United States
Environmental Protection
Agency
Pollution Prevention and
Toxics (7406)
EPA744-R-00-001
March 2000
www.epa.gov/greenchemistry
The Presidential
Green Chemistry Challenge
Awards Program
Summary of 1999 Award
Entries and Recipients
Printed on paper that contains at least 30 percent postconsumer fiber.
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The Presidential Green Chemistry
Challenge Awards Program
Contents
Summary of 1999 Award Entries and Recipients 1
Awards 3
Academic Award 3
Small Business Award 4
Alternative Synthetic Pathways Award 5
Alternative Solvents/Reaction Conditions Award 6
Designing Safer Chemicals Award 7
Entries From Academia 8
Entries From Small Businesses 28
Entries From Industry and Government 38
Index 76
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The Presidential Green Chemistry
Challenge Awards Program
Summary of 1999 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 established to "promote pollution prevention and indus-
trial 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 innovative chemical methodolo-
gies 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 chem-
istry principles into chemical design, manufacture, and use.
Entries received for the 1999 Presidential Green Chemistry Challenge Awards were
judged by an independent panel of technical experts convened by the 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 1999 awards and nationally recognized on
June 28, 1999-
This document provides summaries of the entries received for the 1999 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 methodologies and are recognized for
their beneficial scientific, economic, and environmental impacts.
Note: The summaries provided in this document were obtained from the entries received for the 1999
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 provided in the entries received and, as such, are intended to highlight the nom-
inated 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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Academic Award
TAML™ Oxidant Activators: General Activation of Hydrogen
Peroxide for Green Chemistry
Twenty years of research by Professor Terry Collins at Carnegie Mellon University has led
to the successful development of a series of environmentally friendly oxidant activators based
on iron. These TAML™ (tetraamido-macrocyclic ligand) activators catalyze the reactions of
oxidants in general. Their activation properties with hydrogen peroxide in water are of great-
est environmental significance. TAML™ activators arise from a design process invented by
Professor Collins which is complementary to that employed by Nature to produce powerful
oxidizing enzymes. The activators promise extensive environmental benefits coupled with
superior technical performance and significant cost savings across a broad-based segment of
oxidation technology. Users of TAML™ peroxide activators will range from huge primary
extractive-processing industries to household consumers throughout the world. In laborato-
ry tests, the Collins activators have shown this potential in the major industrial application
of wood pulp delignification and in the broad-based consumer process of laundry cleaning.
Annually, bleached pulp has a global value of approximately $50 billion. The key to qual-
ity papermaking is the selective removal of lignin from the white fibrous polysaccharides,
cellulose, and hemicellulose. Wood-pulp delignification has traditionally relied on chlorine-
based processes that produce chlorinated pollutants. It has been clearly demonstrated that
TAML™ activators can provide the Pulp and Paper Industry (P&PI) with the first low-tem-
perature hydrogen peroxide-based delignification technology for treating pulp. The new
process moves the elemental balance of pulp delignification closer to what Nature employs
for degrading lignin, a strategy reflected in the industry's recent development of totally chlo-
rine free (TCP) bleaching procedures. TAML™ activated peroxide delignification proceeds
rapidly and efficiently at 50 °C indicating that minimal capital will be required to retrofit
existing mills for its use. The new technology is more selective than any other TCP process
and, except at low lignin content, is as selective as the current dominating delignification
technology based on chlorine dioxide. These parameters show that the new technology can
significantly reduce persistent pollutants associated with chlorine-containing delignifying
agents by enabling the industry to use peroxide to remove the majority of lignin from kraft
pulp more selectively and more rapidly.
In the laundry field of use, most household bleaches are based upon peroxide. Here,
TAML™ activators enable the most attractive dye transfer inhibition processes ever developed.
Almost all the approximate 80 dyes used on commercial textiles are safe from TAML™ acti-
vated peroxide while they are bound to a fabric. But in almost every case, should a dye
molecule escape a fabric, the same TAML™ activated peroxide will intercept and destroy it
before it is able to transfer to other fabrics. This attribute and the improved stain removal
properties of TAML™ activated peroxide, offer significant commercial advantages for laundry
products producers. In addition, the combined features translate to both direct and indirect
environmental benefits by enabling laundering that replaces stoichiometric with catalytic
procedures and that requires less water. Numerous other fields of use are anticipated; some
are currently being developed including the use of TAML™ peroxide activators for water dis-
infection.
Terry Collins
Department of
Chemistry,
Carnegie
Mellon
University
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Small Business Award
Biofine,
Incorporated
Conversion of Low-Cost Biomass Wastes to Levulinic Acid and
Derivatives
Using biomass rather than petroleum to manufacture chemicals has numerous advan-
tages. Renewable biomass contributes no net CCh to the atmosphere, conserves fossil fuels,
and leads to a secure domestic supply of feedstocks capable of making a huge array of chem-
ical products. Biofine, Incorporated, has developed a high-temperature, dilute-acid hydrolysis
process that converts cellulosic biomass to levulinic acid (LA) and derivatives. Cellulose is ini-
tially converted to soluble sugars, which are then transformed to levulinic acid. The process
is economical even without receiving waste disposal fees for feedstock, and wet feedstocks can
be used without drying, thereby saving energy.
In August 1997, Biofine, the U.S. Department of Energy, the New York State Energy
Research and Development Authority (NYSERDA), and Biometics, Inc. began manufactur-
ing LA from paper mill sludge at a one-ton-per-day demonstration plant at Epic Ventures,
Inc. in South Glens Falls, New York. Biofme's process had already been demonstrated at a
smaller scale with a variety of cellulosic feedstocks, including municipal solid waste, unrecy-
clable municipal waste paper, waste wood, and agricultural residues. Biofine hopes to serve
the growing need for environmentally acceptable waste disposal options.
LA niche markets provide excellent small-scale opportunities; large-scale opportunities
will open up as Biofine lowers the price of this highly versatile chemical intermediate. LA's
worldwide market is about one million pounds per year at a price of $4-6/lb. Full-scale com-
mercial plants are feasible at 50 dry ton/day of feedstock. At this scale, LA could be produced
at $0.32/lb, and converted into commodity chemicals such as succinic acid and diphenolic
acid, which sell for $2/lb or less, or acrylic acid, which sells for $0.50/lb. Eventually, Biofine
hopes to build larger plants to convert 1,000 dry ton/day of feedstock into $0.04-0.05/lb LA.
The worldwide commercial market for LA and its derivatives could reach one trillion Ibs/yr.
Full-scale plant opportunities are being assessed for several locations in the U.S. and world-
wide. One full-scale commercial plant using 1,000 dry ton/day of feedstock could
manufacture more than 160 million Ibs/yr of product. Fortunately, Biofme's technology is
economical for a broad range of plant sizes; even the one-ton-per-day demonstration plant is
self-sufficient at LA's existing price.
Because LA is a platform chemical, it need not be sold as a commodity chemical.
Derivatives are the key to marketability, and markets for such LA derivatives as tetrahydro-
furan, butanediol, gamma butyrolactone, succinic acid, and diphenolic acid exist.
Fortunately, many economical conversion processes are possible. The National Renewable
Energy Laboratory (NREL), Pacific Northwest National Laboratory (PNNL), and Rensselaer
Polytechnic Institute (RPI) are developing market applications and production methods for
other derivatives, including methyltetrahydrofuran (MTHF), a gasoline fuel additive; 8-
amino levulinic acid (DALA), a broad-spectrum, non-toxic, and biodegradable pesticide; and
new biodegradable polymers.
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Alternative Synthetic Pathways Award
Practical Application of a Biocatalyst in Pharmaceutical
Manufacturing
The synthesis of a pharmaceutical agent is frequently accompanied by the use and gener-
ation of a large amount of hazardous substances. This should not be surprising, as numerous
steps are commonly necessary, each of which may require feedstocks, reagents, solvents, and
separation agents. An example of an effort to reduce these hazards, employed by Lilly
Research Laboratories, is the use of an alternate synthetic pathway designed for the environ-
mentally responsible production of a LY300164, a central nervous system compound in the
early stages of development. The original synthesis which was employed to support early clin-
ical development proved to be an economically viable manufacturing process. The approach,
however, involved several problematic steps. The process required the use of large solvent vol-
umes, chromium oxide (a cancer suspect agent) and led to the generation of disproportional
quantities of chromium waste compared to drug produced. These points provided com-
pelling incentive to pursue an alternate synthetic approach.
The new synthetic pathway successfully increased worker safety and limited environmen-
tal impact by offering a strategy which more appropriately controlled oxidation state
adjustments. The new synthesis involved the implementation of several inventive steps on
large scale. In particular, keto-reductase activity of a common microorganism,
Zygosaccharomyces rouxii, was discovered that led to excellent stereocontrol in the asymmetric
reduction of a dialkyl ketone. Implementation of the biocatalytic process was enabled on a
large scale by employing a novel, yet simple, three-phase reaction system. The protocol over-
came long-standing limitations preventing the practical application of yeast-mediated
reductions by allowing high concentrations of the substrate to be charged to the aqueous
reaction medium and by providing a facile method for product isolation. An unprecedented
autoxidation reaction of a C-l aryl isochroman which involved the treatment of the substrate
with air and sodium hydroxide was also discovered that eliminated the use of transition metal
oxidants.
The new process was developed by combining innovations from chemistry, microbiolo-
gy, and engineering. The process circumvented the use of non-recycled metal and
significantly reduced solvent usage. For example, when conducted on a scale to generate 100
kg of LY300164, the new process avoids the use of approximately 34,000 liters of solvent and
eliminates production of approximately 300 kg of chromium waste. In addition, the syn-
thetic scheme proved more efficient as well, with percent yield climbing from 16 to 55%. The
inventive steps of the process represent low cost, easily implemented technology which
should find broad manufacturing applications.
Lilly Research
Laboratories
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Nalco Chemical
Company
Alternative Solvents/Reaction
Conditions Award
Water Based Liquid Dispersion Polymers
Annually, at least 200 million pounds of water soluble, acrylamide-based polymers are
used to condition and purify water in various industrial and municipal operations. These
water-soluble polymers assist in removing suspended solids and contaminants and effecting
separations. Conventionally, in order to prepare such polymers in liquid form for safety and
ease of handling, the water soluble monomers, water, and a hydrocarbon (oil) and surfactant
"carrier" mixture are combined in approximately a 1:1:1 ratio (to form an emulsion). The
monomers are then polymerized. Regrettably, the oil and surfactant components of these
inverse emulsions lend no value to the performance of the polymers; they simply allow their
manufacture in liquid form. This means that approximately 90 million pounds of oil and sur-
factant are introduced into the environment (at the current consumption rates) as a
consequence of their use. Until now, there has been no alternative technology available to
manufacture liquid polymers without the obvious environmental disadvantages associated
with the oil and surfactant based carrier systems.
In order to overcome the disadvantages of conventional liquid emulsion polymers, Nalco
has developed a series of new polymer products that are produced through a unique poly-
merization technology that permits the manufacture of these widely used polymers as fine
particles dispersed in aqueous solutions of the inorganic salt ammonium sulfate. Thus, while
the chemistry of the active polymer component is the same, the technology allows for the
production of the polymers as stable colloids in water. Since these dispersion polymers are liq-
uid, they retain the virtues of ease and safety of handling, but employing aqueous salt
solutions instead of hydrocarbons and surfactants as the reaction medium and polymer car-
rier means that no oil or surfactants is released into the environment when the polymers are
used in the water treatment application.
By choosing to manufacture water-based dispersions instead of water-in-oil emulsions,
over one million pounds of hydrocarbon solvent and surfactants have been conserved by
Nalco since 1997 on just two polymers in the product line. There are also benefits over the
water-in-oil emulsion polymers for the users of these products as a consequence of their
water-based formulations. For example, as the products contain no oil, they are safer to trans-
port and use since they are non-flammable and emit no VOCs.
As mentioned, the water-based dispersion polymers make use of ammonium sulfate salt,
a waste by-product from the manufacture of caprolactam, the precursor to nylon. The prepa-
ration of water-based dispersion polymers instead of water-in-oil emulsions allows Nalco to
recycle and make use of this by-product from another industry for water treatment and
purification. Choosing to produce these polymers as water-based dispersions instead of as
water-in-oil emulsions allowed Nalco to utilize over 3.2 million pounds of caprolactam-pro-
duced ammonium sulfate in 1998 alone.
Finally, because these new polymers are water based, they dissolve readily in water with-
out the complex and relatively expensive mixing and feeding equipment that is required for
the use of water-in-oil polymers. This distinct advantage provides new opportunities for
medium and smaller sized operations to treat wastewater streams cost effectively.
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Designing Safer Chemicals Award
Spinosad, A New Natural Product for Insect Control
Estimates of monetary losses in crops as a result of uncontrolled insect infestations are
staggering, far in excess of the current $12 billion dollar market for insect control products.
Man's continuing quest to control damaging insect pests in crops or on property has spawned
several eras of agricultural insect control, most recently the advent of synthetic organic chem-
icals as insecticides. However, the development of resistance has reduced the effectiveness of
many of the currently available insecticides, and more stringent environmental and toxico-
logical hurdles have restricted the use of others.
It was against this backdrop that researchers at Eli Lilly and Company introduced high
volume testing of fermentation isolates in agricultural screens in the mid-1980s. From this
program, the microorganism Saccaropolyspora spinosa was isolated from a Caribbean island
soil sample, and the insecticidal activity of the spinosyns, a family of unique macrocyclic lac-
tones, was identified and developed by Dow AgroSciences as highly selective,
environmentally-friendly insecticide.
In Latin, "saccharopolyspora" means "sugar-loving, with many spores", and "spinosa"
refers to the spiny appearance of the spores. The microorganism is an aerobic gram-positive,
non-acid fast, nonmotile, nonfilamentous bacterium. Most of the activity is produced by a
mixture of spinosyn A and spinosyn D, assigned the common name of spinosad. Spinosad
combines highly efficacious control of many chewing insect pests, in cotton, trees, fruits, veg-
etables, turf, and ornamentals with superior environmental profile, mammalian and
non-target safety. Insects exposed to spinosad exhibit classical symptoms of neurotoxicity,
including lack of coordination, prostration, tremors, and other involuntary muscle contrac-
tions eventually leading to paralysis and death. Detailed investigations of the symptomology
and electrophysiology have indicated, however, that spinosad is not acting through any
known mechanism. It appears to effect insect nicotinic and gamma-aminobutyric acid recep-
tor function through a novel mechanism.
Spinosad presents a favorable environmental profile. Spinosad does not leach, bioaccu-
mulate, volatilize or persist in the environment. Hundreds of innovative product
development trials conducted over several years characterized the activity and determined
that spinosad left 70 to 90% of beneficial insects and predatory wasps unharmed. The low
levels of mammalian toxicity result in reduced risk to those who handle, mix and apply the
product. Similarly, relatively high margins of safety for avian and aquatic species translate into
reduced or non-existent buffer zones and fewer regulated non-target compliance measures.
These advantages allow growers to control damaging crop pests with fewer concerns about
human or environmental safety and costly secondary pest outbreaks.
The first product containing spinosad (Tracer Naturalyte™ Insect Control) received expe-
dited review by the U.S. EPA and was granted registration as a "reduced risk" insect control
product for cotton in early 1997- Additional registrations, introduced as SpinTor™, Success™,
Precise™, and Conserve™, have recently been granted for insect control in vegetable and tree
crops and in the urban environment for control of turf and ornamental plant nests.
Dow
AgroSciences
LLC
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Professor Richard P.
Wool, University of
Delaware
Professor Krzysztof
Matyjaszewski,
Department of
Chemistry, Carnegie
Mellon University
Professor Michael R.
