm for use in diaphragm electrol-
ysis cells for die production of chlorine and caustic soda. The Tephram diaphragm uses
nonhazardous Teflon® fluoropolymer microfiber materials to replace asbestos. The Tephram
diaphragm technology offers advantages in decreasing die complexity in handling raw mate-
rials (both asbestos itself and die corrosive chemicals used in asbestos diaphragm deposition)
as well as in die disposal of asbestos materials at die end of dieir useful lives. Tephram
diaphragms not only are easier to handle safely and are more environmentally friendly than
asbestos diaphragms, but they also last much longer dian asbestos diaphragms. At PPG's Lake
Charles, Louisiana, chlor-alkali complex, an advantage in energy efficiency has also been
demonstrated. These advantages of greater durability and efficiency combine to reduce cell
renewal labor and consumption of bodi materials and energy.
Laboratory development at PPG's Chemicals Technical Center, and, over die last diree
years, full-scale demonstrations at PPG's Lake Charles, Louisiana, chemical complex, have
demonstrated performance that has led to die decision to replace asbestos diaphragms in Lake
Charles's largest chlorine production facility, Plant C, widi die Tephram nonasbestos
diaphragm.
SVP-Pure™ C/02 Process Technology
In die water and water-treatment industries, die need to reduce trihalomediane (THM)
and haloacetic acid (HAA) formation, control taste and odor, remove soluble iron and man-
ganese, and effectively eliminate bacteria and viruses has substantially increased the demand
for chlorine dioxide. While several mediods exist to generate CICh, previous technologies
have been limited by low efficiencies, concern over unreacted chlorite, excess
chlorine/hypochlorite, and cost. Eka's SVP-Pure™ C1O2 process technology eliminates these
concerns widi its state-of-the-art aqueous sodium chlorate/acidic hydrogen peroxide process.
SVP-Pure™ is die first sodium chlorate based CiOa process to receive EPA registration
for use as a disinfectant in drinking water and waste water. The two-chemical feed system
adopts Eka Chemicals' patented hydrogen peroxide chemistry and applies a proprietary blend
of sodium chlorate and hydrogen peroxide called Purate™. In comparison to competitive
technologies, SVP-Purc™ chemistry requires no gaseous or liquid chlorine feed and no chlo-
ride ion addition. This process eliminates byproduct chlorine, diereby reducing the potential
for the formation of THM, HAA, and chloroform disinfection byproducts. Eka Chemicals'
proprietary reaction vessel design optimizes mixing of feed chemicals, yielding high conver-
sion rates. Some technologies frequendy overfeed die chlorine and chlorite precursor
chemicals to meet the 95% efficiency standard that results in the pass-dirough of feedstock
chemicals to the receiving water. In contrast, SVP-Pure™ incorporates a microprocessor-
based electronic controller to regulate reactor feed, calculate efficiency, and control output.
Fail-safe emergency shut-down logic programmed into die controller minimizes operator
feedback requirements providing the safest, most user-friendly system.
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Water-Based Synthesis and Purification ofMannich
Base Modified Polyphenols
Polyphenol copolymers are common in industrial and consumer products. Mannich reac-
tion products of polyphenols with formaldehyde solutions and secondary amines produce
unique chelating polymers. These have replaced many hexavalent chromium-containing
treatments and continue as components in new and diverse non-heavy-metal-containing
conversion-coating technologies. Originally, the precursor phenolic polymer was dissolved in
an organic solvent before die reaction. Acidification of die newly acquired amine functional-
ity allows dilution widi water before application. At diis point, the organic solvent
component serves no apparent useful purpose. Since phenols can be ionized and, dius, be sol-
ubilized in water by a strong base such as sodium hydroxide, a water-based synthesis process
was developed. These reactions proceed with paraformaldehyde (eliminating methanol con-
tent) and amine at lower temperatures and higher yields than die solvent-based processes.
Dilution and acidification, followed by deionization through a strong-acid type cation-
exchange column, quantitatively removes die sodium, residual amine, monomeric Mannich
reaction products (small ediylphenol content from die precursor polymer), and odier cation-
ic impurities — resulting in a highly purified 100% aqueous polymer solution. Additional
benefits realized include improved shelf-life and hot/cold stability of die concentrate; elimi-
nation of flash points; biological and chemical oxygen demand and residual formaldehyde
reductions; and die elimination of worker exposure to organic volatiles during manufacture.
The amount of organic solvent eliminated to date is greater dian 500,000 Ibs. This has
been a great help to customers who need to meet ever-decreasing limits on die amount of
volatile organic compounds emitted from their manufacturing plants. These products have
been highly effective at reducing widespread heavy metal use in the past. The continued
application of these new synthesis technologies today helps insure the continued develop-
ment and wise use of these important polymers well into the future.
