United States
Environmental Protection
Agency
Office of Pollution
Prevention and Toxics
(7406)
EPA744-K-96-001
July 1996
The Presidential
Green Chemistry Challenge
Awards Program
Summary of 1996 Award
Entries and Recipients
> Printed on paper that contains at least 20 percent postconsumer fiber.
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Contents
Awards ........................................ .2
Alternative Synthetic Pathways Award 2
Alternative Solvents/Reaction Conditions Award .,,,,....,,,,.. .3
Designing Safer Chemicals Award 4
Small Business Award ,.,....,.,....,.,......,.,....,.,... .5
Academic Award ...,.,....,.,......,.,....,.,......,.,.. .7
........................................ .8
Entries from Academia ......,.,....,.,......,.,....,.,... .8
Entries from Small Businesses ..,.,....,.,......,.,....,.,.. 12
Entries from Industry and Government 16
Index ........................................ .45
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Summary of 1996 Award Entries and Recipients
President Clinton announced the Green Chemistry Challenge on March
16, 1995, as one of his Reinventing Environmental Regulations Initiatives.
According to President Clinton, the Green Chemistry Challenge was estab-
lished to "promote pollution prevention and industrial ecology through a
new U.S. Environmental Protection Agency (EPA) Design for the
Environment partnership with the chemical industry." More specifically, the
program was established to recognize and support fundamental and innova-
tive chemical methodologies that are useful to industry and that accomplish
pollution prevention through source reduction.
EPA Administrator Carol Browner announced the Green Chemistry
Challenge Awards Program on October 30, 1995. She described the program
as an opportunity for individuals, groups, and organizations "to compete for
Presidential awards in recognition of fundamental breakthroughs in cleaner,
cheaper, smarter chemistry." The Green Chemistry Challenge Awards
Program provides national recognition for technologies that incorporate
green chemistry principles into chemical design, manufacture, and use.
Entries received for the 1996 Presidential Green Chemistry Challenge
Awards were judged by an independent panel of technical experts convened by
tlie American Chemical Society. The criteria for judging included health and
environmental benefits, scientific innovation, and industrial applicability. Five
projects that best met the scope of the program and the criteria for judging were
selected for the 1996 Awards and nationally recognized on July 11, 1996.
This document provides a collection of summaries of the entries received for
the 1996 Presidential Green Chemistry Challenge Awards. The approaches
described in these 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 that are less hazardous to human health and the
environment. The approaches described in these summaries also illustrate the
technical and economic feasibility of implementing green chemical methodolo-
gies and are recognized for their beneficial scientific, economic, and environ-
mental impacts.
Note: The summaries provided in this document were obtained from the entries received for the 1996
Presidential Green Chemistry Challenge Awards. They were edited for space, stylistic consistency, and
clarity, but they were not written by nor are officially endorsed by EPA. In many cases, these summaries
represent only a fraction of the information that was 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 conducted on all information contained in the entries received. Claims
made in these summaries have not been verified by EPA.
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Monsanto Company
The Catalytic Dehydrogenation of Diethanohmine
Disodium iminodiacetate (DSIDA) is a key intermediate in the produc-
tion of Monsanto's Roundup® herbicide, an environmentally friendly, non-
selective herbicide. Traditionally, Monsanto and others have manufactured
DSIDA using a well-known process (Strecker process) requiring ammonia,
formaldehyde, hydrogen cyanide, and hydrochloric acid. Hydrogen cyanide
is of particular concern because of its extreme acute toxicity, and its use
requires special handling to minimize risk to workers, the community, and
the environment. Furthermore, the chemistry involves the exothermic gen-
eration of potentially unstable intermediates, and special care must be taken
to preclude the possibility of a runaway reaction. The overall process also
generates up to one kilogram of waste for every seven kilograms of product.
Much of this waste contains traces of cyanide and formaldehyde and must be
treated prior to safe disposal.
In pursuit of safer and environmentally benign chemistry, Monsanto has
developed and implemented an alternative DSIDA process that relies on the
copper-catalyzed dehydrogenation of diethanolamine (DEA). The raw mate-
rials have low volatility and are less toxic than those of other processes.
Process operation is inherently safer because the dehydrogenation reaction
is endothermic and therefore does not present danger of runaway. Moreover,
this "zero-waste" route to DSIDA produces a product stream that, after fil-
tration of catalyst, is of such high quality that no purification or waste cut is
necessary for subsequent use in the manufacture of Roundup*. The new
technology represents a major breakthrough in the production of DSIDA
because it avoids the use of cyanide and formaldehyde, is safer to operate,
produces higher overall yield, and has fewer process steps.
The metal catalyzed conversion of aminoalcohols to amino acid salts was
known since 1945. However, commercial application of this chemistry was
not known until Monsanto developed a series of proprietary catalysts that
make the chemistry commercially feasible. The original dehydrogenative
approach to amino acid salts had apparently been impracticable because the
catalysts, cadmium, nickel, and copper, are either too toxic, poorly selective,
poorly active, and/or physically unstable to be commercially viable. The
patented improvements on metallic copper catalysts made at Monsanto
afford an active, easily recoverable, highly selective, and physically durable
catalyst that has proven itself in large-scale use.
This catalysis technology also can be used in the production of other
amino acids such as glycine. Moreover, it is a general method for conversion
of primary alcohols to carboxylic acid salts and is potentially applicable to
tlie preparation of many other agricultural, commodity, specialty, and phar-
maceutical chemicals.
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The Development and Commercial Implementation of 100 Percent
Carbon Dioxide as an Environmentally Friendly Blowing Agent
for the Polystyrene Foam Sheet Packaging Market
In recent years the chlorofluorocarbon blowing agents used to manufac-
ture polystyrene foam sheet have been associated with environmental con-
cerns such as ozone depletion, global warming, and ground level smog. Due
to these environmental concerns, the Dow Chemical Company has devel-
oped a novel process for the use of 100 percent carbon dioxide COs.
Polystyrene foam sheet is a useful packaging material offering high stiffness
to weight ratio, good thermal insulation value, moisture resistance, and recy-
clability. This combination of desirable properties has resulted in the growth
of the polystyrene foam sheet market in the United States to over 700 mil-
lion pounds in 1995. Current applications include thermoformed meat, poul-
try and produce trays, fast food containers, egg cartons, and serviceware.
The use of 100 percent CO2 offers optimal environmental performance
because CCfc does not deplete the ozone layer, does not contribute to ground
level smog, and will not contribute to global warming since CO will be used
from existing by-product commercial and natural sources. The use of CO
by-product from existing commercial and natural sources such as ammonia
plants and natural gas wells, will ensure that no net increase in global CCfc
results from the use of this technology. Carbon dioxide is also non-flamma-
ble providing increased worker safety and is cost effective and readily avail-
able in food grade quality. Carbon dioxide also is used in such common
applications as soft drink carbonation and food chilling and freezing.
The use of Dow 100 percent CCfe technology eliminates the use of 3.5 mil-
lion pounds per year of hard CFC-12 and/or soft HCFC-22. This technology
has been scaled from pilot line to full scale commercial facilities. Dow has made
the technology available through a commercial license covering both patented
and know how technology. The U.S. Patent Office granted Dow two patents for
this technology (5,250,577 and 5,266,605).
The Dow Chemical
Company
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Rohm and
Company
Designing an Environmentally Safe Marine Antifoulant
Fouling, the unwanted growth of plants and animals on a ship's surface,
costs the shipping industry approximately $3 billion a year. A significant por-
tion of this cost is the increased fuel consumption needed to overcome
hydrodynamic drag. Increased fuel consumption also contributes to pollu-
tion, global warming, and acid rain.
The main compounds used worldwide to control fouling are the organ-
otin antifoulants, such as tributyltin oxide (TBTO). They are effective at pre-
venting fouling, but have widespread environmental problems due to their
persistence in the environment and the toxic effects they cause, including
acute toxicity, bioaccumulation, decreased reproductive viability, and
increased shell thickness in shellfish. These harmful effects led to an EPA
special review of organotin antifoulants and to the Organotin Antifoulant
Paint Control Act of 1988. This act mandated restrictions on the use of tin in
the United States and charged the EPA and the U.S. Navy with conducting
research on alternatives to organotins.
Based on the need for new antifoulants, Rohm and Haas Company began
to search for an environmentally safe alternative to organotin compounds.
The ideal antifoulant would prevent fouling from a wide variety of marine
organisms without causing harm to non-target organisms. Compounds from
the 3-isothiazolone class were chosen as likely candidates and over 140 were
screened for antifouling activity in laboratory and field tests. The 4,5-dichloro-
2-n-octyl-4-isothiazolin-3-one (Sea-Nine™ anti-foulant) was chosen as the can-
didate for commercial development.
Extensive environmental testing was done comparing Sea-Nine™
antifoulant to TBTO, the current industry standard. Sea-Nine™ antifoulant
degraded extremely rapidly with a half life of one day in seawater and one
hour in sediment. TBTO, on the other hand, degraded much more slowly,
with a half life in seawater of nine days and six to nine months in sediment.
Tin bioaccumulated, with bioaccumulation factors as high as 10,000 X, while
Sea-Nine™ antifoulant's bioaccumulation was essentially zero. Both TBTO
and Sea-Nine™ were acutely toxic to marine organisms, but TBTO had
widespread chronic toxicity, while Sea-Nine™ antifoulant showed no chron-
ic toxicity. Thus the maximum allowable environmental concentration
(MAEC) for Sea-Nine™ antifoulant was 0.63 parts per billion (ppb) while the
MAEC for TBTO was 0.002 ppb. Sea-Nine™ antifoulant has been sold
world-wide and hundreds of ships have been painted with coatings contain-
ing it. Rohm and Haas Company obtained EPA registration for the use of
Sea-Nine™ antifoulant, the first new antifoulant registration in over a decade.
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Production and Use of Thermal Polyaspartic Acid
Millions of pounds of anionic polymers are used each year in many indus-
trial applications. Polyacrylic acid (PAC) is one important class of such poly-
mers. In many uses, the polymers ultimately end up in a waste treatment
facility. The ideal disposal for these polymers is via biodegradation by
microorganisms because the degraded endproducts are innocuous. The dis-
posal of PAC is problematic, however, because it is not biodegradable. An
economically viable, effective, and biodegradable alternative is thermal
polyaspartate (TPA).
Donlar invented two highly efficient processes to manufacture TPA;
patents have either been granted or allowed. The first process involves a dry
and solid polymerization converting aspartic acid to polysuccinimide. No
organic solvents are involved during the conversion and the byproduct is
condensated water. The process is extremely efficient - a yield of more than
97 percent of polysuccinimide is routinely achieved. The second step of this
process, the base hydrolysis of polysuccinimide to polyaspartate, is also
extremely efficient and waste free.
The second TPA production process involves using a catalyst during the
polymerization, which allows a lower heating temperature to be used. The
resulting product has improvements in performance characteristics, lower
color, and biodegradability. The catalyst can be recovered from the process,
thus minimizing waste.
Independent toxicity studies of commercially produced TPA have been
conducted using mammalian and environmental models. Results indicate
that TPA is non-toxic and environmentally safe. TPA biodegradability also
has been tested using established OECD methodology, performed in an
independent laboratory. Results indicate that TPA meets OECD guidelines
for Intrinsic Biodegradability. PAC can not be classified as biodegradable
when tested under the same conditions.
Many end uses of TPA have been discovered. In the agricultural sector,
the use of high levels of fertilizer has been practiced to sustain crop yields.
However, the efficiency of fertilizer usage is generally low and unused fertil-
izer can cause not only economic loss, but has an undesirable impact on the
environment. Therefore, a better fertilizer management strategy is warrant-
ed to sustain crop yields and lessen the negative environmental impact of fer-
tilizer runoff. TPA can be an ideal candidate to improve fertilizer or nutrient
management because it increases the efficiency of plant nutrient uptake,
which not only assists in sustaining the nutrient sources, but also protects the
ecology of the agricultural land, while at the same time bringing economic
benefits in the form of increased crop yields.
Donlar Corporation
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TPA also can be used in the water treatment industry. TPA can be used
as mineral scale inhibitors for calcium carbonate, calcium sulfate and barium
sulfate. The efficacy of TPA has been tested extensively and compared with
PAC, the industry standard. Results indicate that TPA is as good as, and in
many instances outperformed, PAC.
There are additional uses for TPA. In the detergent industry, TPA can be
used as an anti-redeposition agent; its efficacy is again comparable to PAC.
In the oil and gas production industry, TPA can serve as scale and corrosion
inhibitors, reducing the need for toxic corrosion inhibitors and lessen the
need for waste treatment.
TPA is an ideal candidate for use in water treatment, agriculture, and
other industries. The processes to manufacture TPA are economically viable
and TPA is proven to be biodegradable, non-toxic, and effective.
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Conversion of Waste Biomass to Animal Feed,
Chemicals, and Fuels
A family of technologies has been developed at Texas A&M that converts
waste biomass into animal feed, industrial chemicals and fuels. Waste bio-
mass includes such resources as municipal solid waste, sewage sludge,
manure, and agricultural residues. Currently these resources are under-uti-
lized; in fact, many have a cost associated with their disposal. Waste biomass
is treated with lime to render it more digestible. Lime-treated agricultural
residues (e.g. straw, stover, bagasse) may be used as ruminant animal feeds.
Alternatively, the lime-treated biomass can be fed to a large anaerobic fer-
mentor in which rumen microorganisms convert the biomass into volatile
fatty acid (VFA) salts such as calcium acetate, propionate, and butyrate. The
VFA salts are concentrated and may be converted into chemicals or fuels via
three routes. In one route, the VFA salts are acidified releasing acetic, pro-
pionic, and butyric acids. In a second route, the VFA salts are thermally con-
verted to ketones such as acetone, methyl ethyl ketone, and diethyl ketone.
In a third route, the ketones may be hydrogenated to their corresponding
alcohols such as isopropanol, isobutanol, and isopentanol.
This family of technologies offers many benefits for human health and the
environment. Lime-treated animal feed can replace feed corn, which is
approximately 88 percent of corn production. Growing corn requires plow-
ing, which exacerbates soil erosion; approximately two bushels of top soil
are lost for each bushel of corn harvested. Also, corn requires intensive
inputs of fertilizers, herbicides, and pesticides, all of which are contaminat-
ing ground water.
Chemicals (e.g. organic acids and ketones) may be produced economi-
cally from waste biomass that has a negative impact on the environment,
such as municipal solid waste and sewage sludge. Typically, these wastes are
landfilled or incinerated, which incurs a disposal cost while contributing to
land or air pollution. By producing chemicals from biomass, nonrenewable
resources such as petroleum and natural gas, are conserved for later genera-
tions. Because 50 percent of U.S. petroleum consumption is now imported,
displacing foreign oil will help reduce the U.S. trade deficit.
Fuels (e.g. alcohols) produced from waste biomass have the benefits cited
above, i.e., reduced environmental impact from waste disposal and reduced
trade deficit. In addition, oxygenated fuels derived from biomass are clean-
er burning and do not add net carbon dioxide to the environment, thereby
reducing factors that contribute to global warming.