Ladisch, Laboratory of
Renewable Resources
Engineering and
Department of
Agricultural and
Biological Engineering,
Purdue University
Entries from Academia
Affordable Composites from Renewable Sources
(ACRES)
In the past two years, the ACRES group examined several hundred chemical pathways to
convert soyoil to high-performance plastics, adhesives, and composites and developed afford-
able soy resins that are compatible with high-volume composite manufacturing processes.
New soy-based plastics and adhesive materials are being evaluated and tested by end-users
and converters for high-volume applications in agricultural equipment (tractors and farming
machines), automotive (car and truck parts), civil (bridges and highway components), marine
(pipes and offshore equipment), rail infrastructure (carriages, box cars, and grain hoppers),
and the construction industry (formaldehyde-free particle board, ceilings, engineered lum-
ber). Recent advances in genetic engineering, natural fiber development, and composite
science offer significant opportunities for new, improved materials from renewable resources
with enhanced support for global sustainability.
Atom Transfer Radical Polymerization
Atom transfer radical polymerization (ATRP) is a new technology that allows for the
development of novel, high-performance polymeric materials. The process utilizes a transi-
tion metal catalyst, which can be recycled, to mediate the control of a radical polymerization.
The polymerization process allows for the direct preparation of polymer in bulk monomer,
precluding the use of volatile organic compounds (VOCs) to moderate the rate of polymer-
ization. Additionally, ATRP can be conducted in environmentally friendly solvents such as
water or carbon dioxide (CC^). The products prepared by ATRP are advanced materials that
can help solve current and future environmental/health concerns. An example is the prepa-
ration of self-plasticizing poly (vinyl chloride) (PVC), which can be used to replace harmful
phthalates that are currently used to soften PVC used in children's toys.
BiobasedAdsorbents for Desiccant Coolers
Revised standards for acceptable indoor air quality have doubled ventilation requirements
for commercial buildings and retail establishments. The need to dehumidify the additional
air flow, combined with concerns about the phase-out of freons and the need to control costs
of dehumidifying and cooling air, have led to an increase in the use of desiccant wheels.
When combined with heating, ventilation, and air-conditioning systems, desiccant wheels
save both capital and operating costs, according to a Gas Research Institute funded study.
Since desiccant wheel systems can dry and cool large volumes of air, they have the poten-
tial to supplant CFC and HFC refrigerants associated with compression-type
air-conditioning systems. The current production of desiccants is about 180 million pounds
per year. Approximately half of this is attributed to molecular sieves, and 25% are silica gels.
The potential of starch and cellulose as drying agents for fuel alcohol was reported in Science
in 1979 and scaled up for industrial use by 1984. Ground corn is used in an adsorption
process that replaces azeotropic distillation to dry approximately 750 million gallons of fuel
ethanol annually. The corn-based adsorbent proved to save energy while avoiding the need to
use benzene as the drying agent.
The fundamental research and demonstration of the potential of starch- and cellulose-
based adsorbents for desiccant air coolers, is an on-going research project at Purdue
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University that evolved from the first application of corn grits to the drying of fuel alcohol.
Cross-disciplinary research at Purdue University has shown that starch, cellulose, and corn-
based materials are potentially suitable for desiccant wheels. These adsorbents are biologically
based (biobased). Unlike silica gels and other inorganic adsorbents, biobased desiccants are
less expensive, biodegradable, and are derived from a renewable resource. Their low cost and
wide availability could hasten adaptation of environmentally friendly air-conditioning sys-
tems for residential as well as commercial uses.
Byconversion of Carbon Dioxide into Organic
Feedstocks
It has been established that emissions of carbon dioxide gas are responsible for about half
of the increase in global warming. Efforts to decrease the consumption of fossil fuels are lim-
ited by increasing human population and industrialization and the fact that alternatives to
fossil fuels all have important limitations. It is a matter of considerable urgency not only to
conserve fossil fuel reserves, but also to search for means to recycle their main combustion
product, which is carbon dioxide. In this regard, a unique bioprocess has been developed that
is capable of converting waste carbon dioxide gas into algae, which is subsequently ferment-
ed into a variety of organic feedstocks, such as methane and acetic acid. Previous attempts to
utilize phototrophic bacteria for fixation of carbon dioxide gas were limited by the following
facts: photosynthesis by phototrophic bacteria requires anaerobic conditions, which requires
that carbon dioxide gas has to be separated from oxygen and is an expensive process; unlike
algae, phototropic bacteria require a wide spectrum of light, which limits their light source to
sunlight.
In the work of Dr. Rakesh Govind and Rajit Singh at the University of Cincinnati, a
marine algae, Tetmselmis suecica, has been used successfully in a photobioreactor using light
emitting diodes (LEDs) with a specific wavelength of 680 nm and a gas residence time of a
few seconds. More than 98% removal efficiency of carbon dioxide gas from typical coal fired
power plant stack gases was achieved experimentally at 3 seconds gas residence time at ambi-
ent temperature and pressure. The algae was separated from the aqueous phase by settling in
a clarifier, and then converted under anaerobic conditions using electrodialytic fermentation
to acetic acid and methane in a batch reactor with yields of over 85% to acetic acid and 89%
to methane gas. Catalytic conversion of methane gas to methanol and other organic feed-
stocks has been established in the literature. Thus, this process offers several advantages:
bioconversion of waste carbon dioxide gas to useful organic feedstocks at ambient tempera-
ture and pressure, high conversion efficiencies of carbon dioxide gas to algae and
subsequently to acetic acid and methane, and rapid reaction rate in the photobioreactor to
produce algae. Economic estimates of the technology have shown that this technology can be
easily implemented at power plant sites and acetic acid can be manufactured at less than half
the current costs of manufacturing acetic acid from natural gas or crude oil resources.
Biosynthetic Production ofp-Hydroxybenzoate Improves
Regiospecificity and Minimizes Byproduct Generation
The work of Steven W Peretti at North Carolina State University illustrates the utility of
biocatalysis in effecting green chemistry by focusing on the development of an innovative,
alternative, biosynthetic pathway for the production of p-hydroxybenzoate (HBA).
Biocatalytic production of HBA provides improved regiospecificity over the two-step Kolbe-
Schmitt carboxylation of phenol, the current state of the art. Due to the specificity of enzyme
Dr. Rakesh Govind and
Rajit Singh,
Department of
Chemical Engineering,
University of Cincinnati
Steven W. Peretti,
Department of
Chemical Engineering,
North Carolina State
University
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Albert Robbat, Jr.,
Chemistry Department,
Tufts University
Dr. Chhiu-Tsu Lin,
Department of
Chemistry and
Biochemistry, Northern
Illinois University
catalyzed reactions, significant source reductions in the generation of waste byproducts are
obtained. Increased levels of safety for both the environment and human health are achieved
due to the mild reaction conditions employed. HBA production can now be achieved by a
single processing step, a unique feature that cannot be accomplished using traditional chem-
istry.
HBA production is achieved by contacting an active cell mass with toluene. The toluene
passively diffuses into the cells and is transformed through a series of intracellular enzymatic
reactions to HBA. Since the pathway for HBA catabolism is blocked through the use of
chemical mutagenesis, the HBA generated from toluene conversion is neither incorporated
into cellular material nor oxidized for energy, but instead is secreted out of the cell and into
the culture media. The HBA can then be recovered by precipitation from an acidified process
stream following removal of cell mass.
Cheminfomatics: Faster, Better, Cheaper Chemical
Analysis Software
Mass spectrometry (MS) data analysis algorithms have been developed that, when com-
bined with large-volume gas chromatography (GC) sample injection, provide quantitative
analysis of a wide range of EPA targeted pollutants in <10 min and semiquantitative data in
five min by GC/MS. Soil analysis data were produced in the field, verified by EPA, and used
to determine risk to ground water and to delineate the extent of contamination within the
airfield at Hanscom Air Force Base. The proposed technology significantly reduces sample
preparation time, solvent consumption, the need for multiple methods of analysis to analyze
the wide range of EPA target compounds, and improves laboratory productivity by a factor
of 3 to 6. In addition to MS, the core algorithms are applicable to any detection system that
produces narrow band, characteristic signals including atomic emission detection (AED) for
metals. For example, the same deconvolution algorithms should untangle overlapping spec-
tral signals, as they do for GC/MS, in techniques such as liquid chromatography/MS
(LC/MS), capillary electrophoresis/MS (CE/MS), and inductively coupled plasma/AED and
MS applications. Faster run times mean less solvent consumption when operating LC/MS
and CE/MS instruments. This is especially important when one considers the explosion in
the number of LC/MS assays that will be required in the biopharmaceutical markets now that
one chemist can synthesize 1,000 to 10,000 new compounds per year as compared to 10
because of advances in combinatorial chemistry technology.
Chrome-Free Single-Step In-Situ Phosphatizing
Coatings
Economic losses resulting from corrosion of metals have been said to amount to billions
of dollars per year and to be of the magnitude of 4 percent of the gross national product. In
commercial practice, organic polymer coatings have been used in both commercial coating
industries and the military to protect metal substrates against corrosion. The current organ-
ic coating on metals involves a multistep process and considerable energy, labor, and control.
The traditional phosphate treatment process for preparing metal prior to painting is a costly
and error-prone process. For example, information provided by Caterpillar Tractor's
Montgomery, Illinois, plant for the cost per year of its hydraulic tube phosphating line is
$330,000 (water/wastewater treatment = $70,000; chemicals = $36,000; labor = $166,000;
steam = $50,000; and electricity = $8,000). In addition, the use of corrosion inhibitors, the
phosphating line baths, and the chromate sealing process in the current multistep coating
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practice generates toxic wastes such as chlorinated solvents, cyanide, cadmium, lead, and car-
cinogenic chromates.
The innovative green chemistry technology of chrome-free single-step in situ phosphatiz-
ing coatings (ISPCs) is a one-step self-phosphating process. The unique chemical principle of
ISPCs is that an optimum amount of in situ phosphatizing reagents (ISPRs) are predispersed
in the desired paint systems to form a stable and compatible one-pack coating formulation.
The formation of a metal phosphate layer in situ will essentially eliminate the surface pre-
treatment step of employing a phosphating line/bath. The ISPRs form chemical bonds with
polymer resin that act to seal and minimize the porosity of the in situ phosphated substrate.
The use of chemical bondings to seal the pores of metal phosphate in situ should enhance
coating adhesion and suppress substrate corrosion without a post-treatment of final rinses
containing chromium (Cr6+).
Design of Rubberized Concrete From Recycled Rubber
Tires
The United States produces about 279 million scrap tires per year. In addition, about 3
billion used tires are currently stored in waste piles throughout the country. Solid waste man-
agement experts recognize the need to recycle, reuse, or reduce the waste rubber tires, since
this would lead to a direct diminution of waste tires in landfills. A number of processes have
been suggested for reusing the waste rubber. Using tires as fuel and as asphalt material has
provided only limited success. The work of Dr. Dharmaraj Raghavan at Howard University
has led to the development of a technology that mixes rubber particles from scrap tires into
portland cement resulting in a lighter material with improved performance of mortar and
probably concrete.
The worldwide production of cement exceeds 1 billion tons annually, with the possibili-
ty of it nearly doubling in the next 14 years. Cement based materials are inexpensive, easy to
produce, and possess valuable engineering properties such as high durability and compressive
strength. One of the major shortcomings of cement based material is the vulnerability of con-
crete to catastrophic failure and to plastic shrinkage cracking. An encouraging finding was
that plastic shrinkage cracking can be reduced significantly and the vulnerability of concrete
to catastrophic failure can be greatly diminished by the addition of sufficient fibrous rubber.
Chemical tests of the rubber retrieved from rubberized concrete showed no evidence of rub-
ber undergoing any degradation and consequently no threat of released chemicals from the
leached rubber into the environment. Possible uses of the rubberized concrete would be in
subbases for highway pavements, highway medians, sound barriers, and other transportation
structures. Currently the United States spends $250 billion annually on infrastructure pro-
jects. Even if rubberized concrete replaced only a small fraction of the conventional
infrastructural material, the ramifications to the civil and composite industries will be sub-
stantial. The technology to reuse rubber tires into cement system yields value-added
infrastructural material, while eliminating the imminent threat of health hazard and explo-
sion potential because of the flammable nature of rubber tires.
Dr. Dharmaraj
Raghavan, Department
of Chemistry, Howard
University
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Gregory Moller, Holm
Research Center,
University of Idaho
Craig L. Hill,
Department of
Chemistry, Emory
University
Ira A. Weinstock, USDA
Forest Service, Forest
Products Laboratory
Effects of the Corrosion of Elemental Iron on Heavy
Metal Contamination from Pyrite Oxidation
The activity of corroding iron metal is examined in the acid rock drainage (ARD) to
determine the effectiveness in neutralizing the ARD and reducing the load of dissolved heavy
metals in solution and soils. In acidic solution, iron hydrolyzes water producing hydride and
hydroxide ion resulting in a concomitant increase in pH, decrease in Eh, and removal of dis-
solved heavy metals by a variety of mechanisms. A colloidal iron batch reactor effectively
treats ARD from Berkeley Pit, Montana. Iron columns effectively treat soil column water and
model ARD solution leachates. A model ARD solution (bisulfate buffer pH = 4) with dis-
solved zinc was treated with colloidal metallic iron. Kinetic studies demonstrated the first
order dependence of the initial rate of reaction on the surface area of metallic iron where the
rate of the disappearance of zinc is —rZn = 1.2*AFe. The reaction half-life of dissolved zinc
removal from solution was 140 minutes. X-ray diffraction analysis of the oxidized bulk solids
from these experiments indicated green rust, magnetite, and goethite structures. Corroding
iron also creates a reducing environment supportive for sulfate reducing bacteria (SRB)
growth, increasing populations 5,000 fold to provide sulfidogenesis as an additional pathway
to further stabilize heavy metal precipitates.
Effluent-Free Process for Use of Oxygen in Place of
Chlorine Compounds in Wood-Pulp Bleaching
A completely new approach to the delignification of wood or wood pulp—composites of
cellulose and lignin—for paper manufacture has been developed. This chemistry achieves a
goal no other technology developed thus far does, but one that is operable in nature—the
selective delignification of wood or wood pulp using only the readily available and nontoxic
agents air and water. Wood is comprised principally of two biopolymers: cellulose, which
imparts strength to trees and paper, and lignin, which imparts color, texture, and mechanical
properties to wood. The goal in the manufacture of high-quality paper is to remove the lignin
with as little damage to the cellulose fibers as possible (high-quality paper is composed of
lignin-free cellulose fibers).
Nature carries out this chemically and technically challenging multistep process by using
a complex ensemble of selective metalloenzymes (glyoxal oxidase, ligninase, and Mn peroxi-
dase). The pulp and paper industry, since its inception many decades ago, has yet to achieve
what nature has. Chlorine compounds, not Ch, have been the dominant oxidants. While
decades of optimization have led to highly selective delignification (minimally damaged cel-
lulose), these man-made technologies produce waste streams that contain environmentally
deleterious phenolic compounds as well as nonbiodegradable chloroaromatics. In conse-
quence, societal and legislative pressure in all developed countries is compelling pulp
manufacturers to phase out chlorine. The most attractive alternative oxidants, hydrogen per-
oxide (H^Ch) or ozone (03) are encumbered by inherent limitations. Hydrogen peroxide is
simply not effective. Ozone processes, while potentially effective, fall far short of the selectiv-
ity required for general commercial use or of the selectivity seen in nature.