Yttrium as a Lead Substitute in Cationic
Electrodeposition Coatings
In 1976, PPG Industries introduced the first Cationic Electrodeposition Primer to the
automotive industry. During the succeeding years, this coating technology became widely
used in die industry so that today, essentially all automobiles are given a primer coat using
die chemistry and processing methods developed by PPG. The major benefits of this tech-
nology to the automotive industry are corrosion resistance, high transfer efficiency (low
waste), reliable automated application, and very low volatile organic emissions.
Unfortunately, the high corrosion resistance property of electrocoat has always been depen-
dent on the presence of small amounts of lead salts or lead pigment in the product. For
over 20 years, PPG and other paint companies have sought a substitute for lead in this
application.
The electrocoat process itself complicates the problem of replacing lead in electrocoat
primers. Most common corrosion-inhibitive materials interfere with the deposidon process,
are environmentally undesirable, or are not active when applied by electrodeposition. Also, a
wide variety of metal substrates are used in the automotive industry. Inhibitors that work well
over one substrate may not perform effectively over another. Furthermore, the performance
of a given inhibitor is dependent on the quality of cleaning and pretreatment of the metal in
question. Metal pretreatments have traditionally relied on nickel and chromium for corrosion
performance and, like lead, these metals have also come under regulation and are often
Henkel Surface
Technologies
PPG Industries, Inc.
53
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removed or used sparingly in modern automotive applications. Thus, obtaining corrosion
resistance over multiple substrates and treatments widiout lead is more difficult today dian
ever before.
During recent years, efforts at PPG to find new organic and inorganic corrosion inhibitors
have identified yttrium as a potentially superior anticorrosive in die electrocoat primer appli-
cation. This is based on several criteria. The pollution prevention assessment of yttrium
performed in cooperation with die U.S. EPA shows yttrium to be of a low level of concern
to aquatic organisms. In addition, yttrium is twice as effective as lead on a weight basis to
produce the required corrosion performance. Thus, die levels of yttrium in commercial coat-
ings will contain less dian one-half die yttrium by weight relative to lead in comparably
performing lead-containing products. Also, when the dust hazard of yttrium (as indicated by
TLV) is compared to diat of lead, it is roughly 100 times safer dian lead at typical levels of
use of each element. Last, it has been found that as yttrium is deposited in an electrocoat film,
it deposits as the hydroxide. The hydroxide is converted to yttrium oxide during baking of
the electrocoat. The oxide is extraordinarily nontoxic by ingestion as indicated from die
LD50 of greater dian 10 g/kg in rats.
Several commercial applications of diis technology are in place, and qualification of yttri-
um containing formulations with Automotive OEM manufacturers is under way. As PPG
customers implement yttrium over die next several years, approximately one million pounds
of lead (as lead metal) will be removed from die electrocoat applications of PPG automotive
customers. In addition, implementation of yttrium should result in the elimination of
25,000 pounds of chromium and 50,000 pounds of nickel (annually) for PPG pretreatment
customers.
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Index
Award winners are indicated with *.
3M
Hydrofluoroethers (HFEs) — The Right Balance of Properties 44
Air Products and Chemicals, Inc.
DEOXO-FLUOK™ Reagent 36
Albright & Wilson Americas, Inc.
A New Environmentally Friendly Corrosion Inhibitor 47
AMSOIL, Inc.
Waste Oil Source Reduction through Extended Oil Service Life 31
Anderson Chemical Company
Total Impact Program (TIP®): An Environmentally Preferable Program
for Laundry 30
Argonne National Laboratory
Clean-Diesel Breakthrough: Simultaneous Decrease in Emissions of Both
Particulates and Oxides of Nitrogen during Combustion 36
Arkenol Holdings, L.L.C.
Sugars from Lignocellulosic Materials for the Production of Bio-Based Fuels and
Chemicals 29
BAT Technologies, Inc.
Primer for Antifouling Paint 27
* Bayer Corporation and Bayer AG
Two-Component Waterborne Polyurethane Coatings 6
Beckman, Eric J., Chemical Engineering Department,
University of Pittsburgh
Catalysts for the Copolymerization of Carbon Dioxide and Cyclic Ethers 10
Beckman, Eric J., Chemical Engineering Department, University of
Pittsburgh
Production of Hydrogen Peroxide Directly from Hydrogen and Oxygen in CO* • • 17
Bergbreiter, David E., Department of Chemistry, Texas A&M University
The Use of Soluble Polymers to Recover Catalysts and to Control
Catalytic Reactions 19
BetzDearborn
Designing an Environmentally Friendly Copper Corrosion Inhibitor for
Cooling Water Systems 37
BIOCORP, Inc.