Professor
Mark Holtzapple,
Department of Chemical
Engineering,
Texas A&M University
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Professor
T. Alan Hatton,
Department of Chemical
Engineering,
Massachusetts Institute of
Technology
Professor
Stephen L. Buchwald,
Chemistry Department,
Massachusetts Institute of
Technology
Professor
Leo A. Paquette,
Department of Chemistry,
Ohio State University
Professor
Tomas Hudlicky,
Department of Chemistry,
University of Florida
Derivatizpd and Polymeric Solvents for Minimizing Pollution
During the Synthesis of Pharmaceuticals
A new class of solvents has been developed that have solvation properties
similar to those of solvents used conventionally in chemical synthesis, sepa-
rations and cleaning operations, but for which the potential for loss by envi-
ronmentally-unfavorable air emissions or aqueous discharge streams is
minimized. These solvents are derivatives of solvents currently used in reac-
tion and separation processes, tailored such that they are relatively non-
volatile and non-water soluble, thereby satisfying the criteria for pollution
source reduction. The solvents can be used as neat reaction or separation
media, or they can be diluted in an inert environment such as higher alka-
lies. Polymeric or oligomeric solvents such as derivatized THF have been
synthesized using macromonomers incorporating the desired functionality.
These polymeric solvents are easily recovered using mechanical separations
such as ultrafiltration rather than energy-intensive distillation processes. This
new concept for solvent design and synthesis offers the potential for significant
source reductions in air and water pollution and can be considered to be wide-
ly applicable to fine chemical and pharmaceutical synthesis, separations, and
cleaning operations.
Environmental Advantages Offered by Indium-Promoted
Carbon-Carbon Bond-Forming Reactions in Water
The development of effective carbon-carbon bond forming reactions in
aqueous media is imperative for the future welfare and growth of the chem-
ical industry. The metal indium, a relatively unexplored element, has recent-
ly been shown to offer intriguing advantages for promoting organic
transformations in aqueous solution. The feasibility of performing
organometallic/carbonyl condensations in water, for example, has been
amply demonstrated for the metal indium. Indium is non-toxic, very resis-
tant to air oxidation, and easily recovered by simple electrochemical means,
thus permitting its re-use and guaranteeing uncontaminated waste flow. In
addition, protection-deprotection of functional groups and an inert atmos-
phere are not necessary when implementing this technology. Commercial
application is immediately possible for this exciting new chemistry and may
have been implemented already. As additional progress is made, adaption to
existing procedures will undoubtedly come quickly.
Enzyme-Assisted Conversion of Aromatic Substances to
Value-Added End Products. Exploration of Potential Routes to
Biodegradable Materials and New Pharmaceuticals
The combination of enzymatic transformations performed in aqueous
media with efficacious, brevity-based design has been shown to yield
unprecedented efficiency in the attainment of important pharmaceuticals
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from metabolites of the arene ds-diol type, more than 200 of which are
known. Such processes lead to pollution reduction at the manufacturing
source by drastically shortening the synthetic process, thus requiring less
reagent and solvent input. Because one or more steps are performed in water
with whole cells of common soil bacteria, the residual mass of such steps is,
after sterilization, judged suitable for disposal to municipal sewers, thus fur-
ther reducing the amount of actual waste. This program has potentially glob-
al impact with attendant benefits to the health and economy of society at
large through managed processing of aromatic waste.
Green Technology for the 21st Century: Ceramic Membranes
Advancing technology in the areas of remediation and such "green" engi-
neering tools as ceramic membranes can make a significant contribution in
terms of environmental clean-up and a healthier world. Ceramic membranes
represent a relatively new class of materials that can be produced from a
variety of starting materials and processed in different ways to yield products
with a broad range of physical-chemical characteristics and an equally large
range of applications. The robust character of ceramic membranes enables
them to withstand broad pH and temperature ranges, elevated pressures,
organic solvents, and chemical and heat sterilization. In addition, pore size
can be controlled in these materials and is typically 5-100 A in diameter.
These characteristics indicate that ceramic membranes could replace their
organic polymeric counterparts in many applications where conditions
would otherwise preclude using an organic polymer membrane. These appli-
cations include separations, catalysis, photocatalysis and energy storage sys-
tems for solar cells and micromotor devices. Ceramic membranes are a
cutting edge technology that could well provide economic growth for exist-
ing industries, in addition to facilitating new growth industries in environ-
mental remediation. A market survey published in 1992 on the economic
benefits from alternate applications of inorganic membrane technology indi-
cated that active implementation of such technology could well result in a $2
billion per year sales market, a $16.6 billion increase in the national GDP, a
$2 billion improvement in the balance of trade, and a decrease in energy use
of 6 quads per year.
A Nontoxic Liquid Metal Composition for Use
as a Mercury Substitute
Mercury is used extensively in switches and sensors, but is toxic to humans
and animals. In addition to being an excellent conductor of electricity, mer-
cury has significant surface tension and, unlike any other metal known,
remains fluid throughout a wide temperature range which encompasses 0°C.
Because of these properties, mercury is found in numerous commercial prod-
ucts such as automobiles, thermostats, steam irons, pumps, computers, and
even in tennis shoes. In each of these cases mercury functions as a liquid elec-
trical switch. Since billions of mercury switches are made worldwide each year,
a non-toxic replacement appears highly desirable. A nontoxic, cost effective
alternative to mercury that has comparable performance characteristics has
been identified at Virginia Tech. This green technology provides a gallium
Professor
Marc A. Anderson,
Water Chemistry Program,
University of Wisconsin-
Madison
Professor
Larry T. Taylor,
Department of Chemistry,
Virginia Tech
Virginia Tech Intellectual
Properties
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Professor
James A. Durnesic,
Chemical Engineering
Department,
University of Wisconsin
Dr. John C. Crittenden,
National Center for Clean
Industrial and Treatment
Technologies,
Michigan Technological
University
Professor
Henry Shaw,
Chemistry and
Environmental Science
Department,
New Jersey Institute of
Technology
Dr. Dan Watts,
Center for Environmental
Engineering and Science,
New Jersey Institute of
Technology
alloy containing indium, zinc, and copper that conducts electricity, freezes
below 0°C, exhibits high surface tension, and possesses a very high boiling-
point and very low vapor pressure. In addition, non-mercury switches and sen-
sors can replace mercury switches and sensors without modifying existing tech-
nology. Mercury also is used in temperature sensors, pressure activated
switches, pumps and filters, slip rings, liquid mirror telescopes, fluid unions,
dental amalgam, and in medical devices such as sphygmomanometers and
bougies. The non-mercury material also can serve as a substitute for elemental
mercury in a many of these applications.
Rational Design of Catalytic Reactions for Pollution Prevention
Chemical products manufacturing is a major industrial source of toxic and
hazardous chemicals. Catalytic technologies hold the key to the development
of more environmentally benign chemical processes and for the continued
improvement of existing processes. Historically, the design of chemical syn-
thesis catalysts was extraordinarily empirical. Yield of desired products and
operational characteristics were normally optimized based on suites of experi-
ments run on catalysts made from various manufacturing conditions and
blends. The ability to correlate catalyst behavior to catalyst surface features
was extremely limited. Accordingly, predicting the desired catalyst features for
a given application and from that, formulating a catalyst manufacturing strate-
gy, was essentially beyond reach. Moreover, the concept of redesigning cata-
lysts so as to inhibit the formation of undesired coproducts, toxic materials, and
wasteful pollutants was fanciful. A methodology for Rational Catalyst
Technologies has been developed at the University of Wisconsin that makes it
possible to design and optimize catalysts by first understanding the nature of
the desired catalyst surface and from that formulate the catalyst. This strategy
for the rational design of catalytic reactions has found wide acceptance world-
wide and has been applied successfully to link surface science research to the
development of industrially important catalytic chemical reactions. Industrial
collaborations and/or applications include ammonia catalysis, the environ-
mental de-NOx reaction, the water gas shift reaction on magnetite, titania sur-
face species, molybdena and vanadia catalysts for clean partial oxidation of
methane, and hydrocarbon cracking over acid Y-zeolite catalysts for the clean
production of isobutylene.
The Replacement of Hazardous Organic Solvents with Water in the
Manufacture of Chemicals and Pharmaceuticals
The use of water as the primary solvent is a realistic approach to green
chemistry and is a very desirable approach for reducing hazardous organic sol-
vents from plant inventories. Multiphase reactors have been developed at the
New Jersey Institute of Technology and other universities that use water as the
reaction medium in order to avoid the use of hazardous organic solvents in the
manufacture of pharmaceuticals and specialty chemicals. The technology is the
first to show that free radical bromination of organics can be carried out in
aqueous systems. A unique semi-continuous droplet reactor also has been
developed for epoxidations. Before pollution prevention became fashionable,
organic chemists found that water-based reactions gave higher yields at faster
10
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rates under milder conditions than organic solvent-based reactions. This is
incentive enough for process change. The fact that these methods offer a new
"non-end-of-pipe" method of eliminating VOC's adds a major incentive for
process modification.
Soapy CQ2
Carbon dioxide surfactant technology, or "soapy CCfc", has demonstrated
the utility of replacing less acceptable organic chemicals with liquid/supercrit-
ical CO2 and thus can have a very positive environmental impact. Carbon
dioxide represents an environmentally friendly alternative to the solvents cur-
rently used in a variety of applications. In order to expand the use of liquid and
supercritical CO, its solvating power for large, hydrocarbon based molecules
must be enhanced. The key to this technology is the development of surfactant
systems for CO% as well as establishing the underlying principles involved with
COa-surfactant combinations. In addition to polymerization processes, tech-
nology extensions of this project are relevant for COi as a cleaning and extrac-
tion media (replacing halogenated hydrocarbons) as well as a solvent/media
for organic reactions. In all of these applications, the production and emission
of hazardous waste would be significantly reduced by replacing the current
technology with carbon dioxide surfactant technology. It must be noted that
CCh is readily available as a waste gas from various sources. Thus no new CCfe
will be produced due to the success of the technology - it will just be borrowed
from the environment for an interim period of time.
The SYNGEN Program for Generation of
Alternative Syntheses
The SYNGEN program attempts to survey all possible synthetic routes to
a target molecule and reduce the vast number of these possibilities quickly
and stringently to focus on only the shortest and cheapest routes. The pro-
gram first focuses on minimizing steps and the central role of prior skeletal
dissection to find the best assemblies of the target skeleton from available
starting skeletons. It then presents the ideal synthesis, of construction reac-
tions only, to create the target just by sequential constructions uniting these
starting skeletons. Finally, the digital basis rigorously, but concisely, defines
all possible molecular structures and their reactions. This basis allows the
new SYNGEN program to propose all the short alternative syntheses of any
product from real starting materials in terms of both their cost and environ-
mental impact.
Professor
Joseph DeSimone,
Department of Chemistry,
University of
North Carolina at
Chapel Hill
Air Products and
Chemicals, Inc.
Professor
James B. Hendrickson,
Department of Chemistry,
Brandeis University
11
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Molten Metal
Technology, Inc.
Altus Biologies Inc.
Catalytic Extraction Processing
Catalytic Extraction Processing (CEP) is a proprietary technology that
uses secondary materials and by-products (that might otherwise be consid-
ered 'wastes') as raw materials in a manufacturing process. CEP manufac-
tures commercial products (i.e., industrial gases, alloys, and ceramics) from
heterogeneous organic, organometallic, and inorganic materials using a
molten metal bath as both catalyst for elemental dissociation and a solution
for reaction engineering. CEP feed materials go through two stages in the
metal bath: dissociation and dissolution of molecular entities to their ele-
ments and reaction of these elemental intermediates to form products. The
waste minimization and environmental performance of CEP is ensured by
the separation of feed from product through elemental dissociation and the
predictable partitioning afforded by the control of thermodynamic operating
conditions. Employed as an off-site, closed-loop process unit, CEP maxi-
mizes environmental performance for a broad spectrum of secondary mate-
rials and by-products through pollution prevention, waste minimization, and
decreased demand on ever-diminishing natural resources.
Cross-Linked En^me Crystal Technology
Enzymes are proteins that can function as highly efficient and selective
catalysts. They have evolved over billions of year's to facilitate the myriad of
biochemical reactions essential to life, and as such, they are compatible by
definition with living organisms. The benefits of enzyme technology have
long been recognized, but to date, the chemical and physical stability of
enzymes has not approached that of conventional heterogeneous catalysis.
Crosslinked Enzyme Crystals (CLEC) are novel catalysts that are suitable for
chemical manufacturing, diagnostic instruments, therapeutics, and for the
detoxification of hazardous materials. The concept of CLEC emerged from
the realization that protein crystals grown for structural studies using X-ray
diffraction were also macroscopic particles that, if properly stabilized, might
present a new and robust class of immobilized enzymes. By extension of this
simple idea, CLECs have been developed that circumvent many of the prac-
tical problems associated with enzyme use. In addition to being environ-
mentally benign, enhanced properties of CLECs include superior catalytic
performance, operating stability, storage stability, compactness, superior uni-
formity, and operational convenience.
12
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Development of a Biodiversity Search and Enzyme
Optimization Technology
Biocatalysis is widely regarded as a promising new approach to source
reduction of pollution associated with chemical manufacturing. It has not
been widely adopted to date, however, due to the limited availability of
process-compatible biological catalysis. Recombinant Biocatalysis, Inc.
(RBI), has developed a whole new tool kit of biological catalysis for chemists.
Catalysts are central to modern chemical manufacturing as well as to life. A
good catalyst accelerates the rate of a desired reaction compared to unwant-
ed, waste generating, side reactions. Enzymes are wonderfully selective and
specific catalysts. Enzymes, however, evolved to work in living systems, and
enzymes that work well in a chemical process plant have not been broadly
available to chemists and chemical engineers. RBI has developed a new
technology specifically to meet that unmet need. By turning state-of-the-art
biotechnology to the problem of making useful enzymes for chemists, RBI
has enabled a step change in the availability of useful protein-based catalysts
for the chemical process industry. RBI has developed and applied a power-
ful, new biodiversity search technology to scan natural sources for new
enzymes. Once the best enzyme that nature has to offer for a particular appli-
cation is identified, RBI applies additional high throughput technology to
optimize the enzyme to make it more useful in a chemical plant. This new-
technology already has produced more than 150 new, robust biological cat-
alysts for the chemical process industry and will generate more than 3,000 by
1997.
Recombinant
BioCatalysis,
Inc.
Development of a Nickel Solution
Historically, electroplaters of duplex nickel had to use formaldehyde and
coumarin-bearing nickel plating solutions to obtain a non-sulfur nickel deposit,
which is essential to the duplex nickel process, for maximum corrosion pro-
tection of external automotive trim and bumpers. The Watts' bath, introduced
in 1916, made it possible to increase the speed of nickel deposit by a factor of
ten by increasing the electrical current density. This development lead to the
modern bright nickel plating baths known today, using organic and inorganic
additives. Organic aromatic sulfonic acid was later introduced to the Watts'
bath to achieve the first practical bright nickel plating solution. In 1936,
formaldehyde was added to the solution followed in rapid succession by other
additives. Coumarin, along with formaldehyde, became the important ingre-
dients in a variety of nickel plating baths referred to as "semi-bright". Today,
semi-bright nickel plating occupies an important position in plating.
Benchmark Products has developed a nickel brightener solution that, while
improving the performance of electroplating, also significantly reduces the
environmental impact by eliminating two toxic ingredients, formaldehyde and
coumarin, and substituting non-hazardous ingredients.
Benchmark
Products, Inc.
13
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Zeller International
Corporation
Enviroblock Technology
Using a new pulverization technology, all types of scrap glass can be ground
into a useful aggregate with the consistency of beach sand or fine gravel. Any
size or form of flat window glass, mirrors, windshields, light bulbs, bottles,
neon tubing, or glass containers can be processed back into a usable form.