The new catalytic biomimetic approach uses versatile, nontoxic, and inexpensive inor-
ganic clusters known as polyoxometalates (POMs) in two steps. The first step involves
delignification of wood pulp (bleaching) by reaction with the oxidized POM providing high-
quality cellulose fibers. As the POM is reversibly reduced, the lignin is oxidized and
solubilized. In the second step, O2 is added to the bleaching liquor and the same POM cat-
alyzes the complete conversion (mineralization) of the dissolved lignin fragments to CO2 and
12
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H2O. The two steps sum to the selective removal of lignin from wood, using only air and
water, an ideal process that only nature has achieved to date. This biomimetic and catalytic
technology eliminates the environmental problems associated with conventional chlorine-
based processes while overcoming the limitations inherent in other chlorine-free pulp
bleaching strategies. It is green in at least six ways including the complete elimination of waste
streams (a "closed process" is achieved). The high selectivity entails less consumption of the
natural renewable resource, wood. It is energy efficient and as current analyses indicate, cost-
effective.
Engineered Baker's Yeast as a Means to Incorporate
Biocatalysis Early in Process Design: Application to the
Asymmetric Baeyer-Villiger Oxidation
While enzymes provide many advantages over traditional chemical reagents, they are gen-
erally applied to processes only during scale-up stages. It would make better economic and
environmental sense to include biocatalytic methods during the initial discovery phase; how-
ever, this would require making biocatalysis accessible to bench chemists who often have no
background in biochemistry or microbiology. Dr. Jon D. Stewart at the University of Florida
has developed designer yeast, ordinary baker's yeast cells that have been engineered to express
one or more foreign proteins. Whole cells of these engineered yeasts can be used directly as a
biocatalyst for organic synthesis. As proof of principle, Dr. Stewart's group has created a yeast
strain that catalyzes a broad array of enantioselective Baeyer-Villiger oxidations. While this
reaction plays an important role in laboratory-scale syntheses, the severe environmental and
safety problems associated with current reagents prohibit its large-scale use. Acinetobacter
cyclohexanone monooxygenase was expressed in Saccharomyces cerevisiae and whole cells of
the engineered yeast were used to oxidize several ketones in good yields and with high enan-
tioselectivities. This process uses atmospheric C>2 as the oxidant and produces water as the
only byproduct. Cell biomass and spent culture medium can be discarded in sanitary sewers
after heat inactivation.
Environmental Advantages Offered by Indium-
Promoted Carbon-Carbon Bond-Forming Reactions in
Water
In view of increasing demands to reduce emissions during the production of chemical and
pharmaceutical end-products, it is imperative to consider the development of effective car-
bon-carbon bond forming reactions in aqueous media. The work of Dr. Leo A. Paquette at
The Ohio State University demonstrates not only that the counterintuitive notion of
organometallic carbon-carbon bond-forming reactions performed in water is indeed work-
able, but also that high levels of stereocontrol are attainable. The key to this safe,
environmentally friendly technology is the utilization of metallic indium as the promoter.
The metal indium, a relatively unexplored element, has recently been shown to offer intrigu-
ing 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 nontoxic, very resistant to air oxidation, and
easily recovered by simple electrochemical means, thus permitting its reuse and guaranteeing
uncontaminated waste flow. The power of the synthetic method, which often can exceed per-
formance levels observed in purely organic solvents, includes no need for protecting groups,
greatly enhanced ease of operation, and greatly reduced pollution risks.
Dr. Jon D. Stewart,
Department of
Chemistry, University
of Florida
Dr. Leo A. Paquette,
Department of
Chemistry, The Ohio
State University
13
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Professor John C.
Warner, Department
of Chemistry,
University of
Massachusetts, Boston
Polaroid Corporation
Chi-Huey Wong, Ernest
W. Hahn Professor of
Chemistry, The Scripps
Research Institute
Dr. Richard H. Fish,
Lawrence Berkeley
National Laboratory,
University of California
Environmentally Benign Supramolecular Assemblies of
Hydroquinones in Polaroid Instant Photography
The work of Professor John C. Warner at the University of Massachusetts, Boston repre-
sents the first example of supramolecular synthesis in a manufacturing system for pollution
prevention. Using the concepts of molecular recognition and self-assembly, a new technique
has been developed for the control of molecules within films and coatings. This process has
a number of environmental benefits including reduced synthetic steps, reduced waste gener-
ation, reduced solvent usage, and the introduction of solventless or aqueous processing.
Instead of performing several time consuming, solvent-based, chemical reactions in order to
synthesize a series of candidate compounds for structure activity studies, this technique allows
for the addition of simple, inexpensive, readily available 'complexing reagents.' For this to be
successful as pollution prevention, these assemblies must significantly reduce the number of
synthetic reactions carried out. Often the formation of these assemblies involve no organic
solvents. The supramolecular structures can be constructed via solid state grinding or aque-
ous dispersing techniques.
Enzymes in Large-Scale Organic Synthesis
This nominated project is concerned with Wong's original contributions in the develop-
ment of novel enzymatic and chemo-enzymatic methods for large-scale organic synthesis.
Three significant achievements in this field include: a breakthrough technology for oligosac-
charide synthesis using genetically engineered glycosyltransferases coupled with in situ
regeneration of sugar nucleotides, which has enabled the large-scale synthesis of complex car-
bohydrates for clinical evaluation; the use of enol esters (e.g., vinyl acetate and
isopropenylacetate) in enzyme-catalyzed transesterification reactions, which has been a wide-
ly used method for enzymatic synthesis of enantiomerically pure hydroxy compounds; and
the use of recombinant aldolases for asymmetric aldol reactions, which has opened a unique
and practical route to novel monosaccharides and related structures, including, for example,
sialic acids, L- configurated sugars, and iminocyclitols. Other important enzymatic methods
developed by Wong include the synthesis of glycopeptides, glycoproteins, chiral amines,
prostaglandins, and numerous chiral synthons. All these synthetic transformations are envi-
ronmentally friendly for use in large-scale processing and are important for the
pharmaceutical and fine chemical industries. They are, however, impossible or impractical to
achieve by nonenzymatic means.
Fluorous Biphasic Catalysis: A New Paradigm for the
Separation of Homogeneous Catalysts From Their
Reaction Substrates and Products, as Demonstrated in
Alkane andAlkene Oxidation Chemistry
Fluorous biphasic catalysis (FBC) is a new concept for homogeneous catalysis where the
fluorocarbon soluble catalyst and the substrates/products reside in separate phases. The work
of Dr. Richard H. Fish, Lawrence Berkeley National Laboratory, presents the synthesis of a
novel fluoroponytailed ligand, tris-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,ll,ll,ll-heptadecaflu-
oroundecyl)-l,4,7-triazacyclononane (RfTACN), that is soluble in the perfluoroalkanes
[Mn(O2C(CH2)2C8Fi7)2] and [CO(O2C(CH2)2CsFi7)2]. The initial results on the function-
alization (oxidation) of alkanes/alkenes, using in situ generated fluorous phase soluble
RfMn2+-RfTACN and RfCo2+-RfTACN complexes (Rf = C8Fi7) as the precatalysts, in the
14
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presence of t-butyl hydroperoxide (t-BuOOH) and C>2 gas as oxidants, demonstrated that
alcohols, aldehydes, and ketones could be produced catalytically and that the oxidation prod-
ucts and fluorous phase soluble precatalysts were indeed in separate phases. The fact that
fluorocarbon solvents are relatively nontoxic provides the FBC concept with an entry to the
new "Green Chemistry" regime of being environmentally friendly, and therefore, attractive
to a wide variety of industrial processes for the ultimate catalytic production of important
organic chemicals worldwide.
Generation of Hydrogen Peroxide in Carbon Dioxide
Hydrogen peroxide is currently produced via the sequential hydrogenation and oxidation
of a 2- alkyl anthraquinone. While H^Ch is generally considered to be a green reagent, the
anthraquinone process generates several waste streams and also exhibits inefficiencies from
both a raw material and energy use standpoint. Functionalized anthraquinones (FAQ's) have
been generated that are miscible with carbon dioxide, thus making it possible to generate
hydrogen peroxide in liquid CC>2. Use of CC>2 as the sole process solvent ameliorates several
environmental and engineering problems inherent to the process, including (a) eliminating
the contamination of the product during its recovery by liquid-liquid extraction into water,
(b) minimizing degradation of the anthraquinone during hydrogenation by allowing control
of residence time distribution in the reactor, and (c) optimizing throughput through each
reactor via elimination of mass transport limitations, which also reduces energy input. Not
only is the use of CC>2 as a solvent a green route to hydrogen peroxide manufacture, but it is
also economically feasible owing to the ability to recover the product without employing a
large pressure drop, ready recycling of the functionalized anthraquinone, and operation at rel-
atively low absolute pressure and in concentrated solution owing to the characteristics of the
FAQ-CO2 phase diagram.
Professor Eric J.
Beckman, Chemical
Engineering
Department, University
of Pittsburgh
Green Chemistry Through the Use of Supercritical
Fluids and Free Radicals
The research of Professor James M. Tanko at Virginia Polytechnic Institute and State
University explores the use of supercritical carbon dioxide (SC-CC^) as a replacement for
many of the toxic and/or environmentally threatening solvents used in chemical synthesis.
The project demonstrated that SC-CCh is a viable, "environmentally benign" alternative, and
there are numerous advantages from a chemical perspective associated with the use of SC-
CCh. This work led to the development of a new, environmentally friendly chemical process
for hydrocarbon functionalization and C-C bond formation.
SC-CO2 is especially attractive because its critical parameters (temperature and pressure)
are moderate, thereby permitting access to the supercritical state without a disproportionate
expenditure of energy. The newly developed hydrocarbon functionalization accomplishes (in
a single, high-yield step) a transformation that would normally require multiple steps and the
use of toxic reagents or strong acids and bases. This reaction should scale-up readily for large
scale (or industrial) applications.
Professor James M.
Tanko, Department of
Chemistry, Virginia
Polytechnic Institute
and State University
15
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Professor Robin D.
Rogers, Department of
Chemistry and Director,
Center for Green
Manufacturing, The
University of Alabama
Dr. Douglas C. Knipple,
Department of
Entomology, Cornell
University
Green Separation Science and Technology: Using
Environmentally Benign Polymers to Replace VOCs in
Industrial Scale Liquid/Liquid or Chromatographic
Separations
One area of opportunity for new chemical science and engineering technology, which will
help meet the goals of Technology Vision 2020, is the development of new separations tech-
nologies that eliminate the use of flammable, toxic VOCs as industrial solvents. Used in
conjunction with, or instead of, appropriate current manufacturing processes, such tech-
nologies would help to prevent pollution and increase safety. The nominated technologies are
based on the use of water soluble polyethylene glycol polymers in either liquid/liquid (aque-
ous biphasic systems—ABS) or chromatographic (aqueous biphasic extraction
chromatographic resins—ABEC) separations. Two patented technologies are highlighted: a)
applications in radiopharmacy to allow the use of cleaner neutron-irradiated isotopes rather
than fission-produced isotopes, and b) applications in remediation where reduction of sec-
ondary waste streams or conventional technologies are anticipated. The separations approach
followed in developing these technologies suggest a wider industrial application for VOC-free
separations. Within a paradigm of pollution prevention and with industry participation, a
tool-box approach to Green Separation Science & Technology can be developed based on the
use of environmentally benign polymers.
In Vivo Synthesis of Lepidopteran Pheromone Precursors
in Saccharomyces Cereviseae: An Economical Process for
the Production of Effective, Nontoxic, Environmentally
Safe Insect Control Products
Since the advent of DDT more than 50 years ago, broad spectrum neurotoxic insecticides
have provided the principal means for the control of economically important insects in agri-
culture and public health programs. Whereas the use of synthetic insecticides initially resulted
in spectacular increases in crop yields and the suppression of some important human and ani-
mal disease vectors, the development of insecticide resistance in insect pest populations and
the environmental damage caused by insecticides were quickly recognized as serious draw-
backs to their use. Today the environmental and human health effects associated with the
manufacture and use of insecticides for pest control are widely recognized, including their
acute toxicity to nontarget organisms (including human applicators), their persistence in the
biosphere, and major point-source pollution associated with their manufacture. Despite these
effects, the scale of release of active ingredients in insecticide formulations into the global
environment is enormous; in the United States alone it is more than 400 million kg/year.
Pheromones have been used on a worldwide basis for the control of insect pests for more
than 15 years. Unlike conventional broad-spectrum insecticides, pheromones are nontoxic
and highly specific for the species they are intended to control. Unfortunately, their effec-
tiveness and selectivity depend upon high chemical and stereo-specific purity, making them
expensive to synthesize. The latter factor has limited their commercial success versus conven-
tional insecticides. The major market for pheromone-based disruption products is in the
United States, and amounts to less than $50 million/year. In contrast, the worldwide insec-
ticide market is greater than $6 billion/year. The goal of the work of Dr. Douglas C. Knipple
at Cornell University is to develop a cheaper process for pheromone synthesis. Toward this
goal, he has proposed to use genetic and molecular technology to clone and functionally
16
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express in vivo genes encoding desaturase enzymes present in the pheromone glands of adult
female moths, which catalyze the formation of key unsaturated pheromone intermediates.
Accomplishment of the technical objectives of this work will contribute materially and
methodologically to development of an alternative biosynthetic process for commercial
pheromone production. Achievement of the latter goal will significantly improve the eco-
nomic competitiveness of existing pheromone products, and could provide the basis for the
expansion of this promising insect control technology into other markets.
Metal Extraction and Recovery Using Carbon Dioxide
Recovery of metals from dilute solution, whether the matrix is solid or liquid, remains a
considerable technical and financial challenge. Methods currently exist whereby metals can
be extracted from either type of matrix, yet these methods consume significant quantities of
reagents and can also generate multiple waste streams in the process. Technology developed
in the lab of Eric J. Beckman, University of Pittsburgh, over the past three years allows effi-
cient application of environmentally benign CC>2 to a number of separation problems
involving metals. For example, biphasic mixtures of CC>2 and water have been employed as a
green acid leach medium. Metals have been extracted from a steelmaking process residue and
then recovered as metal carbonates through depressurization. In this process, metals are
extracted and recovered without the use of reagents other than CC>2 and water, and CC>2 is
sequestered as a solid. In addition, through synthesis of CCh-miscible phase transfer agents,
CC>2 can replace the organic solvent currently used in refining of precious metals. The sensi-
tivity to pressure of phase behavior in a CCVmixture may allow significant streamlining of
the process as well. Finally, CCh-soluble chelating agents have been used to extract toxic met-
als from acidic effluent such as that found in plating facilities.
Microwave-Induced Organic Reaction Enhancement
(MORE) Chemistry for Eco-Friendly Synthesis
Microwave assisted organic synthesis is an emerging technology of great potential. Dr.
Ajay K. Bose at the Stevens Institute of Technology has contributed to this field through the
development of nontraditional methods for using domestic microwave ovens for conducting
a wide variety of organic reactions that are fast, safe, and friendly to the environment. Dr.
Bose's group has shown that for a wide variety of reactions, microwave irradiation of reaction
mixtures in open glass vessels can lead to faster reaction rates, fewer byproducts, and higher
steric control. Since microwaves interact directly with molecules with dipoles, there is little
need for a liquid medium to convey heat from the glass walls as in conventional heating. The
key features of Microwave-Induced Organic Reaction Enhancement (MORE) chemistry
techniques are the use of limited amounts of high-boiling solvents (or no solvents)—enough
to form the reaction mixture into a slurry at room temperature—and efficient control of
microwave energy input to reach the desired reaction temperature without allowing the reac-
tion mixture to come close to its boiling point. Such reactions can be completed on several
hundred grams scale in a few minutes. Larger scale synthesis should be possible by using com-
mercial microwave equipment used by the food industry.
The elimination or reduction of the use of organic solvents, and the purer products
formed, lead to reduced chemical waste (e.g., organic solvents for reactions and recrystalliza-
tion and chromatographic material for purification). To demonstrate 'atom economy (more
products for all the chemicals used) and the versatility of MORE chemistry techniques, Dr.