Biodegradable Thermoplastic Material (Mater-Bi™) 21
Bose, Ajay K., Department of Chemistry and Chemical Biology,
Stevens Institute of Technology
Microwave-Induced Organic Reaction Enhancement (MORE) Chemistry for
Eco-Friendly Syntheses 14
55
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Brennecke, Joan R, Department of Chemical Engineering, University
of Notre Dame, and Beckman, Eric J., Department of Chemical and
Petroleum Engineering, University of Pittsburgh
Ionic LiquidlCO2 Biphasic Systems: New Media for Green Processing 14
Burlington Chemical Company, Inc.
Development of a Practical Model and Process to Systematically
Reduce the Environmental Impact of Chemicals Utilized by the
Textile and Related Industries 23
Cargill Dow Polymers LLC
Process to Produce Biodegradable Poly lactic Acid Polymers 51
CDTech
A New Process for Producing Dimethyl Carbonate 48
Center for Forest Products Research, Inc.
Polymers and Plastics from Lignin Biomass 27
CerOx Corporation
The CerOx Process: A Non-Thermal Alternative for Hazardous
Waste Destruction 22
CHEMECOL, LLC
PVC Alternative Technology 28
Ciba Specialty Chemicals Corporation
Ashless Friction Modifier/Antioxidant for Lubricants 33
Ciba Specialty Chemicals Corporation
New Organic Corrosion Inhibitors Help Replace Toxic Heavy Metals and
Reduce Solvent Emissions 48
ClearMate, Inc.
ClearMate 22
*Dow AgroSciences
Sentricon* Termite Colony Elimination System, A New Paradigm for
Termite Control 7
DuPont Crop Protection
Biocatalytic Production of 5-Cyanovaleramide 34
Dynacs Engineering Company, Inc. and Kennedy Space Center
Oxidizer Scrubber Project 49
Eastman Kodak Company
Minimizing Environmental Emissions by Using Different Solvents in
Manufacturing Processes 47
Eckert, Charles A., School of Chemical Engineering, and Liotta,
Charles L., School of Chemistry and Biochemistry, Georgia Institute
of Technology
Benign Syntheses in Nearcritical Water 9
ECOGAS Corporation
McCommas Bluff Landfill Gas Processing Facility. 46
Eka Chemicals, Inc.
SVP-Pure™ CIO2 Process Technology 52
Environmental Technology and Education Center
High Energy Efficiency, Environmentally Friendly Refrigerants .24
56
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Evergreen Nylon Recycling LLC
Innovative Green Chemistry for Sustainable Manufacture of Caprolactam 44
Freeman, Harold S., Department of Textile Engineering Chemistry
and Science, North Carolina State University
Synthetic Dyes Based on Toxicological Considerations 18
Gleason, Karen K., Department of Chemical Engineering, Massachusetts
Institute of Technology, and Ober, Christopher K., Materials Science and
Engineering, Cornell University
Environmentally Benign Lithography for Semiconductor Manufacturing 11
H and H Associates, Inc.
DUAL-ICE®: A Non-Toxic, Non-Caustic Instant Cold Compress 24
Henkel Surface Technologies
Water-Based Synthesis and Purification ofMannich Base Modified Polyphenols. . 53
Hill, Craig L., Department of Chemistry, Emory University, and
Weinstock, Ira A., U.S. Department of Agriculture Forest Service, Forest
Products Laboratory
Pollution-Free Conversion of Trees to Paper Using Air in Place of
Sulfur and Chlorine 16
Ho, Nancy W. Y., Laboratory of Renewable Resources Engineering,
Purdue University
Genetic Engineering of Saccharomyces Yeasts for Effective Production of
Ethanol and Other Green Chemicals from Renewable Biomass 12
Hudlicky, Thomas, Department of Chemistry, University of Florida
Tandem Enzymatic-Electrochemical Methods for Green Manufacturing: Efficient
Synthesis of Pharmaceuticals from Halogenated Aromatic Waste 19
IBM Research Division
The Chemical Kinetics Simulator Program 35
lonEdge Corporation
Zero-Waste Dry Plating of Cadmium 32
KM Limited, Inc.
The PIX Module Software: Combining Life Cycle Assessment with
Activity-Based Costing to Reduce Global Environmental Impact and
Sustain Industrial Profitability 26
Knipple, Douglas C, Department of Entomology, Cornell University
In Vivo Synthesis of Lepidopteran Pheromone Precursors in Saccharomyces
cereviseae: An Economical Process for the Production of Effective, Nontoxic,
Environmentally Safe Insect Control Products 13
Li, Chao-Jun, Department of Chemistry, Tulane University
Chemical and Material Syntheses by Using Metal-Mediated and Catalyzed
Reactions in Water 10
The Lubrizol Corporation
Durable AMPS® Antimist Polymers for Aqueous Metalworking Fluids 38
Lynd, Lee R., Thayer School of Engineering, Dartmouth College
Overcoming the Recalcitrance ofCellulosic Biomass and Envisioning the Role of
Biomass in a Sustainable World 15
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Madison Chemical Company
Cadmium Replacement in Mechanical Coating 21
Mallinckrodt Baker, Inc.