Scrap glass is fed to an EVIROGRINDER pulverizing machine which deliv-
ers a controlled particle size material. A fine grind sand product is then fed to
a blending machine, the ENVIROMIXER, which dry blends the two basic
substances, ground glass and a reactive binder. These mixed materials are
placed inside the ENVIROFACTOR machine to form blocks. Hard, dense,
naturally insulative/smooth faced blocks are rapidly compacted at low cost
and high volume with a yield of 400 to 600 blocks per hour. Walls built with
glass blocks reduce heating and air conditioning because glass is a natural insu-
lation source. Glass blocks are waterproof, fireproof, strong, and reduce ener-
gy consumption.
National Conversion to Low Sudsing Hand Dish Detergents for
Industrial, Institutional, and Especially Consumer Application
In die United States, almost all dish detergents or liquid detergents used for
hand dish washing are anionic based, with specifically high foaming properties
formulated purposely into the product to deliver a consumer aesthetic. To pro-
vide this sudsing characteristic, multiple anionic and foam boosters are
used/needed to deliver the effect. The addition of all these extra chemicals is
unnecessary to deliver actual cleaning performance and oily soil emulsifica-
tion. This can be achieved by using nonionic surfactants, straight chain linear
alcohol ethoxylates or APGs (alkyl polyglycosides) or other low foaming envi-
ronmentally suitable alternatives to alkylbenzene sulfonate and foam boosters
formulation types. Nationwide use of this technology in all dish detergents
would reduce overall toxicity due to the discharge of high sudsing dish prod-
ucts in rivers and streams. In addition, overall water usage would decrease due
to faster manufacturing and overall reduced energy consumption of operations
providing this product category to all U.S. market sectors: consumer, industri-
al, and institutional. This formulation strategy can be available immediately
nationwide and can be manufactured readily by all national brand companies.
14
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A Non-Toxic, Non-Flammabk, Aqueous-Based Cleaner/Degreaser
and Associated Parts Washing System Commonly Employed in
Automotive Repair Industry
An aqueous based cleaner and associated parts washing system common-
ly employed in the automotive repair industry has been developed that elim-
inates the generation of hazardous waste associated with current parts wash
systems. Currently, the majority of parts washers employ a "Stoddard
Solvent" which, when spent, is manifested as a hazardous waste to a distilla-
tion facility which separates the solvent from the petroleum residue. The new
technology employs a non-toxic, non-flammable, aqueous based
cleaner/degreaser that can be recycled continuously on site by employing
oil/water separation and standard combustion engine filters. Both the oil sep-
aration and filtration apparati are housed within a recently developed parts
washer unit, such that the aqueous cleaner/degreaser is recycled in-situ, elim-
inating the removal and/or transportation and special treatment of spent
cleaner material off-site. Testing results have shown that (i) the resulting oil
skimmed from the cleaner can, under current hazardous waste definitions, be
managed as a "spent oil" and combined with spent engine oil for beneficial
reuse as a secondary fuel, and (ii) the filter can be managed under current
methods used to recycle other used combustion engine oil filters. Circuit
Research Corporation believes there are in excess of 7,000 parts washers in
Minnesota generating approximately 1.5 million gallons of spent Stoddard
solvent annually. Circuit Research Corporation's alternative technology could
significantly reduce the generation of this waste.
Circuit
Corporation
15
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Bayer Corporation
Henkel Corporation,
Emery Group
Aldimine-Isocyanate Chemistry: a Foundation for
Environmentally-Friendly High Solids Coatings
The single greatest challenge that the chemical industry faces today is the
design and manufacture of new chemicals that are not only efficacious, but
just as importantly, environmentally friendly. Within the coatings industry,
these new chemicals play the additional role of aiding in pollution preven-
tion by reducing the amount of volatile organic compounds (VOCs) in the
form of solvents, materials that traditionally have been used at high levels.
The need for raw materials that reduce solvent demand and yet maintain or
preferably improve coating performance is of primary importance.
Commercial coatings systems based on aldimine-isocyanate chemistry have
been developed and are finding widespread acceptance as a solution to VOC
restrictions. Current applications exist in the automotive refinish business
where aldimines are used to make coatings containing only 20 to 25 percent
volatile solvents, replacing products that have 40 to 50 percent volatile sol-
vents by weight. Since the introduction of this technology in 1995, old tech-
nology resin systems requiring more than 100,000 kilograms of additional
organic solvent have been displaced. This volume will triple in 1996 and
approach one million kilograms in 1997. More importantly, the volume of
organic solvents displaced as other market areas adopt this technology is
expected to increase dramatically. Additional benefits of this technology
include: allowing low VOC coatings to be developed, resulting in large sol-
vent savings for a given application without transferring environmental lia-
bility to production or use; it is already in significant commercial use, and
will become a high volume product line by the end of the century, resulting
in nontrivial source reduction of organic solvent emissions; it is compatible
with existing and future coatings systems; it does not require significant cap-
ital investment to employ; and it increases productivity
Alky I Polyglycoside Surfactants
Henkel Corporation's alkyl polyglycoside (APG*) surfactants are a class
of non-ionic surfactants marketed to the detergent and personal care indus-
tries. APG® surfactants are manufactured from renewable resources: fatty
alcohol, derived from coconut and palm oils, and glucose, derived from corn
starch that is supplied from U.S. sources. APG® surfactants have very low
ecotoxicity and are readily biodegradable and, therefore, are more innocu-
ous to the environment than alternative petrochemical-based technologies.
In addition to the environmental friendliness of the chemistry, APG® surfac-
tants demonstrate the following benefits in detergent and personal care appli-
cations: reduction of overall chemical consumption by improving the
cleaning efficiency in detergent formulations; reduction of formulated prod-
uct packaging waste by permitting the formulation of concentrated cleaning
products; reduction of formula stabilizing adjuncts (hydrotropes), such as
sodium xylene sulfonate and ethanol, that do not contribute to cleaning per-
16
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formance and, in the case of ethanol, increase volatile organic emissions; and
excellent cleaning performance with lower skin and eye irritation compared
to other surfactants. APG® surfactants represent an important application of
green chemistry that uses renewable resources. APG® surfactants are cur-
rently manufactured in a new plant producing 50 million pounds per year
for use in the formulation of several hundred detergent and personal care
products in the United States and worldwide.
The Alternative Feedstocks and Biological and Chemical
Technologies Research Programs
The Alternative Feedstocks (AF) program supports development work
that employs alternative, renewable feedstocks in the biological and/or
chemical production of commodity or commodity-like chemicals. The
Biological and Chemical Technologies Research (BCTR) program supports
research and development efforts that provide evidence of the technical and
economic feasibility of advanced chemical and biological concepts that
improve energy utilization, operational efficiencies, and environmental
soundness of current U.S. industry process operations. These two programs
involve both the specific and broad utilization of "green chemistry" in the
fulfillment of their missions. By definition, the AF program is green chem-
istry since it promotes the use of renewables in producing subsidy-free chem-
icals from feedstocks such as corn, lignocellulosics, and oil seed crops on
scales that are or could be commodity chemicals. Many of the technology
hurdles needed to employ biocatalysts as tools or biomass as a feedstock
resource for the chemical processing industry have been addressed by the
BCTR program. For example, efforts ranging from the development of mol-
ecular modeling tools to new, less toxic electrochemical hydrogenation
processes have been undertaken and demonstrated for use in current
processes. Within the federal sector, these two programs have an exception-
al history of applying green chemistry to industrial needs.
An Alternative Solvent, Isomet
The Bureau of Engraving and Printing, the world's largest securities man-
ufacturing establishment, produces currency, postage stamps, revenue
stamps, United States Saving Bonds, and other government securities. Until
1990, the Bureau used Typewash for cleaning the typographic seals, serial
number, numbering blocks of the Cop-Pack (overprinting presses) and
postage stamp printing presses. Typewash is a solvent mixture of methylene
chloride (55 percent), toluene (25 percent) and acetone (20 percent). As of
September 1, 1990, this solvent is no longer in compliance with District of
Columbia Environmental Law and Federal Air Toxic Law. An alternative
solvent, Isomet was developed by the Bureau of Engraving and Printing to
replace Typewash. Isomet is a mixture of synthetic isoparaffinic hydrocarbon
(55 percent), propylene glycol monomethyl ether (10 percent), and isopropyl
alcohol. Initial testing of Isomet found the solvent to be a highly successful
replacement for Typewash and less costly than any commercially available
solvent. Isomet was found to be acceptable in cleaning ability, solvent evap-
oration rate, solvent odor, environmental and safety compliances, and cost.
U.S. Department of
Energy, Office of
Industrial
Technologies
Programs
Bureau of
Engraving and
Printing, Office of
Research and
Technical Support
17
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Pharmacia
Upjohn, Inc.
Los Alamos National
Laboratory
Isomet is currently used for cleaning all Bureau postage stamp and over-
printing presses. Thus a solvent discharged at the rate of 5,000 gallons per
year was made environmentally friendly.
An Alternative Synthesis of Bisnoraldehyde, an Intermediate to
Progesterone and Corticosteroids
For the past 40 years, the steroidal intermediate bisnoraldehyde (BNA)
has been made and used at Pharmacia and Upjohn to produce bulk phar-
maceutical steroids like progesterone and corticosteroids. Recently, an
entirely new route to BNA from waste soya bean residues was implemented
due to the development of an environmentally acceptable and efficient
chemical process for the oxidation of an intermediate, referred to as bisno-
ralcohol (BA), to bisnoraldehyde. The new process uses commercial strength
bleach and a catalyst/co-factor system (4-hydroxy-TEMPO) and is run in a
two-phase reaction medium. This new route to BNA has many human
health and environmental benefits because it: avoids using heavy metal
based oxidants such as hexavalent chromium salts and complexes, man-
ganese oxides, or lead salts; does not produce noxious emissions unlike oxi-
dations which use activated dimethylsulfoxide, dimethylsulfide, or
complexes of sulfur trioxide; does not use toxic or hazardous materials like
organic peroxides, organoselenium compounds, or chlorinated quinones;
avoids potentially hazardous reaction mixtures like those used for ozonoly-
sis, or oxidative dehydrogenation with metal oxides; increases utilization of
soya sterol feedstock from 15 percent to 100 percent; produces non-toxic
aqueous process waste streams and recoverable organic solvent waste
streams; eliminates a process with a running, recycled inventory of 60,000
gallons of ethylene dichloride (EDC), a known carcinogen, and that needs
up to 5,000 gallons of EDC input annually; produces the same product
amount as the previous route with 89 percent less non-recoverable organic
solvent waste and 79 percent less aqueous waste; and has the chemical selec-
tivity required for high quality bulk pharmaceutical manufacture. In addition
to being a new synthetic route for converting soya sterols to therapeutic
steroids, this chemical process is also a general method for converting pri-
mary alcohols to aldehydes that is environmentally superior to currently
available oxidation methods.
Application of Freeze Drying Technology to the Separation of
Complex Nuckar Waste
The nuclear industry must comply with increasingly stringent standards
for radioactive material levels present in liquid effluents. Current conven-
tional methods of decontamination include distillation, ion exchange, pre-
cipitation reactions, or chelating agents. Freeze drying technology (FDT) has
been applied to the decontamination of radioactive liquids and shown to be
thousands of times more effective than conventional methods. Distillation,
ion exchange, and chelating agents often require multiple passes, and
because additional components (resins or chelating agents, which in turn
18
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must be disposed as radioactive) are typically needed by these methods,
reductions in the volume of radioactive waste are rarely realized. FDT will
efficiently separate solvents and volatile acids from complex waste solutions
and process liquids. The separated liquids will be virtually free of radioactive
contamination and can be re-used or discarded as nonradioactive. FDT will
drastically reduce the volume of radioactive wastes. Volume reductions
greater than one thousand times have been achieved in aqueous solutions, but
the exact volume reduction of nuclear waste will depend on its moisture con-
tent. FDT will eliminate the need for storage or destruction of the liquid com-
ponent and will lower transportation costs because of volume and weight
reductions. In addition, this technology can be considered safe; no high tem-
peratures or pressures are used. The process occurs in a vacuum, so the fail-
ure of a component would lead to an inward leak and the potential for
contamination outside the system is significantly reduced. Finally, the refrig-
erant used in this technology is environmentally friendly liquid nitrogen.
Application of Green Chemistry Principles to Eliminate Air
Pollution from the Mexican Brickmaking Microindustry
A new recirculating design for small brickmaking kilns has been investi-
gated as an alternative to conventional operations, which are a significant
source of air pollution. The bricks used in building many houses and offices
buildings in Mexico and other parts of the third world are typically made by
hand and fired in a small kiln using available fuels such as sawdust, treated
wood, paper, trash, tires, plastic, and used motor oil. Although these bricks
cost about of standard high-fired construction bricks, they do not meet the
minimum strength requirements for commercial construction in the United
States. In addition, a major by-product of this brickmaking industry is a high
level of air pollution-both participates and toxic chemicals-that results from
inefficient thermal design and use of cheap but readily available fuels. This
industry is the third leading cause of air pollution in the El Pasojuarez area.
Redesign of the kilns to allow efficient energy recovery and to eliminate waste
from over- and under-firing makes the use of non-polluting fuels (natural gas)
economically attractive. The design challenge is to use inexpensive, readily
available materials and equipment to avoid significant capital outlay.
Laboratory investigations and process modeling have been performed at the
Los Alamos National Laboratory, and field tests are being performed at
ECOTEC in Ciudad Juarez, Mexico, in cooperation with FEMAP, a private
foundation in Mexico, and with the El Paso Natural Gas Company. The direct
benefits of these improvements in the brickmaking process are reduced air
pollution, safer operating conditions, and better bricks. In addition, process
modeling indicates that fuel consumption can be reduced by approximately
55 percent and cost analyses project that this will result in an increase in prof-
it for the brickmakers of about 35 percent.
Los Alamos National
Laboratory
19
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U.S. Department of
Energy,
Office of Pollution
Prevention
U.S. Department of
Energy,
Office of Energy
Research
U.S. Department of
Energy,
Chicago Operations
Office
U.S. Department of
Energy,
Argonne Group
Argonne National
Laboratory
Asarco Incorporated
Application of Microchemistry Technology to the Analysis of
Environmental Samples
"Green" chemistry is an umbrella term addressing such related concepts
as waste minimization, pollution prevention, solvent substitution, environ-
mentally conscious manufacturing, maximum atom utilization, technologies
for a sustainable future, environmental security, and industrial ecology.
Another applicable concept, microscale chemistry (or microchemistry), is the
application of chemical principles and apparatus at a scale much smaller
than currently employed by most bench chemists, thus reducing the volume
of reagents and product by several orders of magnitude. Microscale and
green chemistries both incorporate waste minimization, pollution preven-
tion, and solvent substitution. Adoption of green and microscale methods is
increasingly essential for the environmental analytical community as regula-
tions tighten, the costs of waste disposal escalate, and public scrutiny increas-
es. By applying green chemistry principles and using advances in separation
science, instrumentation, microscale techniques, and solvent substitution,
chemists at Argonne National Laboratory have developed trace environ-
mental analysis methods that incorporate source reduction. The techniques
reduce or eliminate the use of hazardous solvents, decrease analysis turn-
around time, and significantly reduce the generation of secondary wastes
associated with analytical processing. The success of these methods exem-
plifies the opportunities to reduce waste generation at analytical laboratories
across the country. With appropriate institutional advocacy, these principles
can be applied broadly to this large chemical sector.