Bose's group has conducted multistep synthesis (including one-pot reactions for two or more
Eric J. Beckman,
Chemical Engineering
Department, University
of Pittsburgh
Dr. Ajay K. Bose,
Stevens Institute of
Technology
17
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Dr. Mono M. Singh,
National Microscale
Chemistry Center,
Merrimack College
H. Alan Rowe,
Department of
Chemistry/Center for
Materials Research,
Norfolk State
University
Dr. Dharmaraj
Raghavan, Department
of Chemistry, Howard
University
steps) of advanced intermediates for lactam antibiotics, amino sugars, alkaloids, and other
biologically active compounds such as Taxol. They have also found that an efficient and eco-
friendly nitration method can be accomplished by irradiating with microwaves, have
observed mild acceleration of chemoenzymatic reactions under low-intensity microwave irra-
diation, and have devised a very eco-friendly oligopeptide synthesis that needs no
conventional peptide bond forming agents. In brief, MORE chemistry techniques can make
very significant reduction of pollution at the source for small-scale as well as large-scale syn-
thesis and thus make the development and production of life-saving drugs more eco-friendly
National Microscale Chemistry Center: The Leader in
Worldwide Implementation of Microscale Technology
The simplest definition of Green Chemistry is "the use of chemistry techniques and
methodologies that reduce or eliminate the use or generation of feedstocks, products, byprod-
ucts, solvents, reagents, etc., that are hazardous to human health or the environment." While
more commonly being applied to industrial applications, the concepts of Green Chemistry
also have been incorporated into education pedagogy, using microscale laboratory methods.
The microscale chemistry technique is a laboratory-based educational program, resulting in
waste reduction at the source; elimination of toxic emissions, fire, and accident hazards;
enhancement of a healthful laboratory environment; and significant cost savings. Microscale
methodology uses minute amounts of chemicals (50 mg of solids, 500 uL of liquids on aver-
age); new methods for determining physical properties; milder and safer alternative reaction
conditions; alternative benign solvents; and different synthetic pathways, often employing
catalytic and other environmentally safe techniques. The National Microscale Chemistry
Center was established at Merrimack College in 1993- The center offers workshops, training,
and other related support to teachers and industrial chemists in microscale chemistry tech-
niques. Currently, more than 2,000 institutions in the United States have, either fully or
partly, adopted this approach. NMC2 is also the lead site of an international consortium pro-
moting the microscale/Green Chemistry revolution.
New Reducing Sugar Assay
The chemical measurement of reducing sugars [sugars containing hemiacetal/hemiketal
groups] is common in biochemical research and teaching laboratories. The currently avail-
able methods depend on the reaction of copper ions in hot alkaline solution with complexing
and color-forming reagents. Typically, tartrate is used as the complexing agent and a solution
of molybdenum and arsenate ions for the color-forming reagent [the arsenomolybdate
reagent]. The arsenomolybdate reagent has a limited shelf-life and is extremely toxic. This
presents formidable problems in the use and disposal of the assay solution. This solution must
be stored as waste and disposed of commercially. The original assay outlined here is a proce-
dure that uses a more stable complexing agent (EDTA) and replaces arsenate with phosphate
in the color-forming complex. The materials produced in this assay are much more benign.
Novel Applications of Polymer Composite from
Renewable Materials
Metal corrosion costs the United States about 4.2% of its gross national product, or more
than $250 billion in 1996. To improve the longevity of the engineered material, the surface
coatings must be refurbished to meet design requirements. Recoating the surface involves
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paint stripping and application of a fresh paint coating. Traditional stripping methods
employ the organic solvent methylene chloride. Methylene chloride is carcinogenic and poses
a health risk to the maintenance crew. Consequently, the aircraft maintenance industry has
begun to utilize alternative approaches for depainting aircraft. One method that has proved
reliable is dry-blasting to remove the paint coating mechanically. The depainting process
using blast media, however, is reported to be the largest single source of solid waste on mili-
tary bases where aircraft repainting is performed.
The work of Dr. Dharmaraj Raghavan at Howard University addresses the development
of an organic coating removal technique based upon renewable plastic media. As such, the
degradable dry-blast process is developed so as to eliminate 90 to 97% of the waste by bio-
logical or chemical degradation of the spent media. The degradation of solid media waste
(based on renewable polymer) results in the production of speciality solvents that are envi-
ronmentally safe and are value-added chemicals. Another application where degradability of
renewable polymer composite can be exploited is in membrane design. Membranes represent
a worldwide market approaching $1 billion, annually. Membranes have found wide applica-
tions in industry, particularly in the separations industry. In the design of these membranes,
solvents used include acetone, dimethyl sulfoxide, dimethyl formamide, and dimethyl
acetamide. There is a general concern of the exposure of the working crew to carcinogenic
solvents during the preparation of membranes. To address these concerns, Dr. Raghavan has
designed a compatabilizer-based polymer composite, where the major component is renew-
able polymeric material and the minor component is nondegradable synthetic polymer. The
technology is based on the degradability of the renewable polymer in protic solvent/enzymic
system and the ability to formulate a porous microstructure of synthetic polymer. The degra-
dation of the renewable polymer results in the production of chemicals that are
environmentally safe and can be used in the synthesis of renewable polymer.
Novel Chemical Analysis Technologies by Water Liquid
Chromatography, Raman Spectroscopy, and High Speed
Gas Chromatography
Dr. Robert E. Synovec's research addresses the development of novel liquid and gas chro-
matographic chemical analysis technology and related methodologies that are consistent with
the goals of the Green Chemistry Program and pollution prevention. The goal of this research
has been to develop unique chromatographic instrumentation and methods for laboratory,
field, and process analysis that reduce the toxicity and volume of consumable materials used
in separations-based analyses, while enhancing the performance and information gleaned
from the analyzer. This goal is a major research initiative at the Center for Process Analytical
Chemistry (CPAC). The chemical analyzers and methodologies that have been produced by
these research efforts benefit U.S. industry by enhancing the applicability of liquid and gas
chromatography in a variety of arenas: routine and automated EPA methods, industrial
process chemical analysis, conventional bench-top analysis, and remote chemical monitoring.
A reduction in industrial pollution is a key result of these technologies, by minimizing chem-
ical waste through optimum process control.
Novel In Situ Zeolite Coatings in Monoliths
A novel, in situ method of depositing binderless zeolite catalysts in monolith reactor sys-
tems has been developed at the University of Cincinnati. In situ coatings of zeolites on
monolith substrates maximize the effectiveness of the "shape-selective" aspects of zeolite catal-
Dr. Robert E. Synovec,
Department of
Chemistry, University
of Washington
Dr. Jimmy E. Antia and
Dr. Rakesh Govind,
Department of
Chemical Engineering,
University of Cincinnati
19
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Dr. Bala Subramaniam,
Department of
Chemical and
Petroleum Engineering,
University of Kansas
Dr. Nasrin R. Khalili,
Ham id Arastoopour,
and Laura Walhof,
Department of
Chemical and
Environmental
Engineering, Illinois
Institute of Technology
ysis. This technology can be used for a wide variety of zeolites, currently used extensively in
the petrochemical industry It has been shown that binderless zeolites used in monoliths
exhibit enhanced performance, minimizing the formation of high molecular weight hydro-
carbons with minimal diffusional limitations. Two specific studies were conducted to
demonstrate the effectiveness of these binderless zeolites in monoliths: conversion of
methanol to gasoline hydrocarbons and catalytic cracking of n-hexane. The main technical
advantages of monolith reactors are low pressure drop, improved performance due to less
plugging and channeling, and high surface area per unit volume of reactor. The technology
also offers many benefits for human health and the environment. For instance, alcohol
obtained from fermented agricultural wastes can be converted to gasoline-range hydrocar-
bons on monolith reactors. Besides producing useful fuel, this reaction produces no
hydrocarbons larger than Cu, which are difficult to burn and exhibit low biodegradation
rates if released to soil and ground water. Also, this alternative fuel source conserves nonre-
newable resources like petroleum and natural gas while simultaneously reducing dependence
on imported crude oil. As a result of lower heavy hydrocarbon content, these fuels are clean-
er burning and do not add further carbon dioxide to the environment.
A Novel Solid-Acid Catalyzed 1-Butene/Isobutane
Alkylation Process
Alkylation reactions are employed to convert light refinery gases (C3-C5) into gasoline
compounds (C7-C9). Alkylates constitute roughly 15% of the U.S. gasoline pool. At present,
industrial alkylation employs either hydrofluoric acid or sulfuric acid as a catalyst. For more
than three decades, numerous solid acid catalysts have been explored as environmentally safer
alternatives to liquid acids. However, solid-acid catalysts deactivate rapidly due to coke reten-
tion in the pores. In gas-phase media, the heavy coke precursors (such as olefmic oligomers)
are poorly soluble. In liquid-phase reaction media, the transport of coke precursors out of the
catalyst pores is severely restricted resulting in their readsorption and transformation to con-
solidated coke. The work of Dr. Bala Subramaniam at the University of Kansas employs
supercritical reaction media, which offer a unique combination of liquid-like density and gas-
like transport properties for the effective removal of the coke precursors. Employing carbon
dioxide (Pc = 71.8 bar; Tc = 31.1 °C) as an environmentally benign solvent, 1-butene/isobu-
tane alkylation was performed at supercritical conditions resulting in virtually steady alkylate
(trimethylpentanes and dimethylhexanes) production in a fixed-bed reactor on solid acid cat-
alysts (HY zeolite, sulfated zirconia and Nafion) for several days. The carbon dioxide-based
supercritical process thus offers an environmentally safer alternative to conventional alkyla-
tion by eliminating a major technological barrier impeding the application of solid acid
catalysts in alkylation practice.
A Novel Waste Minimization Approach: Production of
Carbon-Based Catalyst or Sorbentfrom Biosolids
Biosolids, a byproduct of wastewater treatment facilities, are currently a major environ-
mental concern. Identified problems associated with the management of biosolids are the
hazardous content, the large mass produced, the difficulties associated with its treatment, and
the few available disposal methods. Furthermore, the production of biosolids has been
increasing due to an increase in the world population. In 1995, the United States produced
9 million tons of biosolids and is expected to produce 11 million tons/year by the year 2000.
Transformation of biosolids is a novel and innovative idea for waste minimization and recy-
cling at wastewater treatment facilities.
20
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An innovative process was developed to convert biosolids to carbon-based sorbents and
catalysts. The feedstocks for the process were biosolids produced at a sewage treatment plant
(Spring Brook Water Reclamation Center in Naperville, Illinois) and wastewater treatment
sludge produced in the paper mill industry (Fort James Corporation in Green Bay,
Wisconsin). The research conducted at the Illinois Institute of Technology suggests two new
innovative ideas for the production of activated carbon from carbonaceous waste material: 1)
exposure of the chemically activated raw material to light and humidity in a controlled envi-
ronment can enhance the surface pore structure of activated carbons by about 20%, and 2)
the time and energy required for the drying of sludge can be reduced by about 98% if
microwave drying is used. The surface properties of the produced carbons were effectively
controlled by varying different chemical, surface, and physical activation processes. This pro-
ject demonstrates a tremendous potential for alleviating serious environmental problems
associated with the mass production and disposal of untreated sludge by development of a
process for converting sludge to activated carbon and catalyst.
Overcoming the Recalcitrance ofCellulosic Biomass and
Envisioning the Role of Biomass in a Sustainable World
This project addresses technical and visionary issues associated with utilizing plant bio-
mass, the only foreseeable sustainable source of organic fuels, chemicals, and materials. The
project involves multiple topics related to consolidated processing, a widely applicable poten-
tial breakthrough in cellulose processing entailing production of cellulose enzymes, hydrolysis
of biomass components, and fermentation of resulting soluble carbohydrates in a single
process step. Additional project elements aimed at overcoming the recalcitrance of cellulose
biomass encompass aspects of applied enzymology and microbiology, kinetics and reactor
design for enzymatic hydrolysis of cellulose, pretreatment of biomass using compressed hot
water, and conversion of paper sludge. Process design and analysis work support the con-
tention that advanced biomass-based processes have the potential to be cost-competitive with
petroleum-based processes even at low oil prices. Accomplishments involving resource and
policy analysis include analysis that identifies and explores the potential of biomass-based
processes to have near-zero net CCh emissions, prioritizes among uses for the large but ulti-
mately limited biomass resource, and seeks to reconcile the vast range of estimates for the
magnitude of potential biomass availability for industrial uses.
Pollution Preventing Lithographic Inks
Conventional printing techniques use solvents that contribute to pollution through evap-
oration and cleaning processes. Professor Cussler has developed a new ink that eliminates
these emissions. A pollution preventing lithographic ink works conventionally at pH less
than 7, but becomes its own emulsifying agent at higher pH. As a result, it can be washed off
printing presses with aqueous base. The emulsification kinetics are not predicted by conven-
tional correlations. Instead, they are consistent with an interfacial reaction between hydroxide
and ink resin, which produces a soap layer that can be removed by shear. The results imply a
strategy for other pollution preventing technologies.
Dr. Lee R. Lynd,
Department of
Engineering,
Dartmouth College
Professor E.L. Cussler,
Department of
Chemical Engineering
and Materials Science,
University of
Minnesota
21
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Dr. Stephen Thompson,
The Center for Science,
Mathematics and
Technology Education,
Colorado State
University
Dr. Rajender S. Varma,
Texas Regional
Institute for
Environmental Studies,
Sam Houston State
University
Dr. Nancy W.Y. Ho,
Laboratory of
Renewable Resources
Engineering, Purdue
University
22
Small Scale Chemistry: Pollution Prevention in
Inorganic Chemistry Instruction Program
Small-Scale Chemistry (SSC) techniques developed by Dr. Stephen Thompson at
Colorado State University build pollution prevention, waste minimization, and student safe-
ty at the design stage rather than controlling it at the disposal stage. SSC inherently manifests
characteristics of "green chemistry" by incorporating the principles and methodologies of
source reduction. The SSC techniques and experiments result in significant waste reduction
and reduced risk of chemical exposure to both students and faculty. This is achieved through
innovative experiments and methodologies that use alternate reaction conditions and alter-
nate synthesis pathways. The concepts of SSC evolved as a solution to many of the serious
problems (e.g., cost, safety, waste disposal, pedagogy) associated with chemistry laboratory
instruction. Drops of chemicals used as their own containers replace liters of chemical haz-
ardous waste in breakable glassware. The innovative use of high-tech plasticware designed for
genetics research reduces cost while maintaining safety and sophistication. SSC techniques
and methodologies provide a realistic approach to green chemistry and allow academic insti-
tutions to institutionalize lasting behavioral changes. SSC provides an easy to implement,
affordable, and wide application remedy to a real environmental management problem faced
by most college and university chemistry programs.
Solvent-Free Chemical Synthesis
An environmentally benign solvent-free synthetic approach was developed by Dr.
Rajender S. Varma at Sam Houston State University. This approach utilizes neat reactants
either in the presence of a catalyst or catalyzed by the surfaces of recyclable support(s) such
as alumina, silica, clay, and 'doped' surfaces such as NalCVsilica, iron(III) nitrate-clay
(clayfen), and persulfate-clay. This occurs under microwave irradiation conditions thus pro-
moting reduction of solvents at the source and excess chemicals in manufacturing. This
pollution preventive strategy has been targeted to industrially significant cleavage, condensa-
tion, oxidation, and cyclization reactions that currently employ toxic, corrosive, and irritant
chemicals and generate hazardous waste. The technology uses material science, molecular
modeling, and synthetic organic chemistry expertise and addresses the needs of broad chem-
ical community (polymers, pharmaceuticals, and fine chemicals) by efficient production of
valuable intermediates (enones, imines, enamines, nitroalkenes, oxidized sulfur species, and
heterocycles). Further, the technology teaches pollution prevention to a younger generation
of scientists and is extendible to in situ destruction of pollutants and hazardous waste.