Hydrogen Sulfide Elimination 44
Maroto-Valer, M. Mercedes, The Energy Institute, The Pennsylvania
State University
Pollution Prevention through Simultaneous Reduction of Emissions and
Commercial Utilization of Energy Related Waste Streams 17
Micell Technologies
The MICARE Liquid CO2 Dry Cleaning Process 25
Mitzel, Thomas, Department of Chemistry, Trinity College
Stereoselective Synthesis ofEpoxy Alkynes: Use of a-Chlorosulfides to Control
Syn/Anti Selectivity in Indium Promoted C-C Bond Formation in an
Aqueous Medium 18
Mobil Oil Corporation
Membrane Separation in Solvent Lube Dewaxing 46
Morton International, Inc.
ADVAFLEX™ Organic Stabilizer 33
Motorola Corporation and ULVAC Technologies, Inc.
Manufacturing Qualification of an All Dry Via Deveil Plasma Process 45
Nalco Chemical Company
Designing an Environmentally Sensible Chlorine Alternative 38
Nextec Applications, Inc.
Solventless Process for Improving Fabric Performance Properties 28
Novo Nordisk BioChem of North America, Inc.
BioPreparation™ of Cotton Textiles: A Cost Effective, Environmentally
Compatible Preparation Process 35
PPG Industries, Inc.
Replacement of Asbestos in the Diaphragm Cell Process for Manufacture of
Chlorine and Caustic Soda 52
PPG Industries, Inc.
Yttrium as a Lead Substitute in Cationic Electrodeposition Coatings 53
Radtech International, North America
Eliminating Air Pollution (VOCandHAP) at the Source through the Use of
Ultraviolet and Electron Beam Polymerization 40
*RevTech, Inc.
Envirogluv™: A Technology for Decorating Glass and Ceramicware with
Radiation Curable Environmentally Compliant Inks 4
Robbat Jr.. Albert Chemistry Department Tufts University
Chemlnformatics: Faster, Better, Cheaper, Greener Chemical Analyses 11
Robbat Jr., Albert Chemistry Department Tufts University
On-Line Detection of Subsurface Pollutants by Thermal Extraction Cone
Penetrometry-Thermal Desorption Gas Chromatography/Mass Spectrometry 15
*Roche Colorado Corporation
An Efficient Process for the Production ofCytovene®, A Potent Antiviral Agent.... 5
58
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Solvox Manufacturing Company
Solvox Special 5501, An Antiagglomerate and Stickles Neutralizerfor the
Paper Industry 29
Sunshine Makers, Inc.
Crystal Simple Green® 23
Tanko, James M., Department of Chemistry, Virginia Polytechnic
Institute and State University
Green Chemistry through the Use of Supercritical Fluids and Free Radicals 12
TechMatch, Inc.
N-Methylmorpholine-N-oxide (NMMO): A Novel, Nontoxic Solvent for
Cellulose for Source Reduction in the Production of Textile Fibers 26
U.S. Army Soldier and Biological Chemical Command (SBCCOM)
Electronic and Photonic Polymers from Biocatalysts 39
U.S. Army Soldier and Biological Chemical Command,
Edgewood Chemical Biological Center
Filter Leak Test Using Ozone-Benign Substances 43
U.S. Department of Agriculture, Agricultural Research Service,
Southern Regional Research Center
Environmentally Benign Antibacterial Agents 41
U.S. Department of Agriculture Forest Service
Pollution-Free Conversion of Trees to Paper Using Air in Place of
Sulfur and Chlorine 51
U.S. Department of Agriculture, National Center for Agricultural
Utilization Research
Environmentally Benign Synthesis ofMonoglyceride Mixtures Coupled with
Enrichment by Supercritical Fluid Fractionation 42
U.S. Department of Agriculture, National Center for Agricultural
Utilization Research
Environmentally Benign Two-Step Synthesis of Fatty Alcohol Mixtures Using
Supercritical Carbon Dioxide (SC-COi) and SC-COJHydrogen Mixtures 42
U.S. Environmental Protection Agency, Office of Research and
Development, National Risk Management Research Laboratory
Oxygenation of Hydrocarbons by Photocatalysis: A Green Alternative 49
U.S. Environmental Protection Agency, Office of Research and
Development National Risk Management Research Laboratory
Paris II Solvent Design Software 50
U.S. Polychemical Corporation
Dispersit™: A Waterbased Oil Dispersantfor Oil Spills in
Salt and Fresh Water 24
*Wong, Chi-Huey, The Scripps Research Institute
Enzymes in Large-Scale Organic Synthesis 3
Wool, Richard P., Center for Composite Materials, University of Delaware
Affordable Composites from Renewable Sources (ACRES) 9
59
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