Asarco - West Fork Biotreatment Project
Asarco has developed a biotreatment system for removing metals from
mine water prior to its discharge to surface waters. Asarco's West Fork Unit
is an underground lead-zinc mine that discharges water from mine dewater-
ing to the West Fork of the Black River under NPDES permit. Recent
changes in the Water Quality Standards required Asarco to explore water
treatment alternatives. Asarco initiated passive biotreatment investigations in
1993 which lead to the design and construction of an anaerobic pilot
biotreatment cell (biocell) in February, 1994. The biocell (designed to treat
20 gallons of water per minute) was filled with a substrate mixture of 50 per-
cent old sawdust, 33 percent mine tailings, 10 percent cow manure, 5 percent
alfalfa hay, and 2 percent lime rock (all material used was obtained locally;
other organic materials such as yard waste and sewage sludge can be substi-
tuted). Sulfate Reducing Bacteria (SRB) were cultivated within the anaerobic
environment of the substrate. SRB are abundant in nature and are found pre-
dominately in bogs and swamps. SRB produce hydrogen sulfide gas as a by-
product that acts as a sulfiding agent to precipitate dissolved lead and other
metals from mine water. The pilot biocell has demonstrated continued suc-
cess in reducing metals from mine water to below Missouri's Water Quality
Standards. The biotreatment cell operated efficiently through extremes of
ambient temperature, water flow rates, and metal loading. Unlike conven-
tional chemical water treatment plants, a biotreatment cell does not require
the introduction of chemicals into the water, does not produce sludges on a
20
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daily basis that must be disposed, does not require a full time operator, is not
subject to mechanical malfunction, can operate at twice the design rate for
short periods of time without a reduction in treatment efficiency, and can be
constructed at a fraction of the cost.
The BHC Company Ibuprofen Process
A new synthetic "green chemistry" process has been developed and com-
mercialized by BHC Company to manufacture ibuprofen, a well known
non-steroidal, anti-inflammatory pharmaceutical (painkiller) marketed under
the names of Advil™, Motrin1M, and others. The new process involves only
3 catalytic steps with approximately 80 percent atom utilization and replaces
technology with 6 stoichiometric steps and less than 40 percent atom utiliza-
tion. The use of anhydrous hydrogen fluoride as both catalyst and solvent
offers important advantages in reaction selectivity and waste reduction. This
chemistry (99 percent atom utilization when including the recovered by-
product acetic acid) is a model of source reduction, the optimum waste min-
imization method topping the Environmental Protection Agency's waste
management hierarchy. Virtually all starting materials are either converted
to product, reclaimed as by-product, or are completely recovered and recy-
cled in the process. The generation of waste is practically eliminated. The
BHC ibuprofen process is an innovative, efficient technology that has revo-
lutionized bulk pharmaceutical manufacturing. Large volumes of aqueous
waste (salts) normally associated with such manufacturing are virtually elimi-
nated. The anhydrous hydrogen fluoride catalyst/solvent is recovered and recy-
cled with greater than 99.9 percent efficiency. No other solvent is needed in the
process, simplifying product recovery and minimizing fugitive emissions. The
virtually complete atom utilization of this streamlined process makes it truly a
waste minimizing, environmentally friendly, green technology.
CleanSystem1 Gasoline
Internal combustion engines produce considerable amounts of nitrogen
oxides (NOx) as a combustion by-product. Nitrogen oxides are an air pollu-
tant in their own right and react with atmospheric organic compounds in the
presence of sunlight to form ozone, a powerful respiratory irritant. Despite a
76 percent reduction in allowable NOx emissions from light duty gasoline
vehicles over the past 25 years, U.S. motor vehicles still emit 3 million tons
of NOx each year. Source reduction in the context of vehicular NOx means
less NOx generated in the engine. Steps in this direction have been few (pri-
marily exhaust gas recirculation) and, being a design feature, are not applic-
able to older vehicles. There is, therefore, a genuine opportunity for
technology which can reduce the NOx generated in vehicle engines on the
road today. Texaco has developed and introduced a patented additive tech-
nology based on novel chemistry which reduces NOx formation in gasoline
engines. This additive is present in all CleanSystem3 gasoline sold in the
United States. Controlled vehicle testing has demonstrated reductions in
tailpipe NOx up to 22 percent. This additive fulfills the role of traditional
deposit control ("detergent") additives in keeping fuel system components
BHC Company
(Hoechst Celanese
Corporation)
Texaco Inc.
21
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clean, and provides additional performance in the area of preventing and
removing combustion chamber deposits. Cleaner combustion chambers
retain less combustion heat from one engine cycle to the next, and the result-
ing lower temperature leads to the formation of fewer nitrogen oxides (NO*).
Lockheed Martin
Tactical Aircraft
Systems
Development and Implementation of Low Vapor Pressure
Cleaning Solvent Blends and Waste Cloth Management
Systems to Capture Cleaning Solvent Emissions
Lockheed Martin Tactical Aircraft Systems (LMTAS) has developed and
patented low vapor pressure organic solvents and has successfully imple-
mented a low vapor pressure cleaning operations and waste cloth manage-
ment and disposal system. The solvent blends and cleaning technology are
being used by the aerospace industry, the military, and various other indus-
tries. Additionally, LMTAS has substituted one of the new solvent blends
(DS-104) for a CFC-113 based general purpose cleaning solvent used in the
surface wiping of aircraft parts, components, and assemblies in all aspects of
aircraft manufacturing. The substitution significantly reduced solvent use
and air emissions, eliminated ozone depleting compounds from cleaning
during aircraft assembly, reduced costs, and improved chemical handling
and usage practices. From 1986-1992, LMTAS used a general purpose wipe
solvent containing 85 percent CFC-113 by weight throughout the manufac-
turing process. The use of the CFC-113 solvent blend resulted in the emis-
sion of approximately 255 tons per year of CFC-113 and 45 tons per year of
volatile organic compounds (VOCs). The implementation of DS-104 has
reduced wipe solvent VOC emissions to 7 tons per year in 1993 and 3 tons
per year in 1994, with no CFC emissions. Other reductions documented and
include: 68 to 71 percent reductions in solvent use by volume, 86 to 88 per-
cent savings in solvent purchase cost, and 95 to 97 percent reductions in total
air emissions.
Rochester Midland
Corporation
Development of a New "Core" Line of Cleaners
Cleaning is an important practice and necessity of modern civilization.
An effective cleaner must be able to penetrate through soil to disrupt/destroy
the complicated types of bonding that cause it to adhere to the surface being
cleaned. Most modern cleaners are comprised of surface active agents that
are derived from petrochemical resources. While these components are
effective, they tend to be environmentally harsh and depend upon a natural
resource whose supply is finite and limited. The market for these products is
estimated to be in the range of $5 billion, which equates to approximately 5
billion pounds of product annually. The impact of developing chemistries
that are less polluting during the extraction, manufacturing, use, and dispos-
al of these products is therefore quite significant, as are the human health and
safety impacts. During the past few years a new family of cleaners has been
developed that are less toxic with reduced impacts to both people and the
environment when compared to traditional products used for the same pur-
pose. The chemistries incorporated into these products have resulted in
products that are readily biodegradable, comprised of zero to very low
22
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volatile organic components and ozone depleting substances, effective in
their intended purpose (cleaning), and economically competitive. In addi-
tion, these products have low human and aquatic toxicity and low corrosiv-
ity. Main molecular components of these products are derived from
renewable, bio-based resources that are lower polluting and typically less
toxic than their petrochemical alternatives. These new "core" line of clean-
ers are an innovative approach to the formulation of an important series of
products and are the safest yet developed in their fields.
Development of a New Process for the Manufacture
of Pharmaceuticals
In an effort to reduce the amount of waste generated at its East Hanover
site, Sandoz Pharmaceutical Corporation has evaluated all processes being
conducted at this site for their susceptibility to improvements in the utiliza-
tion of solvents, to minimize the waste byproduct, and at the same time
improve operating efficiency. One process in particular was identified that
appeared to offer significant opportunities for such process restructuring.
After two years of research all the essential elements of the new process have
now been demonstrated. The new process uses a single new solvent for both
reaction medium and separation, which significantly reduces the overall sol-
vent requirements and permits recycling of the used solvent by simple dis-
tillation. As a result, the process waste index is reduced from the current 17.5
pounds of waste generated per pound of product to 1.5, resulting in a pro-
jected reduction of 170,000 pounds per year in waste generation.
Furthermore, the amount of solvent used per batch is cut in half, thereby sig-
nificantly reducing the usage of solvent with attendant lower risks of worker
exposure and accidental releases into the environment. The decision to pro-
ceed with development of a new process, despite the potential problem of
obtaining FDA approval of the process changes, is due primarily to the
favorable economics of the new process. Conservative estimates of annual sav-
ings are around $775,000, compared to an investment of $2.1 million to develop
and implement the new process, which is equivalent to a return on investment
of 36.7 percent and less than three year pay-back time. It is estimated that over
75 percent of the manufacturing savings are due to process improvements, rather
than disposal costs of unused solvent, illustrating the process optimization bene-
fits characteristic for pollution prevention innovations.
Development of a New Sealant/Adhesive Chemistry for
Automotive Windshields. A New Two Part Chemical System
Using Acetoacetylated Polyol Prepolymers and Aminated
Acetoacetylated Polyol Prepolymers.
Up until this year all automotive windshield adhesives, used when replac-
ing windshields, have been made from unblocked isocyanate prepolymers.
These products may contain one to three percent isocyanates, which pose a
potential severe health hazard to the workers in the manufacture of these
prepolymer adhesives. In addition to chemical workers, installers of these
products and car owners can be exposed to the isocyanate prepolymers,
Sandoz
Pharmaceutical
Corporation
BF Goodrich
Tremco,
a BF Goodrich
Company
23
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U.S. Department of
Energy
Pacific Northwest
National Laboratory
which can pose a health risk. Tremco, a BF Goodrich Company, has been
able to develop a new sealant/adhesive chemistry that is significantly better
than isocyanate adhesives in many respects - it demonstrates more rapid
cure rate, even at low temperatures and low humidity conditions, posses
higher lap shear strengths, and is non-moisture sensitive. In addition, this
product is nonhazardous, nontoxic, contains no isocyanates, and poses no
health risks to chemical workers, installers, or consumers. This new two part
chemical system uses acetoacetylated polyol prepolymers. These prepoly-
rners are made by reacting di and triol polymers with tert-butylacetoacetate
(tBAA). Some of these acetoacetylated polyols are animated with low mole-
cular weight diamines. These acetoacetylated polyol amines are then react-
ed with acetoacetylated polyols to achieve a cured polymer matrix. This
system produces an extremely strong isocyanate type cure and allows for
faster "drive away times" for the car owner and more productivity for the
installer. In addition, an acetoacetylated roofing adhesive using the same
technology is being field tested. This product is completely free of solvents,
is 100 percent solid, and is environmentally friendly.
DOE Methods for Evaluating Environmental and Waste
Management Samples
"DOE Methods for Evaluating Environmental and Waste Management
Samples (DOE Methods)" is a document that provides new technology and
consolidated methods to analytical chemistry laboratories around the country
that are working on one of the world's most challenging environmental issues:
Cold War legacy waste. Sampling and analytical technologies that minimize
waste production have been given priority over traditional methods. It has
been demonstrated, for example, that some of the technologies produce 60 to
70 percent less hazardous and radioactive waste than other available tech-
nologies. The guidance information in "DOE Methods" also helps minimize
the number of analyses and saves time and money. Guidelines are provided
on how to (1) efficiently develop a sampling and analysis program, (2) effec-
tively and efficiently sample waste, (3) handle radioactive samples safely, and
(4) select appropriate analytical methods. Cross references allow the users to
select from currently available standard methodologies. "DOE Methods" has
been available for both DOE and commercial use since 1992. It is updated
every 6 months, thereby accelerating the release of new technology to speed
EM operations. The significance of the document is in its unique application
to the analysis of radioactive components and highly radioactive mixed waste.
The document currently contains about 65 sampling and analytical methods,
many of which are focused on the mixed-waste issue. The highly challenging
world of environmental problems cannot be solved without effective sam-
pling and analytical methods. "DOE Methods" takes a major step in the res-
olution of this problem.
24
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The Dow Chemical Company's Novel INVERT™ Solvents
The industrial cleaning industry, one of the largest consumers of organic
solvents in North America, is an industry in transition. Customers, both end-
users and formulators of cleaning products for the industrial cleaning indus-
try, are seeking alternatives for methyl chloroform and other ozone depleting
chemicals and for ways to reduce the total amount of volatile organic com-
pounds (VOCs) used in their work processes. Any alternative solvents or sol-
vent technology for industrial cleaners must meet specific physical
characteristics that result in performance properties similar to what it is
replacing. To meet industry needs, any new product should be easy to use,
evaporate quickly, prevent any new health or worker safety concerns, and
allow the user to meet emerging environmental regulations. INVERT™ sol-
vents from the Oxygenated Solvents Business of the Dow Chemical
Company are a remarkable advancement in solvent technology. These rev-
olutionary new products maintain the performance properties of organic sol-
vents but incorporate the environmental benefits of water. INVERT™
solvents are best described as the first practical development of solvent con-
tinuous microemulsions that can function as an alternative to traditional sol-
vents. The unique properties of microemulsions have led to their use in a
diverse range of applications that include enhanced oil recovery, environ-
mental remediation, consumer products, pharmaceutical formulations and
media for polymerization.
The Dow Chemical
Company
DryWash™
All conventional dry-cleaning solvents present health risks, safety risks, or
are detrimental to the environment. Currently, the dry-cleaning industry
uses perchloroethylene (85 percent), petroleum based or Stoddard solvents
(12 percent), CFC-113 (less than two percent), and 1,1,1-trichloroethane.
Perchloroethylene is a suspected carcinogen; petroleum based solvents are
flammable and smog producing; and CFC-113 is an ozone depletor and tar-
geted to be phased out by the end of 1995. Health risks due to exposure to
these cleaning solvents and the high costs of implementing and complying
with safety and environmental restrictions and regulations, reduced dry-
cleaning profit margins. Solvents are suspected of contaminating ground
water, air, and food products. For these reasons, the dry-cleaning industry is
engaged in an ongoing search for alternative, safe and environmentally
friendly cleaning technologies, substitute solvents, and methods to control
exposure to dry cleaning chemicals. DryWash™, a Hughes carbon dioxide
technology, has been developed and marketed as a safe, ecologically accept-
able and cost effective alternative to the current dry-cleaning process.
Carbon dioxide is a readily available, inexpensive, and unlimited natural
resource. It is chemically stable, non-corrosive, non-flammable, non-ozone
depleting and non-smog producing. The DryWash™ system reuses a natu-
rally occurring by-product with a multitude of sources. A dry-cleaning devel-
opmental prototype using liquid carbon dioxide has been built and
demonstrated. Completion of a 10 kilogram commercial size cleaning unit is
expected during the first quarter of 1996.
Hughes
Environmental
Systems, Inc.
25
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DuPont Company
California-Pacific
Lab & Consulting
The DuCare "Zen Effluent" Recycle Chemistry System
The Printing and publishing pre-press industry is undergoing a revolu-
tionary change driven by advances in imaging technology from a craft-based
industry to one relying far more on digital imaging and printing technology.