Successful Development of Hazard-Free, User-Friendly
Genetically Engineered Microorganisms for Effective
Production of Environmentally Friendly Chemicals from
Renewable Biomass using Green Chemical
Methodologies
Ethanol is an effective, environmentally friendly, nonfossil transportation biofuel that pro-
duces far fewer pollutants than gasoline. Furthermore, ethanol can be produced from
plentiful, domestically available, renewable cellulosic biomass, thereby reducing our nation's
dependence on imported oil. Although ethanol has been produced by the fermentation of
glucose-based feedstocks with Saccharomyces yeasts since the preindustrial age, the conversion
of cellulosic biomass to ethanol has presented a major challenge. This is because cellulosic
biomass contains two major sugars, glucose and xylose, and the Saccharomyces yeasts cannot
-------
ferment xylose to ethanol. Dr. Ho, at Purdue University, has developed genetically engineered
Saccharomyces yeasts that not only ferment xylose, but effectively coferment glucose and
xylose to ethanol. The genetically engineered yeasts produce at least 30% more ethanol from
cellulosic biomass than the unengineered parent yeasts.
Lactic acid, an important industrial feedstock in the manufacture of inexpensive,
biodegradable plastics from renewable biomass, is traditionally produced by the fermentation
of glucose with lactic acid bacteria. Lactic acid bacteria, however, grow very slowly and can-
not tolerate 1 to 2% lactic acid. Dr. Ho's group has succeeded in genetically engineering a
safe, effective microorganism that can produce lactic acid more than twice as efficiently as lac-
tic acid bacteria. These examples demonstrate that genetic engineering technology, guided by
the principle of green chemistry, is a powerful tool in modifying microorganisms for the pro-
duction of important chemicals from renewable biomass.
Synthetic Dyes Based on Toxicological Considerations
This nomination pertains to the design of nontoxic alternatives to currently used metal-
complexed dyes containing metals designated as priority pollutants. Specifically,
iron-complexed dyes were synthesized as substitutes for metal-complexed dyes currently used
in situations requiring colorants possessing very high photostability and resistance to removal
under wet conditions. The dyes investigated were iron (Fe) complexes of ligands and provid-
ed the foundation for a pollution prevention approach to environmental problems associated
with the manufacture and use of organic dyes based on chromium (Cr) and cobalt (Co). As
a starting point for this study, the Freeman group synthesized and evaluated Fe-complexed
analogs of commercial azo and formazan dyes containing Cr or Co. Fe(II) sulfate was
employed as the metallizing agent because it has exhibited low aquatic toxicity in studies.
This investigation led to the discovery of nontoxic alternatives to high-volume chromi-
um-based commercial black dyes, without compromising the desirable photostability of the
latter. In addition, red and blue 1:2 Fe-complexed dyes (1 iron atom per 2 dye molecules)
were discovered, an achievement heretofore unreported and presumed unachievable. An
explanation for the dull colors that have traditionally characterized Fe-complexed dyes was
also developed, providing a basis for further achievements in this area.
Toward Synthetic Methodology "Without Reagents"
Increased "Effective Mass Yield" for Pharmaceuticals by
Tandem Enzymatic and Electrochemical Oxidations
and Reductions
The prevention of pollution at its source is addressed by the replacement of currently used
methods of oxidation and reduction (i.e., all based on metal reagents) with enzymatic and
electrochemical techniques (i.e., all performed in water, alcohols, or other environmentally
acceptable solvents). The combination of enzymatic transformations with electrochemistry,
along with efficient design, yields unprecedented brevity in the attainment of important
pharmaceuticals from metabolites of the arene cis-diol type. Halogenated aromatic com-
pounds, viewed in many cases as harmful to the environment, are enzymatically converted to
useful synthons and effectively removed from the hazardous waste pool, with added eco-
nomic benefits of strategic conversion that would not be available through outright
incineration of such compounds. It must be emphasized that the enzymatic conversion of the
toxic aromatic materials takes place in the very first step of the synthetic pathway and that all
Harold S. Freeman,
Ciba-Giegy Professor of
Dyestuff Chemistry,
North Carolina State
University
Professor Tomas
Hudlicky, Department
of Chemistry,
University of Florida
23
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subsequent intermediates are harmless. The residual mass from enzymatic or electrochemical
processes is judged suitable for disposal to municipal sewers, thus further reducing the
amount of actual waste. The synthesis of a homochiral cyclitol from halobenzene by several
steps involving essentially no reagents serves as the illustration of the technology. Given that
the length of a synthesis plays a direct role in the attendant accumulated waste mass for the
process, it follows that short and efficient syntheses lead to lesser accumulation of waste and
thus reduce pollution at the source.
Professor David E.
Bergbreiter,
Department of
Chemistry, Texas A&M
University
Use of Soluble Polymers to Recover Catalysts and to
Control Catalytic Reactions
New strategies for use and recovery of homogeneous catalysts and for carrying out chem-
ical processes are of increasing interest because of problems associated with the use of organic
solvents and the costs associated with purification and removal/disposal of byproducts. This
nomination recognizes the work by Bergbreiter's group at Texas A&M that uses polymeric
ligands and new separation strategies to facilitate homogeneous catalysis. This technology
uses the well-known properties of polymers to recover and separate catalysts and ligands for
reuse. By employing relatively simple polymer chemistry, a wide variety of known homoge-
neous catalysts can be attached to such polymers without significant alteration of their
reactivity or selectivity. Separation and recovery strategies that use solid/liquid separation of
precipitate polymers or liquid/liquid separations of polymer solutions/product solutions have
both been demonstrated. The utility of simple linear polymers in formation of aqueous and
fluorous phase soluble catalysts has also been demonstrated by this work. Finally, this tech-
nology has also demonstrated a unique approach to regulate and control reactions using
soluble polymer-bound "smart" ligands that precipitate on heating.
Professor Alan W.
Weimer, Department of
Chemical Engineering,
University of Colorado
Vibrating Fluidized Bed Combustion Nitridation
Processing Using Concentrated Solar Energy
The best way of managing pollution from industrial processes is to devise ways to mini-
mize its production. This is especially true in the synthesis of chemical compounds. New
concepts developed at the University of Colorado attack the problem on four levels: maxi-
mizing yields, avoidance of post processing, use of nontoxic precursors, and minimizing
energy consumption. Professor Weimer and his students have demonstrated model ceramic
synthesis systems that have high yield, avoid needle-like particle growth induced by ther-
mophoresis, use metal powders and nitrogen as precursor material, and use sunlight as the
source of energy for synthesis reactions. High-quality powders of silicon nitride and of alu-
minum nitride, both technologically important materials, have been produced as proof of
concept. The use of a directed energy source for the synthesis produces higher quality mate-
rials and reduces the energy budget, thus reducing the pollution associated with conventional
heating. The use of concentrated sunlight, instead of a laser beam or arc lamp, further reduces
the consumption of fossil fuels to provide the energy for the beam.
24
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Washington State Pollution Prevention, Health, and
Safety Initiative in Academic Chemistry Laboratories
In 1997, the Washington State Department of Ecology and the Educational Service
District 101 began planning workshops to educate chemistry teachers on green chemistry
techniques, health and safety issues, and proper hazardous waste management. The work-
shops included detailed information on better laboratory practices that reduce the risk of
accidents, maintain employee and student health and safety, and reduce the use of hazardous
substances and generation of hazardous waste. Green chemistry techniques such as microscale
chemistry and conducting experiments that use only nontoxic substances or less toxic chem-
icals were also taught. The workshops also included environmental, health, and safety
regulations that schools must observe in the state of Washington. A Step-by-Step Guide to
Better Laboratory Management was produced and used as part of the workshops.
A coordinated multiagency team was formed to plan and implement the workshops. Six
workshops were held throughout the state of Washington in the spring of 1998. Ecology,
ESDs, OSPI, Washington State Department of Health and Washington State Department of
Labor and Industries developed and implemented the workshops. Over 300 chemistry
instructors attended throughout the state.
Ecology trained six staff members and King County Hazardous Waste Program (Metro)
staff to conduct site visits at middle and high schools throughout the state of Washington.
The lab team was trained to: 1) Organize chemicals in compatible storage system; 2) Tag or
remove chemicals of concern that are extremely hazardous, unstable, in poor condition or in
excess; 3) Sort waste chemicals into Department of Transportation shipping categories; 4)
Labpack waste chemicals for shipping and disposal; 5) Explain proper hazardous waste man-
agement and disposal; 6) Assist with preparing a chemical hygiene plan for laboratory; 7)
Assist with creating a complete and up-to-date chemical inventory. To date, about 100
schools have been visited.
Washington State
Department of Ecology
Waste Biomass Utilization in the Production of a
Biodegradable Road Deicer
The effective utilization of bio mass and the residuals from agricultural and food process-
ing operations in the production of fuels and chemicals is one of the cornerstones of policies
aimed at energy conservation and sound environmental management. Biomass wastes such
as liquid whey effluents from the dairy industry are an undue burden on the environment
due to the high biochemical oxygen demand (BOD) of such wastes. Whey is a byproduct
from cheese and casein production operations and contains about 5% lactose and 0.1 to
0.8% lactic acid. About 50% of the total U.S. milk production is used in the production of
cheese, resulting in the generation of approximately 57 billion pounds of liquid whey per
year. Acid whey containing lactose and lactic acid has a very high BOD of about 40,000
mg/L. As such, this waste can be a tremendous burden to the environment if it is discharged
without controls. Treatment of the high BOD waste is both capital and energy intensive.
Thus any viable reuse option is likely to offer large savings in cost and energy utilization.
The work of Alexander E Mathews at Kansas State University is aimed at examining the
use of whey permeate in the production of a road deicer substitute for sodium chloride. Each
year, about $2 billion are spent on U.S. highways alone to maintain driveable conditions dur-
ing winter. The bulk of this expenditure is on the application of chemical deicers, principally
sodium chloride (NaCl). The annual use of NaCl has increased rapidly from 0.5 million tons
in 1947 to about 30 million tons in 1996. Many roads and highways in the snowbelt may
Alexander P. Mathews,
Department of Civil
Engineering, Kansas
State University
25
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Dr. Claudia Lage
Nassaralla, Department
of Metallurgical and
Materials Engineering,
Michigan Technological
University
receive up to 60 tons of salt per km during the winter season. Currently used deicers, such as
NaCl, cause extensive corrosion-related damage to the highway infrastructure and environ-
mental damage by contaminating water supplies and soils.
The main objectives of Mathews' work were to examine the use of biomass wastes in the
production of deicers, calcium magnesium acetate (CMA), and calcium magnesium propi-
onate (CMP). A novel two-stage fermentation process was developed to utilize and convert
inexpensive substrates such as whey permeate to acetic and prop ionic acids for use in the pro-
duction of the deicer. The two-stage process has a substrate conversion efficiency of about 9%
compared to 53% for a single-stage process. Acid concentrations up to 60 gm/1 were obtained
in batch and fed-batch fermentations. In addition, the source of calcium and magnesium in
the CMA/CMP deicer was obtained from water plant treatment sludges (water treatment
operations such as coagulation, flocculation, and chemical softening result in the production
of large quantities of solid byproducts containing calcium and magnesium that can be used
in the production of CMA/CMP deicer).
Waste Reduction and Recycling of Magnesite-Chrome
Refractory into the Steelmaking Process
The primary objective of the work of Dr. Claudia Lage Nassaralla at Michigan
Technological University is to develop the technological basis to minimize the formation of
hexavalent chromium (Cr6+), a well-known carcinogen, within magnesite-chrome refractory
during its production and use in industrial processes. Magnesite-chrome is a high-
temperature refractory used in the steel, copper, cement, and glass industries because of its
excellent resistance to thermal shock and chemical attack. The spent magnesite-chrome
refractory is classified as a hazardous material by EPA when it contains high levels of Cr6+. Of
all the chromium ions, Cr6+ is the only one soluble in water, and as such, can give rise to detri-
mental effects on the environment and food chain because it is strongly oxidizing and easily
penetrates human tissue. The origin of Cr6* in the refractory is due to the reaction between
CaO and C^O^. No other oxide present in the refractory is known to form Cr6+. Until
recently, spent magnesite-chrome refractory was normally disposed of in authorized landfills.
Currently, spent magnesite-chrome refractories with a Cr6+ content above 5 pprn must be
treated before disposal.
The technology being developed by Dr. Nassaralla has the potential to minimize the for-
mation of Cr6+ by carefully controlling the brickmaking and Steelmaking practices. It will also
allow for the reduction of hexavalent to trivalent, and to chromium metal, di- and trivalent
chromium by recycling the brick into the Steelmaking converter and the electric arc furnace,
respectively. No type of preprocessing of the solid waste or installation of additional equip-
ment will be necessary. The waste material can be treated on site, and the contaminated bricks
can also be recycled as part of the flux that has to be added in the Steelmaking converter to
absorb the oxides generated in the production of steel or in the electric arc furnace as a source
of chromium in the production of ferro-chromium. The information generated from this
project can also be used by the copper, cement, and glass industries to design their practices
to minimize the formation of Cr6*. Besides the savings associated with the costs of disposing
spent chrome-magnesite brick, the recycling of Cr6* in the production process and its con-
version to chromium metal, di- and trivalent chromium will avoid contamination of the
environment by possible leaching of Cr6+ after dumping.
26
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Water as Solvent for Chemical and Material Syntheses
Rather than sacrificing one or the other, to synchronize the advancement of science and
technology with the advancement of green chemistry is the key feature of the research carried
out by Tulane. A range of technologies has been developed that uses water as solvent for
chemical, pharmaceutical, and material syntheses. The technologies developed not only offer
many benefits for human health and the environment, but also the use of water as solvent
plays an essential role in the success of this research. The use of large quantities of organic sol-
vent for industrial scale operations eventually adds to environmental problems. In fact,
volatile organic compounds are the principal pollutants of all organic compounds. On the
other hand, water is nontoxic, nonexplosive, nonflammable, as well as the basis and bearer of
life in nature.
Numerous biochemical reactions affecting the living system have inevitably occurred in
aqueous medium. On the other hand, most organic reactions and syntheses have been car-
ried out in organic solvents. At Tulane, Professor Chao-Jun Li has developed various synthetic
methodologies by using water as solvent. By using these methodologies he has synthesized
biologically important natural products, novel electronic and optical materials, and nano-car-
bon materials. In most cases, the studies have the dual advantages of being aqueous and being
"atom economical." Also in most cases, the use of water as the reaction solvent does not only
make them environmentally friendly, but also essential to the success of this research.
Waterborne Coating Formulations for Video Tape
Manufacture
Magnetic tape technology is an important component of the information age and main-
taining a domestic tape manufacturing capability is important to the U.S. economy.
Magnetic tape is manufactured by a continuous web coating process that uses organic sol-
vents, including tetrahydrofuran, methyl ethyl ketone (MEK), methyl isobutyl ketone
(MIBK), toluene and cyclohexanone. MEK, MIBK, and toluene are on the list of 189 haz-
ardous air pollutants and on the list of 18 chemicals for the EPA's 33/50 voluntary pollution
reduction program.
Waterborne magnetic tape coating formulations were designed at the University of
Alabama and used to prepare experimental magnetic tape samples in a pilot coating trial. The
formulations contained a blend of a water-dispersed polyester and an ethylene/vinyl chloride
copolymer emulsion. The coatings were thermally cured with a melamine-formaldehyde
cross-linker to give tensile properties that were comparable to a standard solvent-based binder
composition. The pilot tape trial used existing processing equipment, including calendering
and slitting. The tape had good magnetic properties and excellent adhesion between the pig-
mented magnetic layer and the base film, easily exceeding the 8 mm helical scan tape
standard of 0.96 N peel force. An economic impact analysis for the case of using the water-
borne video tape coating process in a conventional tape manufacturing plant showed an 11
percent decrease in hourly operating costs. The solvent-based process generated almost 650
kg of organic solvent per hour operation, while the waterborne process generated less than 5
kg methanol (from the melamine-formaldehyde cross-linker) per hour. In addition to pollu-
tion prevention, there was a clear economic incentive to adopt the waterborne video tape
manufacturing process.
Professor Chao-Jun Li,
Department of
Chemistry, Tulane
University
Dr. David E. Nikles,
Department of
Chemistry, University
of Alabama
27
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BIOCORP, Inc.
Burch Company
Entries from Small Businesses
Biodegradable Thermoplastic Material
Mater-Bi™ is a completely biodegradable and compostable resin, which has the physical
and mechanical properties of conventional plastics. Mater-Bi™ is designed to be used in the
manufacture of a wide range of disposable products such as trash bags, shopping bags, food
serviceware, and packagings. Mater-Bi™ is a product technology that offers enormous advan-
tages for dealing with the problems of solid waste disposal. Disposal of conventional plastic
products, which constitute the largest share of disposable products, has a significant negative
impact on the environment. Typically, disposable products are landfilled and rapidly dimin-
ish landfill capacity. Being compostable, disposable products made of Mater-Bi™ are fully
recyclable. Biodegradable food serviceware, for example, presents a significant opportunity
for reducing the volume of the solid waste stream. In 1994, nearly 39 billion pieces of dis-
posable cutlery (knives, forks, and spoons) were used in the United States. More than 113
billion disposable cups and nearly 29 billion disposable plates were used. Biodegradables are
being developed for medical products, textiles, and other new and significant applications.
Such products can be transformed into much needed composts and soil amendments for
agricultural and horticultural use. Mater-Bi™ resin used for films and sheets is made of starch
and a polymer, polycaprolactone. Biodegradation time is between 20 and 45 days in com-
posting conditions. Mater-Bi™ resin used for dimensionally stable injection molded items is
made from completely natural products, including cotton seeds and cornstarch.
Biodegradation time is between 75 and 120 days in normal composting conditions.
Burch Apparatus and Method for Selectively Treating
Vegetation to Reduce Pesticides and Fertilizer Use,
Eliminate the Release of Certain Toxins to the
Environment, Reduce Pesticide Runoff, and Reduce the
Potential of Worker Exposure to Toxic Substances
The Burch Wet Blade® is a new discovery and a revolutionary apparatus and method for
controlling vegetation. The Burch Wet Blade® allows for the selective application of various
fluids, such as pesticides, growth regulators, biologicals, and fertilizers (hereinafter "pesti-
cides"), to vegetation by causing a minute amount of pesticide to be immediately absorbed
into the vascular system of a plant at the moment the plant is cut by a blade. This method of
treatment is made possible by bringing a pesticide into contact with a mowing blade designed
not to cause a haphazard chemical spray, but rather a precise transfer of pesticide from only
the bottom surface of the blade into the vascular system of a plant. The Burch Wet Blade® is
a nonspray, enclosed system that provides precise pesticide application thereby reducing the
quantity of pesticide needed and eliminating worker exposure and unwanted releases of
pesticide.
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CerOx Process Technology for Non-Thermal Destruction
of Organic Hazardous Wastes
CerOx (Cerium Oxidation) Corporation has commercialized its process for destroying
hazardous organic waste streams. The unique process, which converts toxic wastes into CC^
and water, is an economical alternative to incineration and landfill. The process also can be
operated on site, eliminating the need for transportation at reduced cost to the generator.
Seven sizes of systems have been designed to meet the needs of various customers ranging
from 300 pounds of destruction per day to over 3 tons per day. The CerOx process is an elec-
trochemical process that allows for the destruction of organic hazardous wastes at near
ambient conditions. At the heart of the system is a proprietary reactor cell. The cell is
designed to be manufactured in volume from high-density plastics, using advanced injection
techniques. The result is a system that is inexpensive to manufacture, service, and replace. In
addition, the necessary data for EPA-required reports is recorded and stored. The flexible scal-
ability of the CerOx Process allows it to be placed onsite for destruction of hazardous waste
materials at their point of origin thereby eliminating the transportation of these wastes. The
relatively mild reaction conditions of the CerOx Process eliminates any of the explosion
potential associated with current high-temperature and/or pressure thermal methods such as
incineration and molten metal pyrolysis.
Chemically Modified Crumb Rubber Asphalt
A process was developed for producing Chemically Modified Crumb Rubber Asphalt
(CMCRA). The Chemically Modified Crumb Rubber (CMCR) was produced by using
H2O2 (free radical generator; in this case, carbonium ion generator) to produce carboxylic
sites on the surface of crumb rubber by utilizing the oxygenated sites of carbon black [these
oxygenated sites will obtain hydrogen from a source and then be converted into carboxylic
acid (COOH) groups]. These sites in crumb rubber could possibly be the cause of devul-
canization and could interact with functional groups available in asphalt, resulting in a
homogenous modified asphalt. Compared to controls, asphalt modified using this process
has improved rheological properties at both low and high temperatures, as well as improved
separation and homogeneity characteristics. Several asphalts were tested and were found to
have improved rheological properties (high and low temperature), homogeneity, and separa-
tion characteristics. Since rubber, the main component of CMCR, is known as a poor
conductor of heat, it is probable that CMCRA can be used in constructing asphaltic pave-
ments at lower pavement temperatures than other neat or modified asphalts. The first
pavement test installation was successfully made at a lower pavement temperature than that
recommended by the Connecticut Department of Transportation, suggesting that CMCRA
can extend the pavement construction season.
Development and Commercialization of High-Value
Chemical Intermediates from Starch and Lactose
Synthon has developed a method for the utilization of high-volume carbohydrate feed-
stock for the production of fine chemicals. One of the major tasks facing the chemical
industry today is the identification and development of high-volume, renewable, commer-
cially viable raw materials that can assume a large part (if not all) of the central role that
oil-based materials play in that industry. Starch is one of the most abundant materials obtain-
able in pure form from biomass. As a raw material for the practice of chemistry from
environmentally benign and renewable resources, it holds much promise and seemingly as
CerOx Corporation
SaLUT Inc.
Synthon Corporation
29
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Burlington Chemical
Company
many challenges. Three of the most important aspects of starch structure and chemistry that
are in step with requirements for a green chemistry feedstock are its solubility in water, the
richness of functional groups, and its optical purity. The same is true of lactose, a material
that is underutilized and available in thousands of metric tons per year from cheese making.
These three promising features represent the three most difficult technical challenges in
attempts to use starch and lactose as raw materials. They are practically insoluble in other
environmentally friendly solvents such as alcohols and esters thus limiting the range of rele-
vant chemistries. The high density of functional groups (polyhydroxylation) has made it
(until now) nearly impossible to do anything useful with these on a grand scale in a selective
fashion. The optical purity is embodied in functionalities that make conserving it a challenge.
Over the past 3 years, Synthon Corporation has been working to overcome these techni-
cal barriers by developing, demonstrating, and commercializing a new chemistry that will
fundamentally revise the position of these two important and critical raw materials on the list
of renewable resources for manufacture of chemical commodities. In the process, these mate-
rials are oxidized in dilute aqueous sodium hydroxide under controlled conditions with
peroxide anion to form (S)-3,4-dihydroxybutyric acid and 2-hydroxyacetic acid (glycolic
acid) with very high conversion. (S)-3,4-dihydroxybutyric acid can be converted to the lac-
tone by acidification and concentration. Glycolic acid and the lactone can be utilized in the
production of a variety of fine chemicals for particular use in the pharmaceutical, agrichem-
ical, and polymer industries. Glycolic acid, for example, is used in the manufacture of
specialty polyesters and in the preparation of paints. It is normally made by the environ-
mentally unfriendly method of chlorinating acetic acid and hydrolyzing the chloro derivative
with sodium hydroxide. The Synthon product brochure now lists over 30 such products
available from gram to ton quantities. The process has allowed Synthon to take a substantial
lead in the area of high-valued chiral intermediates through the green chemistry approach
where the pool of natural raw resources is tapped.
Development of a Practical Model and Process to
Systematically Reduce the Environmental Impact of
Chemicals Utilized by the Textile and Related Industries
It was discovered in the early 1980s that discharges from textile dyeing and finishing oper-
ations were adversely impacting publicly owned waste treatment facilities. The results of early
toxicity reduction evaluations pinpointed toxic and poorly degraded textile chemicals and
surfactants as culprits. It was decided that elimination of toxic agents prior to formulation
was an important long-term objective to provide for a sustainable textile industry in the
United States. To achieve products "Designed for the Environment," a means to inexpen-
sively screen chemicals and raw materials and communicate results internally and externally
to consumers and regulators was needed.
It was discovered by Burlington Chemical that the results from three OECD tests, OECD
301D, 202, and 209, could be related in an expert computer system (AQUATOX®) to design
textile chemicals with greatly reduced environmental impacts. This discovery led to the devel-
opment of a waste/toxicity reduction program, Burco® Care, based on this information.
Burco® Care has resulted in the production of low-impact wet processing chemicals. It
spawned a system of comparing textile chemicals for environmental impact that can be uti-
lized in purchasing decisions by textile manufacturers and has been found suitable by U.S.
textile market leaders. Burco® Care is a giant leap away from simple regulator compliance to
the creation of a systems-based, thinking approach to building value by reduction of risk and
improvement of the environment.
30
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High Energy Efficiency, Environmentally Friendly
Refrigerants
Environmentally safe alternatives to CFC, HCFC, and HFC refrigerants are badly need-
ed. The phaseout of CFCs and HCFCs and increasing concern about greenhouse gases create
the urgent need for nontoxic, nonflammable, environmentally safe refrigerants with high
capacity and energy efficiency Dr. Jonathan Nimitz and his co-inventor, Lance Lankford,
have discovered and patented a family of improved refrigerants based on blends containing
trifluoromethyl iodide (CFal). CFal has attractive physical properties, is a combustion
inhibitor, has zero ozone depletion potential (ODP), low global warming potential (GWP),
and relatively low toxicity Cp3l can be combined with high-capacity, energy-efficient, envi-
ronmentally friendly, but flammable refrigerant compounds to obtain excellent refrigerant
blends that remain nonflammable. The result is an energy-efficient, environmentally friend-
ly, safe refrigerant.
The inventors and Dole Food Company have formed a new company, Ikon, Inc., to sup-
port testing and commercialization of the refrigerants. The first formulation developed, Ikon®
A, has extremely low GWP and can be used in R-12 or R-134a systems. Ikon® A has been
demonstrated for over 3 years in Dole Food Company refrigerated transports, with excellent
results. Ikon® A was also tested in a newR-134a domestic refrigerator, with results of 19 per-
cent higher energy efficiency and 15% greater volumetric cooling capacity versus R-134a.
Ikon® B was developed as a less expensive version of Ikon® A; it has been tested and demon-
strated in refrigerated transport units, a 5-ton water chiller (sponsored by NASA Kennedy
Space Center), and a new R-134a domestic refrigerator (sponsored by EPA). The use of Ikon®
refrigerants will result in improvements to human health and air and water quality, reduc-
tions in skin cancer, and ecological and crop damage from UV radiation.
The LCAPIXModule Software: Combining Life Cycle
Assessment with Activity Based Costing to Assist in
Preservation of the Global Environment and Sustained
Economic Growth
Life cycle assessment (LCA) is a technique that was developed in the late 1960s to address
the socioeconomic and politically charged issues of use and reuse of all man-made products,
processes, or services. The LCAPIX module is a software tool that efficiently enhances facili-
tation of both the LCA process and entices industrial management (of chemical and other
industries) to perform these studies by yielding a simultaneous activity based cost (ABC)
analysis .
By using an industrial engineering approach employing drivers and driver values, the
model and relational database provides for a unique combination of two strategies that com-
plement and enhance the implementation of an Environmental Management Strategy
(EMS). This software tool has been used to compare different products, processes, and ser-
vices for not only their potential environmental burden potential (i.e., using different
valuation techniques such as selected weighted emphasis on global warming, ozone depletion,
acid rain, deforestation, or biodiversity), but also to understand and illustrate how different
techniques can be used to diminish these burdens while improving internal, external, unseen,
or unknown ("hidden") costs. This software tool is multifunctional, providing inexpensive,
simple, rapid LCA strategic or environmental comparisons of any product, process, or ser-
vice.
Environmental
Technology and
Education Center, Inc.
(ETEC)
KM Limited Inc.
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TechMatch,
Incorporated
Novon International
Solvent Kleene Inc.
N-Methylmorpholine-N-Oxide (NMMO): A Novel,
Nontoxic Solvent for Cellulose as Source Reduction in
the Production of Textile Fibers
For decades, scientists had been searching for an environmentally friendly means of form-
ing a cellulosic fiber. The standard procedure for producing cellulose fibers has been the
viscose process, invented in 1894. There were no neutral organic solvents for dissolving cel-
lulose, until 1965 when Dee Lynn Johnson, working in the laboratories of Eastman Kodak,
discovered that N-methylmorpholine-N-oxide (NMMO) is a solvent for cellulose. In addi-
tion, he demonstrated that the cellulose solution can be filtered and the cellulose filaments
regenerated by precipitation into water. Furthermore, the NMMO could be recovered by
evaporating the water and reused. This new solvent has now been commercialized by
Huntsman Petrochemical Corporation, and several fiber manufacturers have developed com-
mercial processes for producing the fibers. Fibers made by use of NMMO are called lyocell
fibers, meaning cellulose spun from solution. The previous viscose process produces rayon
fibers, but it requires a chemical reaction between carbon disulfide and cellulose in the pres-
ence of a strong base to produce a xanthate complex. Carbon disulfide is highly flammable
and toxic to humans as well as being a greenhouse gas. Further, to produce fibers the xan-
thate must be regenerated by extrusion into an acid coagulating bath where it decomposes
and produces polluting byproducts that are discharged into water.
Natural Recycling of Plastics Through Chemical and
Biological Degradation
Modern synthetic polymer manufacturing has reached a high level of efficient resource
utilization. An energy-efficient system of producing additives based on natural polymers and
other chemicals provides an effective means of achieving an alternative to plastics recycling
by allowing timed degradation followed by systemic incorporation back into natural organic
cycles. The system is based on the continued use of conventional plastics processing machin-
ery and results in a product that has the advantages of existing plastics materials with the
added benefit of timed degradation in appropriate environments. After disintegration, the
elements are available to be incorporated into humus and other soil constituents. The addi-
tives work by providing degradation catalysts based on natural organic unsaturated fatty acids
and other unsaturates and benign metal cations with multiple oxidation states (such as iron).
By combining these with conventional thermoplastic polymers, oxidative degradation of typ-
ical plastics can be achieved. In addition, a naturally biodegradable polymer, such as starch or
cellulose, is combined initiating biological attack and microbial colonization of the plastic. In
natural environments this starts a slow oxidative biodegradation, similar to that for lignin,
which allows incorporation of the carbon directly into humus and growing plants.
Nonhazardous Degreaser That Degreases as Efficiently as
Trichloroethane and Outperforms Aqueous Products
Degreasing techniques have relied heavily on chlorinated solvents. While these solvents
are highly effective in removing grease and oils from metals, at the same time they raise seri-
ous environmental and health concerns. Ozone depleting products like 1,1,1 Trichloroethane
(1,1,1 TCA) and Trichlorotrifloroethane (CFC 113) have been phased out under the 1990
Clean Air Act Amendment, leaving users of these products little choice other than to replace
them. A number of new nonhazardous cleaners have been introduced as alternatives, but few
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provide the effectiveness of a chlorinated solvent and most require users to accept a longer
cleaning process and add costly new equipment. Solvent Kleene, Inc. developed D-Greeze
500-LO as a safe replacement degreaser/cleaner that does not force companies to compro-
mise cleaning performance for safety. In independent testing, D-Greeze 500-LO was
identified as a safe alternative that could also outperform trichloroethane. While safe prod-
ucts such as aqueous-based cleaners are slow to perform, require heating, and involve an
investment in costly new equipment and processes such as wastewater treatment, D-Greeze
500-LO can be easily integrated into an existing cleaning environment without a significant
investment in new equipment or processes. Additionally, D-Greeze 500-LO is recyclable. A
spent solution can be easily recovered and reused, minimizing both the hazardous waste
stream generated and purchases of new cleaner.