From a user perspective, this new technology is more environmentally
benign than the process it replaces. Several iterations of improvements in
hardware and software will be required before digital imaging completely
replaces conventional chemical imaging. The DUCARE system is a "bridge"
between the current and developing systems. It is designed as a "drop in" for
conventional processing and enables the customer to continue utilizing their
current equipment, thus avoiding a financial burden while still eliminating
the adverse environmental impact. DUCARE is an environmentally proac-
tive way for customers to prevent any film processor effluent from going
down their drain. Typically customers discharge the effluent to the drain, pay
to have it hauled away and disposed, or use expensive high maintenance
equipment for on-site treatment. The effluent contains hazardous chemicals
(as defined by SARA Title III), very high BOD and COD, high silver and
pH extremes. DUCARE, offered only by DuPont, solves these problems
using several industry firsts. A new developer was invented which has no
SARA Title III chemicals and is based on a vitamin C isomer. The chemistry
is designed to use 25 to 40 percent less product than conventional chemistry
and is recycled at its manufacturing sites to insure high quality and "like
new" performance. The wash-water recirculating unit reduces water use up
to 99 percent. This system can be used worldwide, wherever a cost effective
reverse distribution system can be set up.
The ECO Funnel
The ECO Funnel and Container is a new product designed to prevent
volatile toxic air contaminants from evaporating into the laboratory work
environment and into the atmosphere through the laboratory fume hood sys-
tem. Typically, a simple funnel is used in pouring waste solvent into a waste
bottle or carboy. In most cases the funnel is left on top of the bottle perma-
nently during the day, resulting in significant emission due to evaporation of
volatile organic compounds (VOCs) from the bottle into the laboratory envi-
ronment or fume hood. It may seem that contamination of the atmosphere
from such sources may not be large enough to be important or significant;
however, exact measurements have proven the contrary. For example, an 8
liter carboy filled with 8 liters of dichloromethane will emit 500 mL (1.5
pounds) of this solvent into the atmosphere in 5 days. The emission will vary
depending on the type of solvents used. The fume hood face velocity also
can affect the evaporation rate. However, for a typical fume hood at 700
cubic feet per minute and a typical 4 liter waste bottle with a regular funnel
containing 1000 mL tetrahydrofuran, 1000 mL acetone, and 1500 niL
dichloromethane, the emission rate was 0.09 pounds per 8 hours or 33
pounds per year. California-Pacific Lab and Consulting designed and patent-
ed a new funnel that has a lid connected to a shut-off ball which double seals
the system. The funnel stem is also longer and sealed to the bottle cap in
order to prevent emission from the side of the stem. Under the same condi-
26
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tions as described above for the 4 liter waste bottle with a standard funnel,
the ECO Funnel and Container resulted in zero emissions.
Elimination of Ozone-Depleting Chemicals in the Printed Wire
Board and Electronic Assembly and Test Processes
IBM Austin is a manufacturing and development facility. Operations
include the manufacture of printed wiring board (PWB) in the Panel Plant
facility and electronic circuit cards in the Electronic Card Assembly and Test
(ECAT) facility. In 1992 IBM Austin completely eliminated the use of CFCs
and other ozone depleting substances from its PWB and ECAT processes.
This elimination program resulted in 100 percent reduction of CFC-113
(1988 peak usage of approximately 432,000 pounds) and 100 percent reduc-
tion of methyl chloroform (1988 peak usage of approximately 308,000
pounds) from IBM Austin's PWB and ECAT processes. These accomplish-
ments were achieved by converting to an aqueous-based photolithographic
process in the PWB facility in 1989, an interim aqueous cleaning process in
the ECAT facility in 1991 and 1992, and a final No-Clean process (eliminat-
ing the aqueous cleaning process) in the ECAT facility. Changing from a sol-
vent-based photolithographic process to an aqueous-based process
eliminated methyl chloroform (MCF) from PWB panel manufacturing (1988
usage of 181,000 pounds). The interim process changes to aqueous cleaning
eliminated MCF from manufacturing processes in ECAT (1989 peak usage
of 196,000 pounds) and were largely responsible for eliminating CFC-113
from all manufacturing processes at the IBM site. Although CFC-113 was
eliminated from the site in 1991 and MCF was eliminated in 1992, ECAT's
ultimate goal was to convert all ECAT processes to No-Clean manufacturing
processes. This conversion was completed in 1993.
The Emission Quantification Model
In the semiconductor manufacturing process, liquid and gaseous chemi-
cal mixtures are used to manufacture submicron devices. These chemicals
are categorized into four general groups: corrosives, organics, toxics, and flu-
orinated compounds. Local, state, and federal environmental regulations
governing these materials are becoming more stringent and facilities must
ensure protection of human health and the environment. To help accomplish
this, ADM developed the Emissions Quantification Model (EQM) as a
method to identify and quantify the chemicals used in manufacturing
processes and incorporate them into a comprehensive environmental man-
agement system. Based on a modified mass balance model, pollution pre-
vention and control outcomes were used to develop a real-time
measurement method. The EQM provides information such as toxicity,
usage, and emission rates and is an invaluable tool for assessing human
health and environmental impacts as well as identifying opportunities to
optimize, reduce, reuse, recycle, and eliminate chemicals. The EQM has ini-
tiated many improvements at AMD's Austin site. For example, chemicals
with potential teratogenic properties were identified and replaced with less
toxic chemicals that still meet the specifications required to produce semi-
conductors. Methyl ethyl ketone, a hazardous air pollutant as well as a SARA
IBM-Austin
Advanced Micro
Devices (AMD),
Austin
Environmental
Department
27
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U.S. Department of
Defense,
Office of Munitions
U.S. Department of
Energy,
Weapons Supported
Research
Lawrence Livermore
National Laboratory
DuPont Company
313 reportable chemical, was replaced by methyl propyl ketone, a much less
hazardous substitute. Data from the EQM assessments identified chemicals
used in large quantities, including sulfuric acid and isopropyl alcohol, that
could be recycled. Currently, ADM is recycling 50 percent of the sulfuric
acid used in these facilities and is evaluating isopropyl alcohol recycling. In
the near future, all sulfuric acid used in these facilities will be recycled, and
if the capital expenditure is justified, feasible, and approved, isopropyl alco-
hol reprocessing will be implemented.
Environmentally-Driven Preparation of Insensitive
Energetic Materials
An innovative approach has been developed at Lawrence Livermore
National Laboratory to the synthesize l,3,5-triamino-2,4,6-trinitrobenzene
(TATB) and other insensitive energetic materials through the use of Vicarious
Nucleophilic Substitution chemistry (VNS). TATB is a reasonably powerful
insensitive high explosive (IHE) whose thermal and shock stability is consid-
erably greater than that of any other known material of comparable energy.
The high cost of TATB ($100 per pound) has precluded its use for civilian
applications such as deep-hole oil explorations. TATB is manufactured in the
United States by nitration of the relatively expensive and domestically
unavailable 1,3,5-trichlorobenzene (TCB) to give 2,4,6-trichloro-l,3,5-trini-
trobenzene (TCTNB) which is then animated to yield TATB. The new VNS
method developed at Lawrence Livermore National Laboratory for the syn-
thesis of TATB has many "environmentally friendly" advantages over the cur-
rent method of synthesis of TATB. Most significantly, it allows the elimination
of chlorinated species from the synthesis of insensitive energetic materials.
The new synthesis of TATB uses unsymmetrical dimethylhydrazine
(UDMH), a surplus propellant from the former Soviet Union, and ammoni-
um pi crate (Explosive D), a high explosive, as starting materials in lieu of the
chlorinated species, TCB. Several million pounds of Explosive D are targeted
for disposal in the United States; 30,000 metric tons of UDMH also await dis-
posal in a safe and environmentally responsible manner. The use of these sur-
plus energetic materials as a feedstocks in the new VNS method of
synthesizing TATB allows an improved method of demilitarization of con-
ventional munitions that also should offer significant savings in production
thereby making this IHE more accessible for civilian applications.
The INFINITY Dyeing Process
The INFINITY dyeing process was developed as an alternative method
to manage the dyeing cycle for nylon textiles. Over 8 billion pounds of nylon
textiles are consumed each year, and most are dyed to meet aesthetic and
functional demands. In the United States alone, consumption of dyes for
nylon exceeds 30 million pounds, much of which is left in the spent dye bath
after the fabric is dyed. This waste must be treated to avoid pollution of
downstream waterways. Mills are meeting regulatory requirements through
conventional process control techniques and end of pipe treatment. The
INFINITY dyeing process lets mills reduce their consumption of dyes and
other chemicals by 25 percent, and in some applications, water and steam
28
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use per dye cycle is cut in half. Conventional methods use up to 4,000 gal-
lons of water, 20 pounds of dye and 10 pounds of dye assist chemicals per
1,000 pounds of fabric. The INFINITY dyeing process uses only 75 percent
of the dye previously required, half the water, and less dye assist chemicals
to get tlie same fabric color. In addition, dye discharge into mill effluent
streams can be reduced as much as tenfold. A mill with a 90 percent exhaust
rate may discharge 500 pounds of unused dye into the mill's wastewater
treatment stream each week. With INFINITY, the same mill can move to 99
percent exhaust, reducing the amount of dye discharged to 50 pounds per
week; a significant step toward attacking waste at the source. The process is
currently being used at nylon textile mills in the United States, and work has
begun on the feasibility of using the process on wool, cotton, and polyester
blend fabrics. Cost savings by most mills using this process could easily
exceed $100,000 per year.
Innovative Techniques for Chemical and Waste Reductions in the
Printed Wire Board Circuitize Process
IBM produces 1.7 million square feet of multi-layer circuit boards per
year in a manufacturing plant in north Austin. Aqueous chemical baths and
rinse water are processed at a pretreatment plant where acidity is neutralized
and dissolved copper is removed prior to discharge to a sanitary sewer for
further treatment in a POTW. In 1991, the treatment process produced 1,417
tons of metal hydroxide sludge, a RCRA F006 hazardous waste. In 1992, a
team of environmental engineers, manufacturing engineers, and laboratory
personnel was formed to reduce hazardous waste sludge generation at the
water treatment plant by minimizing waste generation in the imaging line.
Two areas were identified for their waste minimization potential: acid used
in cleaning operations and developing solutions used prior to etching opera-
tions. Minimizing acid in the waste water reduces the amount of lime need-
ed to neutralize the solution and reducing developing solution reduces the
carbonates in the waste water which precipitates as calcium carbonate in the
presence of lime. By 1994, the team accomplished a 90 percent reduction in
hydrochloric acid used in cleaning for an annual savings of approximately
$340,000 in chemical cost. Additional work allowed for a 40 percent reduc-
tion of developing and stripping solutions used in the imaging area, for an
annual savings of approximately $75,000. These changes resulted in an
approximately 75 percent decrease in use of lime at the pretreatment plant.
This decrease in combination with reduced carbonate usage in developing
solutions resulted in a decrease in sludge production of over 670 tons per
year (based on first half 1994 results), a 47 percent reduction from 1991
sludge generation, for an additional savings of $250,000 in sludge disposal
costs. This project has shown that waste minimization through chemical
source reduction can reduce expenses as well as reduce waste.
IBM-Austin
29
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Rohm
Company
Praxair, Inc.
Invention and Commercialization of CONFIRM™ Selective
Caterpillar Control Agent
CONFIRM™ is a breakthrough in caterpillar control. It is chemically,
biologically, and mechanistically novel. It effectively and selectively controls
important caterpillar pests in agriculture without posing significant risk to the
applicator, the consumer, or the ecosystem. It will replace many older, less
effective, more hazardous insecticides. CONFIRM™ received full registra-
tion in the United States for codling moth control in walnuts in early 1995
and was used effectively in 1994/5, under emergency exemption, to combat
severe beet armyworm outbreaks in cotton and vegetables in several south-
ern states. CONFIRM™ insecticide controls caterpillars through an entirely
new and inherently safer mode of action than current insecticides. It acts by
strongly mimicking a natural substance found in the caterpillar's body, called
20-hydroxy ecdysone, which is the natural "trigger" that induces molting and
regulates development in insects. CONFIRM™ disrupts the molting process
in caterpillar pests, causing them to stop feeding within hours of exposure
and to die soon thereafter. Although CONFIRM™ is a potent mimic of 20-
hydroxy ecdysone in caterpillars, it is a surprisingly poor mimic in most
other insects and arthropods, and therefore is remarkably safe to a wide
range of key beneficial, predatory, and parasitic insects such as honeybees,
ladybeetles, parasitic wasps, predatory bugs and lacewings. In addition to its
novel and selective mode of action, CONFIRM™ does not bioaccumulate,
volatilize, leach, or persist unreasonably long in the environment. All of
these reasons make CONFIRM™ one of safest, most selective, and most use-
ful caterpillar control agents ever discovered.
Liquid Oxidation Reactor
Praxair has developed a unique process that allows the safe oxidation of
organic chemicals with pure or nearly pure oxygen. This technology, known
as the Liquid Oxidation Reactor (LOR) provides significant environmental
advantages compared to conventional, air-based oxidation processes. The
use of oxygen in place of air reduces the total gas throughput to the reactor,
thereby reducing the compression energy and the amount of vent gas that
must be treated prior to atmospheric release. In addition, the oxygen use can
positively affect the chemistry of the reaction, allowing the operation of the
process at lower temperatures and/or pressures, thereby improving selectiv-
ity without sacrificing production rate. The use of the Praxair LOR increas-
es the overall rate of reaction and volumetric productivity of hydrocarbon
oxidations while increasing selectivity and reducing the loss of solvent and
reactant to carbon oxides. The increased chemical efficiency with oxygen
results in substantial raw materials cost saving, and a 96 percent reduction in
the quantity of waste gases. The cost of product purification and waste dis-
posal is reduced substantially. In addition, the lower temperature operations
afforded by the LOR process reduces the loss of reactant and/or solvent to
by-products and to waste streams that also can contribute to environmental
problems and must be treated prior to release. The LOR will enable a large
and important segment of the U.S. chemical industry to realize more efficient
use of raw materials, reduced environmental emissions, and energy savings.
30
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Because the LOR also allows for higher productivity, lower capital costs,
and, consequently, improves competitiveness, there are significant incentives
for the implementation of the technology. Average operating-cost savings
and productivity gains worth $5-$20 million per plant per year have been
projected
Magnetic Separation for Treatment of
Radioactive Liquid Waste
High Gradient Magnetic Separation (HGMS) is the application of intense
magnetic fields to selectively separate solids from other solids, liquids, or
gases. The HGMS process has demonstrated promise for treatment of waste
streams containing actinide at Los Alamos National Laboratory (LANL).
The caustic liquid waste generated by operations in the LANL Plutonium
Processing Facility (TA-55) can produce up to 30,000 L of liquid effluent
annually, with an average alpha activity of 1010 dpm/L. Treatment and dis-
posal of the liquid effluents at the LANL Waste Water Treatment Facility
(TA-50) can ultimately produce up to 15 tons of TRU solid waste per year.
In order to avoid the TA-50 treatment, the goal at TA-55 is to reduce the
radioactivity in the waste streams to less than 5.8 x 10s dpm/L. Physical sep-
aration processes, such as HGMS, are particularly attractive because no
additional waste is generated during processing. HGMS is capable of con-
centrating tlie actinides in process waste streams to form a low volume,
actinide-rich stream for recycling, and a high-volume, actinide-lean stream
for direct discard. The proposed technology has been demonstrated success-
fully on a laboratory scale at TA-55 where results from screening experi-
ments on radioactive caustic liquid waste water indicate that over 99.9
percent extraction of Pu activity can be achieved using HGMS (represents
decontamination levels of three orders of magnitude to about 4.4 x 10s
dpm/L). The application of this technology to radioactive liquid waste efflu-
ents would eliminate radioactivity from the source, in addition reducing the
volume of transuranic solid waste that is produced with the current treatment
technologies. The hazard of pumping radioactive liquid waste to offsite facil-
ities would also be eliminated because treatment of TA-55 effluent would
occur prior to transportation.
Los Alamos
National
Laboratory
A Microwave Oven Dissolution Procedure for a Ten Gram, Sampk
of Soil Requiring Radiochemical Analysis
A microwave soil dissolution procedure was incorporated into a standard
analytical method for testing soils for americium and plutonium. This modi-
fication displaces several hot plate dissolution steps by incorporating a
microwave oven with new commercially available products. The new pro-
cedure uses a commercially available microwave oven that has the capabili-
ty to monitor and control the pressure and temperature of a control vessel
using a feed back system. The ability to repeatedly obtain and control
desired temperatures and pressures has resulted in improved analytical pre-
cision because the reaction conditions can be reproduced. This new proce-
dure also reduces the consumption of hazardous substances, the amount of
Los Alamos
National
Laboratory
31
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DuPont Company
Nalco Fuel Tech
air pollution produced, worker exposure to hazardous substances, and sam-
ple preparation time. The use of closed vessels in this modified procedure
also results in reduced hazardous reagents use. Less reagents means less haz-
ardous waste and air pollution are produced, and reduced worker exposure
to the reagents. In addition, die use of the microwave oven reduces the time
requirements from two to three days for the hot plate procedure to eight
hours.
NAFION Membrane Technology
Membrane technology is now recognized as the state-of-the-art for chlo-
ralkali chemical production, which constitute the second largest commodity
chemical volume produced globally. NAFION membranes are acknowl-
edged as the world leader in bringing about a technology "revolution," which
has made the membrane electrolyzer system the technology of choice over
the incumbent mercury amalgam cells and asbestos diaphragm electrolyzers.
While significantly reducing the environmental impact of the old technolo-
gies, membrane systems confer the advantages of a new electrolysis process
with lower investment and lower operating costs. Before NAFION and
membrane technology, the production of chloralkali chemicals was depen-
dent on either mercury amalgam cells or asbestos diaphragm systems. While
these systems may be operated safely, they pose health and environmental
concerns in use and disposal. Membranes, such as NAFION, now offer a
more environmentally-friendly and economically attractive alternative,
which accounts for the rapid global adoption of membrane technology.
Another rapidly emerging application of NAFION is in the area of alterna-
tive energy, where electricity is produced from the "combustionless burning"
of hydrogen with oxygen in air via a membrane fuel cell. Fuel cell technolo-
gy, with hydrogen as a fuel, is pollution-free. NAFION membranes often are
cited in the many commercial developments of membrane fuel cell systems.
As membrane fuel cells mature in the commercial mass market, more glob-
al energy needs will be served by renewable, sustainable, and environmen-
tally-friendly sources of power.
Nalco Fuel Tech NOxOUT® Process
Nalco Fuel Tech is a joint venture of Nalco Chemical Company and Fuel
Tech formed to develop and market air pollution control technologies. Nalco
Fuel Tech's flagship technology, NOxOUT®, selectively reduces harmful
nitric oxide emissions from the flue gases of stationary combustion sources
to yield nitrogen gas and water, leaving no solid residue requiring disposal.
The NOxOUT® Process meets many of today's environmental challenges
such as employing less toxic chemistries, reducing or eliminating toxic
releases to the environment, converting wastes to more environmentally
acceptable discharges, and by using these chemistries, enables reduced ener-
gy consumption. The NOxOUT® Process provides an economical solution
for meeting the stringent regulatory requirements for NO* reduction from
fossil fuel and waste fuel combustion sources. NOxOUT® is capable of pro-
viding up to 75 percent reduction of NO* emissions (existing combustion
32
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modification such as low NO* burners, flue gas recirculation, and overfire air
are effective, yet normally only provide NO* reductions in the range of 20 to
50 percent). The process uses chemicals and sophisticated injection equip-
ment to convert NO* to harmless species - nitrogen and water. In the
NOxOUT* Process, an aqueous solution of proprietary chemicals is intro-
duced into the flue gas of the combustion equipment. The program is
designed according to the type, size, and operating load of the boiler, and
NO* reduction required. The NOxOUT® Process is being used commercial-
ly and has been demonstrated in tests on a wide range of combustion
processes and fuels. The process is well-suited to new combustion units of all
sizes - from small industrial units to large utility installations. In addition, the
system can be retrofitted to most existing units. The environmental benefits
are: high NO* reduction, no disposal by-products, no SARA Title III chem-
ical reporting requirements, and increased energy efficiency due to the low
cost per ton to remove NO*.
New, stricter NPDES discharge limits for effluent metals are impacting
both metal and non-metal industries. Stringent NPDES plant effluent metal
concentration limits focus on effluent toxicity reductions that impact both
metal and non-metal industries. Traditional metal removal programs use
multiple chemicals and toxic components such as dialkyldithiocarbamates,
sodium sulfide, and ferrous sulfide. In addition, the concentration limits for
heavy metals such as copper, lead, nickel and zinc often cannot be met by
traditional metal precipitation processes. Nalco Chemical Company devel-
oped NALMET®, a patented, low-toxicity program for metal removal that
includes a liquid polymer containing a metal chelating functional group that
simultaneously precipitates metals and clarifies the waste stream. It is effec-
tive on soluble, mixed metal wastes and in many cases, reduces final sludge
volumes by 30 to 75 percent. NALMET® also allows some RCRA hazardous
sludges to be reclassified as non-hazardous. Automated chemical feed with
patented sensor technology makes the NALMET® program easier to use,
substantially decreases product overfeed, and assists with waste minimiza-
tion. More significantly, this product offers a remedy to environmental man-
agement problems by helping Nalco customers consistently meet their
extremely low NPDES metals discharge limits. NALMET® offers a realistic
J o
approach to "green" chemistry because the technology is based on high mol-
ecular weight polymers that express low toxicity, is easy to implement, does
not require extensive changes in plant design or capital investment, and is
broadly applicable and readily transferrable to other industry sectors.
Nalco Chemical
Company
Nalco PORTA-FEED® Advanced Chemical Handling Systems
Nalco Chemical Company is a manufacturer and marketer of specialty
chemicals for industrial water treatment and process applications. In the
early 1980s, drum disposal and the associated chemical residue was becom-
ing a health and environmental risk for Nalco customers and the general
public. In response, Nalco developed the PORTA-FEED® Advanced
Chemical Handling System consisting of returnable containers to help
Nalco Chemical
Company
33
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reduce chemical waste and the potential risks associated with non-returnable
drums. The Nalco PORTA-FEED* System has more than 96,000 returnable,
stainless steel containers of various sizes, ranging from 15 gallons to 800 gal-
lons to accommodate all Nalco customers and applications. It is the largest
fleet of returnable chemical containers in the world. All the units are owned,
tracked and maintained by Nalco as a cradle-to-grave risk management
process. Since it began, the PORTA-FEED* pollution prevention program
has helped Nalco customers eliminate the need to dispose more than three
million drums and more than 30 million pounds of chemical waste. In 1985,
33 percent of the Company's annual sales were shipped in non-returnable
drums and required 500,000 drums. Ten years later, only 7 percent of sales
are shipped in non-returnable drums and the number of drums has been
reduced 80 percent. By the year 2000, Nalco expects to have eliminated the
need to dispose of 10 million drums and 100 million pounds of chemical
waste worldwide as a result of the PORTA-FEED* program. The
PORTA-FEED® System provides several benefits both to users of Nalco
chemicals and to the environment, which includes eliminating drums, the
associated residual chemicals, and long-term environmental risk; reducing
the likelihood of spills, leaks, and container damage during transportation
and use; simplifying chemical handling, which enhances worker safety by
reducing exposure; and reducing the need for on-site chemical inventory
and chemical storage.
Nalco Chemical
Company
Nalco Technology
Nalco Chemical Company is the largest water treatment specialty chemi-
cal company in the world. Customers range from water treatment plants in
large industrial complexes that produce commodities such as steel, electrici-
ty, paper, gasoline, and fertilizer to smaller water facilities in hotels, hospi-
tals, breweries, canneries, and public sewage treatment facilities. Nalco
programs such as TRASAR* Technology, Diagnostic TRASAR®, and
TRA-CIDE™ are impacting the way the world manages water by helping
customers reduce pollution at its source and conserving energy. These appli-
cations are a complete cradle-to-grave approach to water management.
TRASAR® Technology has several aspects that can be grouped in "stages"
for discussion. In stage I, an inert fluorescent material "trace" is blended into
TRASAR® treatment products. The signal from the "trace" is used to control
the treatment chemical application and injection rate changes are made
instantaneously and automatically. It is common to see a 20 to 30 percent
reduction in total chemicals used when customers convert to a TRASAR®
program. Stage II of TRASAR* Technology relies on the direct, automatic
detection of the treatment chemical. Where stage I might be analogous to
adding microscopic, glowing ping-pong balls to the chemical product, stage
II is like putting a bar code on the active ingredient molecule. Nalco has
taken fluorescent materials and chemically bonded them to the active ingre-
dients. Stage II TRASAR® Technology allows Nalco to correlate variations
in the consumption of the chemical with variations in the way the water sys-
tem is operated. Stage III TRASAR® Technology is based on performance
(e.g. corrosion protection, prevent foaming, etc.). Nalco monitors how well
its products inhibit corrosion, disperse suspended solids, and prevent foam-
ing. The dosage is further adjusted based on the performance measures.
34
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Nalco ULTIMEK™ Polymer
Most industrial processes use water as a raw material or as a processing
aid. Typically, water taken from the environment must be conditioned to
remove suspended solids, organic matter, and other materials that may be
harmful to die industrial process before it is used. Water that has been used
in industrial processes often must be treated to remove harmful wastes and
contaminants before being reintroduced to the environment. Solids/liquids
separation unit operations are critical to cost-effective and safe operation of
most industrial operations. High molecular weight, water-soluble polyacry-
lamides are commonly used to assist solids/liquids separation in many indus-
trial water and waste treatment applications. In 1995, shipments of
polyacrylamides in the United States are expected to be over 200 million
pounds. Worldwide, the market for polyacrylamides is presently at least one
billion dollars. As flocculants, these polyacrylamides are extremely effective.
The last major technical improvement in flocculant technology might be
considered the invention and development of inverse emulsion polymers by
Nalco Chemical Company in the late 1970's. In 1995, Nalco continued its
technological innovation in this area by introducing the first major innova-
tion in water treatment flocculants since the development of inverse emul-
sion cationic polyacrylamides-ULTIMER™ polymers. ULTIMER™
polymers are a new product line of high molecular weight cationic poly-
acrylamides that are formulated without oils or surfactants. ULTIMER™
Polymer technology is more effective in purifying industrial processes and
wastewater than traditional technology and eliminates toxic components and
has worldwide applicability in all industrial nations. Its toxic use reduction
and pollution prevention is achieved by eliminating environmental dis-
charges that present environmental hazards.
Nalco Chemical
Company
New Catalyst for Producing ULTEM* Thermoplastic Resin
GE Plastics produces an engineering thermoplastic known as ULTEM™
polyetherimide resin. The production of this resin involves several compli-
cated synthetic conversions and generates both an aqueous waste stream
containing organic materials and an organic waste stream. The key step in
the process depends on a catalyst that has been a research "target of oppor-
tunity" for several years. Laboratory studies indicated that the amount of
waste generated from this step could be significantly reduced using several
members of a new catalyst class. A small plant trial verified the early find-
ings. In 1995, the most promising member of this new catalyst class was
streamlined, and a full plant trial was conducted in the ULTEM® manufac-
turing plant. Based on the full plant trial, the following pollution prevention
benefits were demonstrated: the volume of organic waste stream for off-site
disposal was reduced by 90 percent or 123,000 pounds a year; the water-
based organic waste for on-site thermal oxidization was reduced by 60 per-
cent or 300,000 pounds a year; 50 percent less catalyst was consumed due to
greater effectiveness per pound of catalyst; the amount of waste from the
manufacture of the catalyst itself was reduced by 75 percent or 39,000
pounds a year; the amount of energy required to produce each pound of the
resin was reduced by 25 percent or 5 x 109 BTU/yr; and the amount of a
workplace hazardous by-product was reduced by 90 percent. In addition to
GE
(General Electric
Corporation)
35
-------
CTS Corporation
Networks
Technic, Inc.
U.S. Department of
Energy
Lawrence Livermore
National Laboratory
these health and environmental benefits, the new catalyst system also offers
several significant economic advantages. This catalyst technology is the cor-
nerstone of new process chemistry for manufacturing the ULTEM® resin that
will eliminate completely the need for a thermal oxidizer.
No-Clean Soldering
CTS Corporation Resistor Networks produces solid ceramic resistor net-
works in various single in-line, dual in-line, surface mount, and through-hole
packages with standard or custom circuit designs. Soldering operations were
a major source of hazardous waste generation at CTS's Berne facility. Oil on
top of the solder, flux, and cleaning solvents to remove the oil after solder-
ing, generated large quantities of hazardous waste. A solder process, new to
CTS, was developed and implemented on all manufacturing lines. The No-
Clean soldering process was implemented in March of 1993 and eliminated
the use of wave oil, soldering fluxes, and cleaning solvent. Changing to a No-
Clean soldering process involved installing hoods with an inert atmosphere
over the solder pots, which eliminated the need for oil and flux. The parts
are clean after solder and thus no solvent cleaning is needed. In 1992, waste
generated from CTS's soldering operations included 21,767 pounds of wave
oil; 15,792 pounds of flux; 9,900 pounds of 1,1,1-trichloroethane solvent
(TCA); and 226,000 pounds of 1,1,2-trichloroethylene solvent (TCE). In
1995, waste oil, flux, TCA, and TCE from soldering operations was com-
pletely eliminated. The elimination of solvent-based cleaning operations also
has resulted in a reduction in air emissions from 1992 levels of 99,000
pounds per year of TCA and 250,000 pounds per year to zero (estimated for
1996). By eliminating these chemicals from soldering operations, the hazards
from releasing these chemicals to the environment is eliminated and work-
ers are no longer exposed to fumes from fluxes, oils, and cleaning solvents
that are typical of the solvent-based soldering operations. In addition, the
product quality has improved.
Non-Cyanide Silver Electroplating
A proprietary, non-cyanide silver electroplating process, Techni-Silver
Cy-Less L, was developed by Technic. Cyanide based processes for electro-
plating have been extensively used in the United States for the last fifty years.
Due to the hazardous nature of cyanide, extensive safety precautions must be
incorporated when manufacturing electroplating chemicals, transporting die
solutions to user sites, using the electroplating process, and disposing waste
solutions. For example, if cyanide based solutions become too acidic, large
amounts of poisonous cyanide gas are created. Historically, the electroplating
industry has suffered many accidents due to the use of cyanide and on a few
occasions have resulted in death. Alternatives to cyanide-based solutions had
been developed for all metals commercially electroplated except silver. The
non-cyanide silver electroplating process developed by Technic provides an
alternative that is noticeably less toxic than the cyanide process and one that is
inherently safer with regard to accident potential. In addition, tests clearly
show that the non-cyanide formulation is capable of producing sound, thick
(around 125 pm) silver deposits that are extremely fine-grained and exhibit
36
-------
properties comparable to those produced in silver cyanide formulations. With
the success of the non-cyanide chemistry, Technic has made it possible to oper-
ate an entire plating facility without having to use any cyanide compounds.