Non toxic Antifouling
IMC has developed a process to apply pure copper to a variety of substrates including alu-
minum, wood, fiberglass, and steel as a near permanent nontoxic antifouling that will not
leach poisons into the environment and does not use solvents in the application process. The
process is achieved through an electric arc used to melt the metal propelled by clean com-
pressed air. The coating is permanently welded to the substrate and repels all types of marine
nuisances, including the "zebra" mussels which are now a very expensive problem through-
out the United States. The process is being used currently to protect power plants, cooling
water intakes, ships, buoys, and other structures.
Paclitaxel Process Improvements
Paclitaxel is a chemotherapeutic agent used to treat ovarian, breast, and other cancers.
Hauser has developed a green technology centered around a self-patented process improve-
ment by which cephalomannine and related ozone oxidizable compounds are separated from
paclitaxel and other non-oxidizable compounds in biomass extract (ozonolysis technology).
Hauser develops, manufactures, and markets special products from natural sources. Hauser's
proprietary extraction and purification processes enable the company to produce natural
extracts at a higher quality, yield, and concentration than conventional procedures. Hauser
employs proprietary technologies in combination with conventional techniques to process
natural raw materials and to produce specialized natural products. Hauser utilizes this tech-
nology to produce bulk quantities of the anticancer compound paclitaxel from Yew trees.
The implementation of Hauser's ozonolysis technology in the isolation of paclitaxel
spurred many environmental and human health benefits. Several processing solvents (includ-
ing methylene chloride), their subsequent air emissions (43,000 pounds annually), and
significant wastes (254,000 pounds annually) have been eliminated. In addition, the use of
natural resources was improved by incorporating renewable feedstocks (422,000 pounds
recycled annually). A filter media that required disposal as a hazardous waste was also replaced
with an indefinitely reusable alternative (eliminating 100,000 pounds of waste annually).
Most importantly, these improvements have made the most effective anticancer drug in his-
tory more cost-effective to produce and more affordable to those in need. The financial
impact of all of the process changes has resulted in a 50% decrease in the cost of manufac-
turing paclitaxel.
International
Metalizing Corporation
Hauser, Inc.
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BAT Technologies Inc.
Radiance Services
Company
Nextec Applications,
Inc.
Primer for Anti-Fouling Paint
This technology and material is a primer to be used in conjunction with the bottom paint
(anti-fouling paint) that is found on the bottoms of all ocean-going boats. Every ocean-going
boat must have its anti-fouling paint removed and reapplied every year. Current technology
mandates that the paint be sanded off. The resultant powder is dangerous; it is blown into
the water and inhaled by the people sanding the bottom of the boat. Every year, 1.5 million
pounds of copper oxide paint dust are dumped into the ocean in the United States alone.
A method and material have been developed that allow anti-fouling paint to be removed
quickly, in large sheets, without sanding. The primer uses a sophisticated wax/water emul-
sion. Once the water from the emulsion has evaporated, the anti-fouling paint is applied. The
boat is used, as usual. When the boat is to be hauled and the anti-fouling paint is to be reap-
plied, the old anti-fouling paint is removed with just hot water. The temperature of the water
must be above the melting point of the wax. The spent anti-fouling paint is easily collected
and disposed of in drums. The spent paint can easily be disposed of in a hazardous waste dis-
posal site or can be recycled.
The Radiance Process: A Quantum Leap in Green
Chemistry
The Radiance Process is a novel, dry, nontoxic cleaning technology for surface prepara-
tion. It employs the quantum mechanical effects of laser light in combination with an inert
gas, ordinarily nitrogen, to clean surfaces. The light lifts the contaminant from the surface
and the flowing gas sweeps it away without the pollution now associated with surface clean-
ing. The process has potential application in the manufacturing of semiconductors,
photomasks, flat panel displays, storage media, and optics. Radiance cleans without emis-
sions, discharges, or wastes, thus preventing pollution and conserving natural resources. It is
designed to supplant the use of wet chemicals in surface cleaning and preparation.
Solventless Process for Improving Fabric Performance
Properties
The Nextec process delivers fabric performance benefits through a process that utilizes no
solvents, has no volatile organic compounds (VOCs), utilizes essentially nontoxic starting
materials, and yields inert residuals that have passed biocompatability testing. The unique
patented technology that is being practiced by Nextec Applications, Inc. replaces processes in
which rubbers are dissolved in toxic aromatic or chlorocarbon solvents and coated or spread
on fabrics. Nextec's process allows precise placement of thin polymeric films around fibers
and crossover points and filling in or leaving open interstitial spaces within fabrics. The
choice of polymer, substrate and placement of polymer allows for improvement of properties
such as breathable barrier performance, controlled porosity, resistance to fluids, and adhe-
sion/release behavior. This technology has found applications including aerospace,
automotive, apparel, and medical.
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Sugars from Lignocellulosic Materials for the Production
of Bio-Based Fuels and Chemicals
Arkenol, Inc. has developed an environmentally sound and cost competitive technology
for a carbohydrate industry. While completely analogous to the petrochemical industry,
Arkenol's technology uses innocuous and renewable feedstocks. The Arkenol process utilizes
concentrated sulfuric acid to break down the cellulosic structure in lignocellulosic feedstocks
and then, with water, complete the new formation of individual C6 and C5 sugars for fur-
ther processing into chemicals and fuels. The lignin is processed for soil amendment or solid
fuel. Silica, uniquely present in rice straw, can be recovered and converted to high value pre-
cipitated silicas or zeolites. Trace amounts of sulfuric acid in the sugar solution are converted
into gypsum for soil amendment or ammonium sulfate for fertilizer. The sugars can be con-
verted into alcohols and carbon dioxide, acids, ethers, solvents, or surfactants either by direct
chemical conversion or through fermentation or a combination of both.
The successful implementation of Arkenol's technology will lead to decentralized and eco-
nomic production of fuel ethanol and other biobased chemicals. Arkenol's ability to use a
wide variety of feedstocks will enable placement of production facilities (or "biorefmeries")
near the market for the products. Large scale conversion of waste materials into fuels and
chemicals is a novel solution to waste management, pollution prevention, and economic
development.
Total Impact Program—An Environmentally Preferable
Program for Laundry
Anderson Chemical Company's Total Impact Program® employs chemistry with a more
positive environmental profile for human health and the environment than that used in con-
ventional laundry systems. The TIP® program incorporates a neutral pH detergent enhanced
with enzymes and surfactants that pose low environmental concerns, oxygen bleach, and
biodegradable softeners. The program also saves water and energy and extends fabric life. The
program targets three main impact areas: user safety and health, environmental impact for
pollution prevention via source reduction, and efficiency through resource consumption
reduction by decreasing processed pound costs (decrease in water consumption, energy costs,
and reduced effluent costs resulting from volume and pH factors).
Waste Oil Source Reduction Through Extended Oil
Service Life
According to National Petroleum Refiners Association (NPRA) estimates, 1.1 billion gal-
lons of oil were used in passenger vehicles, and 916 million gallons were used in diesel engine
vehicles in the United States in 1996. Much of the motor oil changed by passenger vehicle
owners is improperly introduced into the environment. The management of used oil is a
major environmental issue because of its hazardous nature. Used oil contains toxins such as
lead, benzene, cadmium, chromium, and other heavy metals. These contaminants can cause
illness in plants and animals and contaminate drinking water. Waste oil has been granted spe-
cial regulatory status, exempting its management from conventional hazardous waste rules in
an attempt to encourage its beneficial use as a source of energy. Overall, this has had some
success in the management of used oil in the business sector. Used oil generated by house-
Arkenol, Holdings, L.L.C.
Anderson Chemical
Company
AMSOIL Incorporated
35
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lonEdge Corporation
holds, however, is currently disposed of improperly at an alarming rate nationally—220 mil-
lion gallons per year as estimated by the U.S. Department of Energy.
In 1972, AMSOIL Inc., introduced the first 100% synthetic motor oil to meet American
Petroleum Institute service requirements, passing performance testing for gasoline fueled con-
sumer passenger vehicles. AMSOIL Inc. has since developed synthetic oil formulas that
extend oil service life up to 11 times that of conventional petroleum lubricants in consumer
and commercial automobile and truck service, and much longer when used with an oil analy-
sis program. AMSOIL Inc. also manufactures extended life, premium-grade lubrication and
related products for commercial and industrial applications, including hydraulics, compres-
sors, gears, and diesel-engine power plants. The scope of AMSOIL lubricating products'
ability to provide uncompromising engine and machine wear protection, while reducing the
volume of waste oil generation at the source, benefits the consumer, the commercial goods
and services provider, and the upstream industrial entity. Synthetic oil basestocks are com-
prised of well-defined particular molecule types that can be designed for specific performance
characteristics. One distinct advantage over crude petroleum is that they can be tailored to fit
the requirements of the application. The uniform molecular structure of synthetic oil bases-
tocks reduces the lubricant volatility (aromatic boil off) in extreme heat, which in turn
reduces oil consumption. With long drain synthetics, the average American can use 75% less
oil, reducing the volume and potential for accidental environmental contamination.
Zero-Waste Dry Plating of Cadmium
Electroplated cadmium is widely used in the defense and aerospace industries for the cor-
rosion protection of steels. Cadmium, however, is a known toxic material. In addition, the
electroplating process generates large quantities of toxic sludge and effluents. A typical medi-
um-sized electroplating shop, for example, discharges well over 100,000 gallons of effluents
daily and disposes 15 to 20 tons of hazardous sludge per week. As an alternative to this con-
ventional process, lonEdge Corporation has developed and commercialized a novel
"zero-waste" dry plating technology. The dry plating does not use liquid chemicals and recy-
cles solid materials in situ resulting in elimination of waste. In this dry plating technique, a
vapor-bath concept has been used in vacuum as opposed to the liquid bath of electroplating.
This vapor-bath allows for multidirectional and economical plating of cadmium only on the
intended parts resulting in a green technology. In addition, the amount of water used, fil-
tered, and deionized on the line is reduced by at least an order of magnitude, and the energy
consumption in the dry plating operation is only 35% of that in electroplating. Estimated
waste treatment and disposal cost savings on the dry plating line are greater than $ 1,000 per
day, and the capital costs in setting up the line are substantially lower. At lonEdge
Corporation's facility in Fort Collins, Colorado, a complete dry plating line has been set up
for production. The plating line consists only of four processes and a quality inspection as
opposed to more than a dozen baths and related operations in the electroplating. This plat-
ing line has been certified by a major aerospace parts supplier, and two dry plating machines
are in service for plating cadmium on aerospace components.
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The Zyvax "Watershield" Mold Release
Zyvax Watershield is a unique material for its intended purpose as a mold release for aero-
space adhesively bonded parts or fiberglass and other composite aircraft/spacecraft structures.
It contains no volatile organic compounds, ozone depleting chemicals, or other solvents and
materials considered hazardous by EPA or state or local regulatory agencies. Furthermore, as
a wiping agent, the Watershield could be used as a precleaner for molds for both initial and
subsequent applications. And its residues could be easily removed with water or water solu-
ble cleaners, therefore significantly reducing the need for solvents to remove Watershield
residues prior to painting or sealing. It therefore avoids environmentally sensitive materials
not only in its formulation, but also by its proper use. Watershield was so effective a release
agent that its use was enthusiastically adopted by a number of aerospace companies who
found they could eliminate significant solvent use, satisfying environmental, health, and safe-
ty concerns. Watershield eliminated hazardous materials in an area of aerospace
manufacturing that EPA had exempted from its regulation because of the absence of avail-
able replacement technology and the critical nature of the application. Therefore it allowed
the elimination of hazardous material without an absolute regulatory requirement.
Zyvax Incorporated
37
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Morton International,
Inc.
IMC-Agrico Company
Entries from Industry
and Government
ADVAFLEX™ Organic Stabilizer
ADVAFLEX™ Organic Stabilizers (ADVAFLEX) are novel organic PVC heat stabilizers
primarily geared toward flexible PVC applications. While PVC is a versatile polymer with
many useful properties, it cannot be processed without the addition of heat stabilizers.
Conventional flexible PVC stabilizer technology relies on complex mixtures consisting of as
many as 10 components, with primary active ingredients that include lead, cadmium, and
barium compounds with metal contents in the range of 8 to 10%. Most of the components
originate from nonrenewable resources and many are health and environmental hazards.
ADVAFLEX™ is an entirely new concept in PVC heat stabilizer technology that offers
numerous advantages over conventional stabilizers. First and foremost, these are two-com-
ponent systems containing new organo-sulfur chemistry and low levels of metal activators
such as zinc. The performance advantages include excellent thermal performance, competi-
tive costs, good secondary performance attributes, compatibility with co-additives
chemistries, and simplicity of PVC formulation. The environmental and health benefits
include very low metal content (as low as 0.4%); low odor and volatility; and the absence of
barium, cadmium, lead, phosphorous, alkylphenol, and other aromatic chemicals that are
used in conventional technology. ADVAFLEX™ has undergone a thorough toxicity screening
that demonstrates the product is essentially nontoxic, and not mutagenic, carcinogenic, or
environmentally hazardous. The metal activators in ADVAFLEX™ formulations are general-
ly required at catalytic levels and the preferred metal, zinc, is a required element of the human
diet. ADVAFLEX™ technology is a commercially attractive alternative that improves on all
aspects of conventional technology, especially with respect to human and environmental safe-
ty-
AGROTAIN-(n-butyl) Thiophosphoric Triamide
Urea is now the favored form of solid nitrogen-containing fertilizer and is rapidly dis-
placing anhydrous ammonia in the nitrogen fertilizer market. The market share of world
nitrogen consumption has risen from 5% in 1962 to 37% in 1986 for urea. There are many
reasons for this increase. Urea is a source of nitrogen for crop fertilization that is easily han-
dled and transported, higher in nitrogen content than other common solid nitrogen
fertilizers, and can be readily bulk blended with other fertilizer components such as potassi-
um chloride, diammonium phosphate, and other materials to prepare multinutrient
fertilizers. While urea has many advantages over other nitrogen sources and has already cap-
tured a greatly increasing market share, a major drawback to the use of urea is its tendency
to lose a substantial portion of the nitrogen values by ammonia volatilization. These losses
can easily exceed 30% of the available nitrogen in urea under certain climatic and soil con-
ditions.
AGROTAIN® is a formulation containing N-(n-butyl) thiophosphoric triamide (NBPT)
the precursor to the active ingredient, N-(n-butyl) phosphoric triamide (BNPO, the oxygen
analog of NBPT). BNPO is far too unstable to be an article of commerce. NBPT serves as
an effective precursor to BNPO, a urease enzyme inhibitor that inhibits the hydrolysis of urea
by inhibiting the activity of the urease enzyme that catalyzes its hydrolysis. This activity is the
result of an interaction between the urease enzyme and the urease inhibitor. There is no inter-
action with soil microbes that generate the urease enzyme. Moreover, the recommended
38
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NBPT treatment rate is only 0.4 Ib/acre, and NBPT is relatively unstable and presents no
problems with long-term buildup in the soil. The use of NBPT with urea is also ideally suit-
ed for no-till agriculture applications. No-till agriculture is an environmentally friendly
approach that involves little or no disturbance of the topsoil, resulting in less soil erosion and
less energy intensive operation. Urea, however, has not been well suited for use with surface-
applied no-till applications until the advent of NBPT because of the possibility of substantial
ammonia volatilization losses.