Poly carbonate/Poly dimethylsiloxane Copolymers for
Thermal Print Media
The process to make polycarbonates using bischloroformat.es and bisphe-
nols or diols was developed and commercialized in the early 1990's by the
Polymer Products Unit of the Eastman Kodak Company in Rochester, New
York. The original process to produce the polycarbonate of bisphenol A,
dietliylene glycol, and bisaminopropyl polydimethyl-siloxane was developed
in 1992 and commercialized in 1993 for use in a new Thermal Print Media
product. Concerns over waste and air emissions, as well as cost and capacity
issues, prompted a research and development effort to replace this polymer
before production volumes increased to forecasted high levels. The new
process to produce a similar polycarbonate/polydimethylsiloxane copolymer
was certified early in 1994. Improvements include the following: (1) the new-
process is made in the solvent in which the polymer is coated, and is deliv-
ered to the manufacturing department dissolved in that solvent, eliminating
the methanol precipitation, methanol washing, and vacuum drying steps; (2)
in the new process, triethylamine is used as the acid acceptor instead of pyri-
dine, making the water wash waste streams less hazardous; (3) the new
process uses the commercially available diethylene glycol bischloroformate,
eliminating the need to manufacture the bisphenol A bischloroformate at
Kodak in Rochester (the bisphenol A bischloroformate synthesis uses phos-
gene as a key reactant, and its purification produces large quantities of haz-
ardous waste containing heptane and silica gel). The new process will yield
over 1.2 million pounds of hazardous waste reductions and more than 3,000
pounds of air emissions reductions from 1994 to year end 1996.
Kodak
Company
The Removal of Oxides of Nitrogen by In Situ Addition of
Hydrogen Peroxide to a Metal Dissolving Process
An innovative technology for the removal of oxides of nitrogen (NO*) in
a metal dissolving process by adding hydrogen peroxide was developed and
implemented by Mallinckrodt. Salts are produced by dissolving metals in
nitric acid and during the dissolving process, approximately 30 tons per year
of NOx emissions are generated. A study was completed to determine the
best method for reducing NO* emissions from the process. While the litera-
ture suggests that NO* is required to catalyze the dissolution reaction, this
theory was challenged and it was proposed to oxidize the NO* back to nitric
acid by adding hydrogen peroxide directly to the process. Trial runs using
this technology were completed and resulted in complete elimination of NO*
emissions. The full scale hydrogen peroxide addition process has eliminated
the generation and evolution of approximately 30 tons per year of gaseous
NOx waste, while at the same time reducing nitric acid usage by approxi-
mately 109 tons per year. Further, approximately 13 million gallons of scrub-
ber waste water were eliminated annually since the scrubber, traditionally
Mallinckrodt
Chemical, Inc.
37
-------
Monsanto Company
Los Alamos National
Laboratory
used by the chemical industry to control the NO* that is generated and
released from reactions, is no longer needed. This technology can be used by
any process in any industry that generates NO* emissions when dissolving-
metals in nitric acid or pickling metals using nitric acid.
Roundup Ready™ Technology
The Roundup Ready™ Technology is the mechanism by which crop
selectivity to Roundup*, the world's largest selling herbicide, has been intro-
duced into crop plants. The technology is the result of the discovery of a
unique set of genes and the introduction of these Roundup Ready™ genes
into crop plants. These genes were identified following many years of
research on the mode of action and environmental fate of die active ingredi-
ent of die Roundup® herbicide. The Roundup Ready™ Technology genes
protect the crop plant from damage by inserting a new version of the
enzyme, which is normally inhibited by the herbicide, so that the enzyme is
now insensitive to the herbicide. In addition, the Roundup Ready™
Technology provides a mechanism for die plant to degrade the herbicide
taken into the plant. Initial commercial launch will be in soybean, cotton,
and corn in the United States in the 1996-1998 time frame. The technology
is widely applicable to other crops. Potential applications include wheat, rice,
forestry, and vegetable and salad crops. This technology extends to a wider
aspect of agriculture and food production, the ability to use one of the most
beneficial and environmentally benign farm chemicals ever discovered. The
impacts will be seen in die shift in die spectrum of herbicides possible for in-
crop use. Farmers who plant Roundup Ready™ soybeans in 1996, for exam-
ple, will be able to reduce herbicide use in those soybean fields by up to
one-third and still control weeds better. In addition, Roundup Ready™ tech-
nology is compatible with no-till crop production, a practice that is expand-
ing in the United States and around the world.
Solvent Replacement and Improved Selectivity in Asymmetric
Catalysis Using Supercritical Carbon Dioxide
The use of supercritical carbon dioxide as a substitute for organic solvents
already represents an important tool for waste reduction in die chemical
industry and related areas. Coffee decaffeination, hops extraction, and essen-
tial oil production as well as waste extraction/recycling and a number of ana-
lytical procedures already use this nontoxic, nonflammable, renewable, and
inexpensive compound as a solvent. The extension of this approach to chem-
ical production, using COa as a reaction medium, is a promising approach to
pollution prevention. Of die wide range supercritical carbon dioxide reac-
tions that have been explored, one class of reactions has shown exceptional
promise. Los Alamos National Laboratory has found that asymmetric cat-
alytic reductions, particularly hydrogenations and hydrogen transfer reac-
tions, can be carried out in supercritical carbon dioxide with selectivities
comparable or superior to diose observed in conventional organic solvents.
Los Alamos has discovered, for example, that asymmetric hydrogen transfer
reduction of enamides using ruthenium catalysts proceeds with enantiose-
lectivities that exceed those in conventional solvents. The success of asym-
38
-------
metric catalytic reductions in CO is due in part to several unique properties
of CO including tuneable solvent strength, gas miscibility, high diffusivity,
and ease of separation. In addition, the insolubility of salts, a significant lim-
itation of CCfe as a reaction solvent, has been overcome by using lipophilic
anions, particularly tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BARF).
These discoveries demonstrate an environmentally benign and potentially
economically viable alternative for the synthesis of a wide range of specialty
chemicals such as pharmaceuticals and agrochemicals.
Stepan Company PA Lites Polyester Polyol
Stepan Company's Polyester Polyol product, manufactured using the
Phthalic Anhydride Process Light Ends (PA Lites), uses a previously catego-
rized waste as a raw material in its manufacture, thereby eliminating the
material's disposal via incineration. This Polyester Polyol is the basic raw
material for manufacture of various types of insulating wallboard used in the
home construction and commercial building industry. By substituting tradi-
tional raw materials with PA Lites, Stepan Company is providing the con-
struction industry and consumer a cost effective alternative to traditional
building construction products. Using the phthalic anhydride distillation by-
product as a raw material for the polyol process eliminates an entire waste
stream. In 1994, 235,300 pounds of Phthalic Anhydride Light Ends was used
as a feedstock and 454,420 pounds were shipped out as a waste for fuel
blending. In 1995, approximately 700,000 pounds of PA waste were used as
a feedstock in the polyol process, thus eliminating an estimated 350 tons per
year of organic waste material. Benefits from this product substitution go
beyond eliminating a waste requiring disposal. With its substitution as a raw
material, it has reduced the requirement for phthalic anhydride, the tradi-
tional raw material for the polyol product, and the air emissions associated
with its manufacture. Since this previously categorized waste material is now
used on-site to produce Polyester Polyol, potential exposure to the general
public during off-site transportation to disposal facilities has been eliminated.
This technology also provides significant cost savings. The savings associat-
ed with the transportation and disposal via fuel blending for energy recovery
is expected to be $200,000 per year. The raw material savings due to the
replacement of pure PA with PA lites material on a pound per pound basis
is $20,000 per year.
Tetrakishydroxymethyl Phosphonium Sulfate (THPS) Biocides
The United States industrial water treatment market for non-oxidizing
biocides is 40 million pounds per year and growing at six to eight percent
annually. Tetrakishydroxymethyl phosphonium sulfate (THPS) biocides rep-
resent a completely new class of antimicrobial chemistry that combines supe-
rior antimicrobial activity with a relatively benign toxicology profile. THPS
provides a reduced risk to both human health and the environment when
substituted for more toxic biocides. The human and environmental health
risks of THPS have been compared with other biocides that currently com-
prise an estimated 80 percent of the U.S. industrial water treatment market.
THPS poses much less risk to the environment than many of the alternative
Company
Albright & Wilson
Americas Inc.
39
-------
U.S. Department of
Energy
Los Alamos National
Laboratory
Professor
Jonathan Phillips,
Department of
Chemical
Engineering,
Pennsylvania
University
U.S. Department
of the Navy,
of
Research
U.S. Department
of the Navy,
Naval Surface
Warfare Center
products currently on the market. THPS biocides are aqueous solutions and
do not contain VOCs; they are also halogen-free and do not contribute to
dioxin or AOX formation. THPS does not bioaccumulate and can rapidly
breakdown through hydrolysis, oxidation, biodegradation, and photo-degra-
dation before it enters the environment. The degradation products have
been shown to be non-toxic. THPS is also the only biocide, compared to
high volume alternatives, for which the typical dose rate is below the LC50 for
fish. Because of its low overall toxicity when compared to alternative prod-
ucts, THPS provides an opportunity to reduce the risk of health and safety
incidents.
Two-Stage Catalyst for NO* Reduction, CO Oxidation, and
Hydrocarbon Combustion in Oxygen Containing
Exhaust Mixtures
A unique catalyst system has been developed for removing oxides of
nitrogen from automobile exhaust. These catalysts operate in a lean burn
environment (excess oxygen in the engine) and represent a significant
improvement over existing technologies. Automobile manufactures prefer to
operate engines with excess oxygen to completely combust the fuel, improve
efficiency, and reduce pollution. The principle impediment to designing such
an engine is the inability of existing exhaust system catalysts to reduce oxides
of nitrogen in the presence of oxygen. Some progress has been made in
resolving this problem, specifically, copper impregnated zeolites are found to
reduce oxides of nitrogen in the presence of oxygen. This material is not,
however, without problems, including, low conversion of the oxides of nitro-
gen. We have demonstrated a two stage catalysts system that significantly
improves the conversion of oxides of nitrogen to environmentally acceptable
gases. We have shown that a heterogeneous catalyst system consisting of two
beds in sequence, each containing a different catalytic material, is superior
for the removal of NO* from exhaust streams containing oxygen, to the cur-
rent generation of single stage catalysts. The character of each of the catalyst
beds is fairly specific. The first bed consists of any high surface area refrac-
tory oxide such as silica, alumina, titania, zirconia, ceria, zeolite, etc. The sec-
ond bed consists of any metal loaded catalytic material known to reduce NOx
species in the presence of oxygen such as copper exchanged zeolite (e.g. Cu-
ZSM-5). Many other materials, including zeolites exchanged with other met-
als, high surface area silica or alumina impregnated with metals, also are
known to reduce NOx species in such environments, and thus also are can-
didates for second bed materials.
Use of Carbon Dioxide as an Alternative Green Solvent for the
Synthesis of Energetic Thermoplastic Elastomers
Thermoplastic elastomers based on triblock oxetane copolymers contain-
ing azido functional groups offer an improved binding material for solid,
high energy formulations. Current technology uses chemically cross-linked
energetic prepolymer mixes that introduce the problems of thermally labile
chemical linkages, high end-of-mix viscosities, and vulnerability to prema-
40
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tare detonation. These materials are also nonrecyclable and generate large
amounts of pollution during disposal. The use of energetic thermoplastic
elastomers eliminates the need for chemical cross-linking agents, makes pro-
cessing easier due to their low melt viscosities, and eliminates the need for
solvents during casting. Their superior processing qualities and the ease of
demilitarization and recycling make these materials a much more environ-
mentally sound choice for energetic binders. However, their synthesis still
involves the use of large quantities of toxic chemicals such as methylene chlo-
ride as solvents. Carbon dioxide has been proven to be a viable, environmen-
tally responsible replacement solvent for many synthetic and processing
applications. It is cheap, easily recyclable, and available from current sources.
Research at the University of North Carolina has shown that carbon dioxide is
a viable solvent for the polymerization of vinyl ether monomers. Furthermore,
polyoxetanes can be polymerized in carbon dioxide with molecular weight,
molecular weight distribution, and functionality maintained. The University of
North Carolina has demonstrated the synthesis of both nonenergetic and ener-
getic homopolymers and random copolymers.
The Use of Chlorine Oxide, the Foundation of Elemental
Chlorine-Free Bleaching for Pulp and Paper, as a Pollution
Prevention Process
The use of chlorine dioxide as part of a pollution prevention process to
substantially or completely replace chlorine in the first stage of chemical pulp
bleaching is a unique implementation of chlorine dioxide chemistry. It can be
applied to the entire bleached chemical pulp and paper industry, both in the
United States and abroad. By employing raw material substitution and
process modifications, this technology has allowed the pulp and paper indus-
try to meet the source reduction objectives of the Pollution Prevention Act of
1990. With this new application of sophisticated chlorine dioxide chemistry,
the pulp and paper industry virtually eliminated dioxin from mill waste
waters and our nation's water bodies. This technology has answered the
industry's calls for a more benign chemical pulp bleaching agent. Virtual
elimination of dioxin from mill waste waters and continuing nationwide eco-
system recovery provide a strong measure of chlorine dioxide's success and
the industry's environmental progress. In fact, downstream of U.S. pulp mills
bleaching with chlorine dioxide, fish dioxin body burdens have declined
rapidly and aquatic eco-systems continue to recover. For example, the Mead
Paper Company's Escanaba Mill in Michigan implemented pollution preven-
tion strategies beginning with the use of low precursor defoamers in 1989, fol-
lowed by increased substitution of chlorine by chlorine dioxide in 1990. In
less than four years, downstream dioxin body burdens declined more than 90
percent. These indicators of progress toward broader eco-system integrity
demonstrate the success of chlorine dioxide as "green chemistry."
Professor
Joseph DeSimone,
Department of
Chemistry,
University of North
Carolina
Aerojet Propulsion
Alliance for
Environmental
Technology (AET)
41
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Lockheed Martin
Tactical Aircraft
Systems
Merck & Co., Inc.
Use, Regeneration, and Analysis of Aqueous Alkaline Cleaners
Lockheed Martin Tactical Aircraft Systems (LMTAS) was the first aero-
space company to implement innovative aqueous cleaning technology for
cleaning tubing and honeycomb core. Tubing is used in the aerospace indus-
try for transferring pressurized oxygen within an aerospace vehicle.
Honeycomb core is used in the aerospace industry for producing bonded
structural parts. Both applications require that the parts meet stringent clean-
liness requirements. These requirements were previously met by using cold
cleaning and/or vapor degreasing with chlorinated solvents such as 1,1,1-
trichloroethane (TCA) and trichloroethylene (TCE), both of which are toxic
and ozone depleting compounds. These solvents have been successfully
replaced with LMTAS' aqueous cleaning technology. Since May of 1994, 100
percent of both tubing and honeycomb core manufactured at LMTAS have
been cleaned using the aqueous cleaning technology. Coulometric titration
data indicates that the LMTAS aqueous cleaning technology is as effective or
more effective than TCE vapor degreasing for cleaning aluminum tubing and
honeycomb core. In addition, implementation of the aqueous cleaning tech-
nology at LMTAS has eliminated approximately 360 tons of air emissions per
year and has resulted in a cost savings of $490,000 per year. LMTAS also has
explored the use of environmentally safe methods for quantifying surface con-
taminants on parts cleaned by various cleaning technologies. Traditionally,
extraction with CFC-113 followed by gravimetric or FTIR analysis has been
/ o J
used for quantifying contaminants. LMTAS has demonstrated the usefulness
of carbon dioxide coulometry for determining the amount of residue remain-
ing on a surface after cleaning and has used this technique for comparing the
cleaning effectiveness of various cleaning technologies. Finally, LMTAS has
demonstrated that ultrafiltration is a viable technology for the regeneration of
aqueous cleaners for reuse. Regeneration of aqueous cleaners can greatly
reduce replacement and disposal costs.
Waste Minimization in the Manufacture of an Antibiotic Produced
by Chemical Synthesis
PRIMAXIN is an injectable, broad-spectrum antibiotic commercialized in
1985. Development and implementation of an effective manufacturing
process for PRIMAXIN was an immense challenge due in part to the com-
plexity of the imipenem molecule and instability. The manufacturing process
initially proposed for PRIMAXIN involved 18 steps and would have created
one ton of waste for every pound of product. While still in the development
lab, however, Merck's chemists and engineers found a way to eliminate
500,000 gallons of annual toxic waste. After production began, Merck con-
tinued to improve the process by eliminating a mixture that prevented sol-
vents from being reused, developing an innovative extractive hydrolysis
technology that improved yield, and reducing use of another solvent. For
example, one of the process steps involved the use of methyl isobutyl ketone
(MIBK) and acetonitrile. Process development work indicated that MIBK
could be eliminated. This allowed acetonitrile to be recycled, which previ-
ously was sent off-site for disposal. In a separation step, the number of cycles
between regeneration of a chromatographic column using acetone/sulfuric
acid was increased tenfold. These solvent recovery opportunities resulted in
42
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an annual savings of $50,000. Even after PRIMAXIN was in full scale man-
ufacturing, several waste minimization process modifications were imple-
mented that resulted in dramatic waste load reductions. The most significant
is the 82 percent reduction in the use of methylene chloride by eliminating
materials that made methylene chloride recovery impractical, modifying
processes to allow the use of recovered material, and improving recovery
techniques. This dramatic waste reduction resulted in an annual savings of
over $1 million, and the process is still undergoing modification in order to
further reduce waste generation. Development, implementation, and ongoing
improvement of the process to manufacture PRIMAXIN (imipenem) is a
prime example of Merck's contribution to the promotion of environmentally
benign technology.
Waste Reduction in the Production of an Energetic Material by
Development of an Alternative Synthesis
1,3,3-Trinitroazetidine (TNAZ) is a promising new melt-castable explosive
that has significant potential for providing environmental benefits and capa-
bility improvements in a wide variety of defense and industrial applications.
Initial life-cycle inventories on various munitions revealed that up to 50 per-
cent of the life-cycle pollution burden was associated with the demilitarization
of the munitions, and in particular, the use of thermoset polymeric binders
that require removal with water jet cutting. TNAZ is the only energetic mate-
rial other than trinitrotoluene (TNT) that can be melt-cast in existing TNT
loading plants. Demilitarization of TNAZ simply requires heating the device
above the melting point and pouring the liquid out, rattier than the compli-
cated and destructive methods used for RDX- and HMX-based plastic-bond-
ed explosives. The stability of TNAZ in the melt allows it to be easily
recycled. TNAZ has performance slightly greater than that of HMX, the most
powerful military explosive in current use. Thus, TNAZ may offer 30-40 per-
cent improvements in performance as a replacement for TNT-based formula-
tions such as Composition-B. The alternative synthesis of TNAZ developed at
the Los Alamos National Laboratory allows TNAZ to be produced in a waste-
free process that also eliminates the use of halogenated solvents. This alterna-
tive synthesis produces 5.3 pounds of waste per pound of product compared
to the original synthesis of TNAZ which produces 1200 pounds of waste per
pound of product. The alternate technology has been transferred to industry,
where it has been scaled up to production-plant quantities. Further improve-
ments in waste reduction have been demonstrated in the laboratory that may
eventually lead to a process giving little more waste than one pound of salt
per pound of TNAZ.
Water-Dispersible Sulfopolyester for Reduced VOC
Consumer Products
The reduction of airborne emissions is a major focal point for legislation
to safeguard public health. Volatile organic compounds (VOCs) are one of
the major sources of air pollution that arise from both consumer and indus-
trial products. Legislation proposed at the state level, particularly in
U.S. Department
of the Navy,
Office of Naval
Research
U.S. Department
of the Navy,
Naval Surface
Warfare Center
U.S. Army
Armament
Research,
Development
and Engineering
Center
Los Alamos
National Laboratory
Aerojet
Eastman Chemical
Company
43
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California, is targeting consumer and personal care products for VOC con-
tent reductions. One of the largest product areas is in hairsprays, which a
very large, diverse segment of the population uses daily. Consumers, how-
ever, demand that "green" products have the same if not better performance
characteristics. Eastman Chemical Company has developed a new product,
known as EASTMAN AQ^ 48 Ultra, for this general need that not only
reduces VOCs, but actually may improve performance. EASTMAN AOw48
Ultra is a water-dispersible sulfopolyester that allows hairsprays to be for-
mulated with 55 percent ethanol, which is significantly less than the current
industry standard of 80 percent VOC. Switching all of the hairspray market
from the current standard of 80 percent VOC to 45 percent VOC would
result in a total reduction of VOC emissions around 55 million pounds per
year. In general, sulfopolyester dispersions may be used as low VOC film-
formers for a variety of cosmetic products in addition to hairsprays; there-
fore, an even larger potential for VOC emission reduction exists. Finally, the
process chemistry is completed in the melt phase. There are no organic sol-
vents used in the synthesis of sulfopolyesters at Eastman Chemical
Company. The synthesis also does not release any toxic by-products.
The Green Chemistry Challenge is a voluntary program that operates
through a broad consortium that includes members of the chemical indus-
try, trade associations, scientific organizations, and representatives from
academia. The program is open to all individuals, groups, and organiza-
tions involved in chemical design, manufacture and use.
Additional Information about the Green Chemistry Challenge is avail-
able from EPA's homepage on the internet (http://www.epa.gov; select
"Offices," then "Prevention, Pesticides, and Toxic Substances," then
"Toxics") and from EPA's Toxic Substance Control Act Assistance
Information Service (202-554-1404; TDD: 202-554-0551), or call EPA's
Industrial Chemistry Branch at 202-260-2659.
44
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Index
Award winners are indicated with *.
Advanced Micro Devices (AMD), Austin Environmental Department
The Emission Quantification Model 27
Albright & Wilson Americas Inc.
Tetrakishydroxymethyl Phosphonium Sulfate (THPS) Biocides 39
Alliance for Environmental Technology (AET)
The Use of Chlorine Oxide, the Foundation of Elemental Chlorine-Free
Bleaching for Pulp and Paper, as a Pollution Prevention Process ........... .41
Altus Biologies Inc.
Cross-Linked Enzyme Crystal Technology 12
Anderson, Marc A., Water Chemistry Program, University of
Wisconsin-Madison
Green Technology for the 21st Century: Ceramic Membranes 9
Asarco Incorporated
Asarco — West Fork Biotreatment Project 20
Bayer Corporation
Aldimine-Isocyanate Chemistry: a Foundation for
Environmentally-Friendly High Solids Coatings 15
Benchmark Products, Inc.
of a Nickel Brightener Solution 13
BF Goodrich and Tremco, a BF Goodrich Company
Development of a New Sealant/Adhesive Chemistry for Automotive Windshields. A
New Two Part Chemical System Using Acetoacetylated Polyol Prepolymers and
Aminated Acetoacetylated Polyol Prepolymers 23
BHC Company (Hoechst Celanese Corporation)
The BHC Company Ibuprofen Process 21
Bureau of Engraving and Printing, Office of Research and
Technical Support
An Alternative Solvent, hornet 17
California-Pacific Lab & Consulting
The ECO Funnel 26
Circuit Research Corporation
A Non-Toxic, Non-Flammable, Aqueous-Based Cleaner/Degreaser and
Associated Parts Washing System Commonly Employed in
Automotive Repair Industry 15
45
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CTS Corporation Resistor Networks
No-Clean Soldering .36
DeSimone, Joseph, Department of Chemistry, University of
North Carolina at Chapel Hill, Air Products and Chemicals, Inc.
Soapy COi 11
*Donlar Corporation
* Production and Use of Thermal Polyaspartic Acid 5
*The Dow Chemical Company
*The Development and Commercial Implementation of 100 Percent
Carbon Dioxide as an Environmentally Friendly Blowing Agent for
the Polystyrene Foam Sheet Packaging Market .3
The Dow Chemical Company's Novel INVERT™ Solvents ............... .25
Du.in.esic, James A., Chemical Engineering Department, University
of Wisconsin and John C. Crittenden, National Center for Clean
Industrial and Treatment Technologies, Michigan Technological
University
Rational Design of Catalytic Reactions for Pollution Prevention 10
DuPont Company
The DuCare "Zero Effluent" Recycle Chemistry System .26
The INFINITY Dyeing Process .28
NAFIONMembrane Technology 32
Eastman Chemical Company
Water-Dispersible Sulfopolyester for Reduced VOC Consumer Products 43
Eastman Kodak Company
Polycarbonate/Polydimethylsiloxane Copolymers for
Thermal Print Media .37
GE Plastics (General Electric Corporation)
New Catalyst for Producing ULTEM* Thermoplastic Resin 35
Hatton, T. Alan, Department of Chemical Engineering,
Massachusetts Institute of Technology, and Stephen L. Buchwald,
Chemistry Department, Massachusetts Institute of Technology
Derivati^ed and Polymeric Solvents for Minimising Pollution during
the Synthesis of Pharmaceuticals 8
Hendrickson, James B., Department of Chemistry, Braedeis
University
The SYNGEN Program for Generation of Alternative Syntheses .11
Henkel Corporation, Emery Group
Alkyl Polyglycoside Surfactants 16
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*Holtzapple, Mark, Department of Chemical Engineering,
Texas A&M University
Conversion of Waste Biomass to Animal Feed, Chemicals,
and Fuels .7
Hudlicky, Tomas, Department of Chemistry, University of Florida
Enzyme-Assisted Conversion of Aromatic Substances to Value-Added End
Products. Exploration of Potential Routes to Biodegradable Materials and
New Pharmaceuticals 8
Hughes Environmental Systems, Inc.
DiyWasW 25
IBM-Austin
Elimination of Ozone-Depleting Chemicals in the Printed Wire Board and
Electronic Assembly and Test Processes 27
Innovative Techniques for Chemical and Waste Reductions in the Printed Wire
Board Circuittze Process .29
Lockheed Martin Tactical Aircraft Systems
Development and Implementation of Low Vapor Pressure Cleaning
Solvent Blends and Waste Cloth Management Systems to Capture
Cleaning Solvent Emissions 22
Use, Regeneration, and Analysis of Aqueous Alkaline Cleaners 42
Los Alamos National Laboratory
Application of Freeze Drying Technology to the Separation of
Complex Nuclear Waste ........................................ 18
Application of Green Chemistry Principles to Eliminate Air Pollution
from the Mexican Brickmaking Microindustry 19
Magnetic Separation, for Treatment of Radioactive Liquid Waste 31
A Microwave Oven Dissolution Procedure for a Ten Gram Sample of
Soil Requiring Radiochemical Analysis 31
Solvent Replacement and Improved Selectivity in Asymmetric Catalysis Using
Supercritical Carbon Dioxide . .38
Mallinckrodt Chemical, lee.
The Removal of Oxides of Nitrogen by In Situ Addition of Hydrogen
Peroxide to a Metal Dissolving Process 37
Merck & Co., Inc.
Waste Minimiyition in the Manufacture of an Antibiotic
Produced by Chemical Synthesis 42
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Molten Metal Technology, Inc.
Catalytic Extraction Processing ................................... 12
*Monsanto Company
*The Catalytic Dehydrogenation of'Diethanolamine 2
Roundup Ready™ Technology 38
Nalco Chemical Company
Nalco NALMET* 33
Nalco PORTA-FEED® Advanced Chemical Handling Systems ........... .33
Nalco TRASAR* Technology . .34
Nalco ULTIMER™ Polymer Technology .35
Nalco Fuel Tech
Nalco Fuel Tech NOxOUT* Process 32
Paquette, Leo A., Department of Chemistry, Ohio State University
Environmental Advantages Offered by Indium-Promoted Carbon-Carbon
Bond-Forming Reactions in Water .8
Pharmacia and Upjohn, Inc.
An Alternative Synthesis of Bisnoraldehyde, an Intermediate to
Progesterone and Corticosteroids .18
Praxair, Inc.
Liquid Oxidation Reactor 30
Reeombinant BioCatalysis, Inc. (RBI)
Development of a Biodiversity Search and Enzyme
Optimization Technology 13
Rochester Midland Corporation
Development of a New "Core" Line of Cleaners .22
*Rohm and Haas Company
* Designing an Environmentally Safe Marine Antifoulant .4
Invention and Commercialization of CONFIRM™ Selective
Caterpillar Control Agent 30
Sandoz Pharmaceutical Corporation
Development of a New Process for the Manufacture of
Pharmaceuticals . .23
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Shaw, Henry, Chemistry and Environmental Science Department,
New Jersey Institute of Technology and Dan Watts, Center for
Environmental Engineering and Science, New Jersey Institute of
Technology
The Replacement of Hazardous Organic Solvents with Water in the
Manufacture of Chemicals and Pharmaceuticals 10
Stanson Corporation
National Conversion to Low Sudsing Hand Dish Detergents for Industrial,
Institutional, and Especially Consumer Application. 14
Stepan Company
Stepan Company PA Lites Polyester Polyol 39
Taylor, Larry T., Department of Chemistry, Virginia Tech;
Virginia Tech Intellectual Properties
A Nontoxic Liquid Metal Composition for Use as a
Mercury Substitute 9
Technic, Inc.; U.S. Department of Energy; and Lawrence
Livermore National Laboratory
Non-Cyanide Silver Electroplating 36
Texaco Inc.
CleanSystem3 Gasoline .21
U.S. Department of Defense, Office of Munitions; U.S.
Department of Energy, Weapons Supported Research;
and Lawrence Livermore National Laboratory
Environmentally-Driven Preparation of
Insensitive Energetic Materials 28
U.S. Department of Energy, Office of Industrial
Technologies Programs
The Alternative Feedstocks and Biological and Chemical
Technologies Research Programs ................................... 17
U.S. Department of Energy, Office of Pollution Prevention,
DOE Office of Energy Research, DOE Chicago Operations
Office, DOE Argonne Group and Argonne National Laboratory
Application of Microchemistry Technology to the Analysis of
Environmental Samples 20
U.S. Department of Energy; Pacific Northwest National Laboratory
DOE Methods for Evaluating Environmental and
Waste Management Samples 25
U.S. Department of Energy; Los Alamos National Laboratory; and
Professor Jonathan Phillips, Department of Chemical Engineering,
Pennsylvania State University
Two-Stage Catalyst for NO* Reduction, CO Oxidation, and Hydrocarbon
Combustion in Oxygen Containing Exhaust Mixtures 40
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U.S. Department of the Navy, Office of Naval Research; U.S.
Department of the Navy, Naval Surface Warfare Center;
Professor Joseph DeSimone, Department of Chemistry,
University of North Carolina; and Aerojet Propulsion
Use of Carbon Dioxide as an Alternative Green Solvent for the
Synthesis of Energetic Thermoplastic Elastomers 40
U.S. Department of the Navy, Office of Naval Research; U.S.
Department of the Navy, Naval Surface Warfare Center; U.S. Army
Armament Research, Development and Engineering Center;
Los Alamos National Laboratory; and Aerojet
Waste Reduction in the Production of an Energetic Material by
Development of an Alternative Synthesis 43
Zeller International
Enviroblock Technology 14
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