Air Liquid PFC Recycle Process
Perflourocompounds (PFCs), including C$6, CF4, Np3, CHF3, SFe, and C^F$ are essen-
tial to many manufacturing processes in the semiconductor industry. However, these gases
are also classified as greenhouse gases; they are much more potent than carbon dioxide, due
to their extremely long lifetime and strong absorption in radiation. Environmental scientists
believe these gases may last as long as 50,000 years in the atmosphere. Over 1.6 million
pounds of PFCs were used in 1995 in the U.S. semiconductor industry, at an estimated cost
of over $45 million. This amount could double by the year 2000. The U.S. government has
responded to its international commitment (Rio Earth Summit '92) by promoting reduction
in PFC emissions in various industries. The semiconductor industry has currently two choic-
es for addressing the immediate emission reduction: (1) abating these gases at considerable
financial and environmental cost or (2) recycling of PFCs developed by Air Liquid. Air
Liquid has developed a system to capture these gases from process exhaust to further con-
centrate, purify, and recycle. This process went through a rigorous qualification test under the
umbrella of SEMATECH and demonstrated both the capture and concentration of the PFCs
above 95%. In summary, this technology improves the environment by reducing PFC emis-
sions that are targeted by the global warming reduction objective. It does this by allowing the
semiconductor manufacturers to maintain their current process chemistries and operate at a
lower cost than any other emissions control alternatives.
Analysis of Liquid Hazardous Waste for Heavy Metals
by Energy-Dispersive X-Ray Fluorescence (EDXRF)
Spectrometry
The laboratory-based elemental analysis of nonaqueous liquid hazardous waste has tradi-
tionally been performed using inductively coupled argon plasma (ICP) and atomic
absorption spectrometry (AAS). The preparation of samples and analyses using these tech-
niques, however, generates a large amount of acidic, heavy metal-bearing hazardous lab waste.
Laboratory-based energy-dispersive X-ray fluorescence spectrometry (EDXRF) is a mainstay
analytical technique in many industries, but has received very limited attention in the envi-
ronmental field. Within the last five years, ASTM Committee D34 on Waste Management
has formally approved two Standard Test Methods for the elemental analysis of liquid waste
by EDXRF spectrometry. In many cases, data quality objectives can be easily met using
EDXRF spectrometry instead of ICP or AAS. The main environmental benefit of using
EDXRF spectrometry is the significant decrease in the generation of laboratory waste in com-
parison to traditional methods. The primary reasons for this reduction in waste generation
are that samples do not require dissolution in concentrated acids and calibration standards
are not dissolved in acidic solutions and diluted to large volumes. Samples and standards are
simply mixed with a nonhazardous substrate such as carbon or alumina prior to analysis or
calibration. Also, the frequency of preparing and running standards is much less than tradi-
American Air Liquid
American Society for
Testing & Materials
(ASTM)
39
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Ciba Specialty
Chemicals Corporation
tional techniques because of the inherent stability of EDXRF systems. It is an environmen-
tally friendly technique because it virtually eliminates the generation of hazardous lab waste.
Ashless Friction Modifier!Antioxidant for Lubricants
Cars consume roughly half the oil used in the United States and account for about one
quarter of the greenhouse gases generated. There are at least two important benefits to
improving passenger car fuel economy: conserving natural petroleum resources and improv-
ing the environment through reduced volatile emissions. While automobile manufacturers
work on improving vehicle fuel economy through upgrading engine efficiency and utilizing
lighter weight materials in automobile construction, products that can improve the perfor-
mance of cars already on the road could have a more immediate impact. Development of
engine oils that improve engine efficiency are in this category.
Engine oil is a mixture of petroleum base stock and additives that protect the metal sur-
faces, expand the useful temperature range of the lubricant and extend the useful life of the
oil. Additives in a typical engine oil include detergents to keep the metal surfaces deposit free;
dispersants to keep the insoluble particles suspended in the oil; viscosity modifiers, which sta-
bilize lubricant thickness at various temperatures; antiwear agents, which reduce
metal-to-metal contact; metal deactivators, which reduce friction between metal parts in
motion; and antioxidants, which reduce oxidation and breakdown, preserving the lubricant's
properties over its lifetime.
Developing a combination friction modifier/antioxidant reduces the number of additives
that a lubricant requires. More importantly, it has the capability to extend the durability of
the friction modifier, leading to improved lubricants. This in turn can positively influence gas
mileage and reduce environmental emissions. Irgalube F10 is a unique ashless, multifunc-
tional, combination friction modifier and antioxidant. Chemically it is a high molecular
weight phenolic antioxidant with hydroxyl functionalities providing friction modifying prop-
erties. It has been designed to replace glycerol mono oleate (GMO), a friction modifier which
tends to promote oxidation at higher temperatures, and molybdenum dithiocarbamates
(MoDTC), which are metal-containing and can form undesirable, metal-containing inor-
ganic particulates upon combustion.
Irgalube F10 is made via the reaction of coconut oil, glycerol, and a phenolic antioxidant
and as such is the only commercially available, metal-free, multifunctional friction
modifier/antioxidant in the world. Irgalube F10 passed the ASTM fuel economy test proce-
dure, registering a fuel economy improvement of 1 to 1.5% over the standard test oil. A
fuel-efficiency improvement of 1% could have an annual impact of reducing carbon monox-
ide by 1.2 billion pounds, NOx emissions by 240 million pounds, and particulate matter
emissions by 17 million pounds (based on National Air Quality and Emissions Trends
Reports, 1996).
Pacific Northwest
National Laboratory
Biocatalytic and Biomimetic Process for the Synthesis of
Nitroaromatic Intermediates and Destruction of
Nitrocompounds, Including Explosives
Nitroaryl and nitroheterocyclic compounds—found in antibiotics, radio sensitizers,
explosives, dye intermediates, herbicides, and pesticides—require a technology to synthesize
and destroy nitrocompounds. The massive stockpiles of explosives alone and the contamina-
tion they cause in water, soil, and sediment around the world pose a serious threat to
humankind, health, and the ecology. Currently, there are no acceptable technologies or
40
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resources to demilitarize aging stockpiles and clean up their contamination. Current stock-
piles of energetic materials requiring resource recovery or disposition (RRD) weigh in at
about 449,308 tons. Through 2001, over 1.2 million tons will pass through or reside in the
RRD account (Joint Ordnance Commands Group, 1995).
A totally different, but significantly similar challenge exists in cleaning up the sites where
soil and ground water are contaminated with TNT, RDX, HMX, and other nitro-based
explosives. Today technicians use incineration, open burning, and open detonation tech-
nologies to eliminate explosives. The cost of incineration is beyond our means and resources,
and open burning and detonation are environmentally unacceptable. Researchers at Pacific
Northwest National Laboratory (PNNL) have developed a technology solution that is envi-
ronmentally friendly, offers economic benefits, and can be easily implemented over
incineration, open burning, open detonation, and several other technologies.
The PNNL destruction technology uses enzymes (biocatalysts) and biomimetic process-
es; the synthesis technology uses biocatalysts. The enzymes for these applications were
discovered to be ubiquitous in plants, microorganisms, and dairy products. Nitro reductase
enzymes from these sources are used to synthesize nitroaromatic intermediates such as
hydroxylamines and aminophenols, and were used successfully to synthesize phenylhydroxy-
lamine and p-aminophenol from nitrobenzene, an important industrial chemical for dye and
headache medicine using nitroreductase enzymes from spinach.
Spinach enzymes also were used to synthesize 4-hydroxylamino-2,6-dinitrotoluene from
2,4,6-trinitrotoluene, TNT, which can be used in the production of antioxidants. This TNT
conversion process provides a "zero" cost alternative for disposing of unusable TNT stock-
piles located worldwide. Unlike incineration, the PNNL biomimetic process, based on
potassium superoxide, destroys explosives under mild reaction conditions. Contrary to other
processes, this technology synthesizes and destroys nitrocompounds at room temperature—
without leaving and using organic solvents. These emerging enzyme and biomimetic
technologies provide an environmentally benign, safe, and cost-effective method to synthe-
size and destroy nitrocompounds—including explosives.
The Chemical Kinetics Program
Computer simulators offer a powerful means of minimizing waste generated through
physical experimentation during process development and optimization, a waste stream not
usually addressed in green chemistry programs. The potential impact of simulations will not
be realized, however, unless they are widely accessible in an organization. The Chemical
Kinetics Simulator (CKS) Program, developed at the IBM Almaden Research Center to meet
this need, is a general purpose, easy-to-use package that allows outcomes of reactions to be
predicted for a broad variety of gas, solution, and solid phase systems in static and flowing
reactors. Its basic computational method is well founded in theory and has been significant-
ly enhanced through new algorithms that have been awarded U.S. patents. CKS has been in
use at IBM for three years for process research and development. Since May 1996, the pack-
age has been available globally for a no-cost license through the World Wide Web and is used
in many other industries for process research and development because of its exceptional ease-
of-use and functionality. It also has been frequently licensed by environmental researchers in
universities, corporate and government laboratories, and environmental regulatory agencies
to develop models and evaluate hazards.
Almaden Research
Center, IBM
Corporation
41
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Albany Research
Center, U.S.
Department of Energy
Argonne National
Laboratory
Chloride-Free Processing of Aluminum Scrap
According to the U.S. Geological Survey, U.S. year-to-date aluminum scrap consumption
totaled 724 million pounds. Other than can scrap, which is processed separately, the bulk of
the aluminum is consumed by the secondary aluminum industry. In spite of the fact that
scrap is carefully selected so that a specific charge will meet product specifications, the molten
charge typically contains up to 1.0% magnesium (Mg). Because the specifications for most
diecast aluminum alloys call for a Mg level of less than 0.1% Mg, the charge must be
demagged. The excess Mg is removed through the addition of chlorine (Ck) gas, or occa-
sionally through the addition of AlFa. Most of the demagging reaction schemes use Ci2 and
in practice require 6 Ib of Ci2 gas to remove 1 Ib of Mg as MgCk (approximately 4,500 Ib of
Ci2 per batch). Both techniques require both careful handling of the materials to insure oper-
ator safety and air pollution controls to insure the protection of the environment. If wet
scrubbers are used in the air pollution control systems, then the fugitive chlorides that are
captured in the water require additional treatment to meet clean water standards.
A more ideal approach is to remove and recover the Mg from the melt using a technolo-
gy that is inherently safer and cleaner because it does not require additions of Ci2 gas or Alp3
and requires a minimum of processing steps. The Albany Research Center (ALRC) has con-
ducted very successful research to investigate the synthesis and scavenging properties of
ionically conducting ceramic oxides such as lithium titanate (L^^Oy) for demagging the
aluminum scrap melts. The process known as engineered scavenger compound (ESC) tech-
nology offers an alternative to the conventional demagging technology that has distinct safety
and/or environmental advantages over previously employed methods. The ESC technology
neither generates fugitive chloride emissions nor hard to dispose of drosses or slags. The ESC
reaction is easily reversible so that the recovered species is available for recovery and repro-
cessing as a metal product rather than as a salt in the older process.
Clean Diesel Breakthrough: Simultaneous Decrease in
Emissions of Both Particulates and Oxides of Nitrogen
During Combustion
One of today's most challenging environmental problems is air pollution by oxides of
nitrogen (NOx) and particulates, created largely by diesel engines, particularly in urban areas.
NOx and particulate emissions from diesel engines are a major source of urban air pollution.
Particulate matter contains organic compounds that may potentially cause cancer or muta-
tions. Nitrogen oxides contribute to the formation of acid rain, ground-level ozone, and
smog. Although the availability of oxygen enrichment in diesel engines has long been known
to reduce particulate levels, it has not been a feasible technology because it increased the NOx
levels. By using only a modest increase in oxygen level in engine intake air and optimizing
fuel conditions, Argonne National Laboratory (ANL) has broken through the technical bar-
riers to create an oxygen enrichment technology that simultaneously reduces both
particulates and NOx.
The breakthrough came when ANL tested a new combination of three changes to engine
operating conditions: 1) increased oxygen content in the engine air supply, 2) retarded tim-
ing of fuel injections, and 3) increased fuel flow. ANL tests were the first to adjust all three
parameters. Previous strategies had changed only one or two of these conditions. This break-
through technology is made practical by the development of a compact advanced polymer
membrane that is a passive design and can be retrofitted to existing engines. The mass-pro-
duction cost is expected to be modest ($75 to $160) compared with particulate traps ($200
42
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plus 2 cents per gallon to operate) and NOx treatment catalytic converters ($300 plus peri-
odic maintenance).
This is the first oxygen enrichment technology to simultaneously reduce both NOx (by
15%) and particulates (by 60%). It is an all-in-one, in-cylinder treatment that solves the
emissions problem at the source, does not drain engine power (in fact, increases gross power
by 18%), and improves fuel efficiency (2 to 10% improvement in brake-specific fuel con-
sumption across the entire load range in a locomotive notch schedule). This breakthrough
technology will be important to diesel engine manufacturers, who are faced with helping
their customers meet lowered regulatory standards beginning in model year 2002.
Designing an Environmentally Friendly Copper
Corrosion Inhibitor for Cooling Systems
Copper alloys are widely used in industrial cooling systems because of their good heat
transfer qualities. However, unless they are protected by an inhibitor, copper alloys will cor-
rode in cooling systems. This corrosion produces extremely toxic copper compounds that are
then released into the environment. Azole materials are the best available copper corrosion
inhibitors and, in general, they protect copper very well. Tolyltriazole (TTA) is by far the
most frequently used azole and is considered to be the industry standard. However, azole
materials have a serious drawback in that they are not compatible with oxidizing halogens,
such as chlorine and bromine. Oxidizing halogens are the most common materials used to
control microbiological (MB) growth in cooling water systems. TTA reacts with chlorine,
producing a chlorinated species that is not protective to copper. When corrosion protection
is lost, TTA feed rates are usually increased in an attempt to overcome the reaction with chlo-
rine and maintain a high enough residual to protect the copper surface. Very high TTA
dosages are frequently applied in order to improve performance, often with limited success.
BetzDearborn has developed a new Halogen-Resistant Azole (HRA) that does not react
with chlorine and protects copper when chlorine is present. The substitution of this new
material for TTA provides substantial environmental benefits. These were demonstrated in a
field test at a nuclear power plant that was utilizing chlorine for MB control. HRA was com-
pared to TTA with respect to copper corrosion rates and discharge toxicities. Upon
examination of the discharge, it was clear that copper-containing compounds, formed as a
result of copper corrosion, were the most significant causes of toxicity to aquatic species.
The use of HRA resulted in a five-fold decrease in the amount of copper released to the
environment, compared to TTA. Since HRA does not react with oxidizing biocides, consid-
erably less chlorine or bromine is required for prevention of MB activity. A reduction in
chlorine usage of 10 to 20% was observed at the above nuclear power plant, and reductions
of 35 to 40% have been observed at other industrial sites. Lower chlorine usage means lower
amounts of chlorine- or bromine-containing compounds ultimately being released in dis-
charge waters. In addition, substantially lower concentrations of HRA are required for copper
alloy protection compared to TTA. At the nuclear power plant trial, the five-fold reduction
in the copper discharged was obtained with 2.0 ppm HRA compared to 3-0 ppm TTA.
Furthermore, a mass balance showed that only 9% of the TTA was recovered (compared to
90% of the HRA). The TTA loss was due to the reaction with chlorine and the formation of
a chlorinated azole. Thus, the use of HRA resulted in a net reduction in the amounts and
types of azole and halogenated azole compounds that were released into the environment.
Finally, direct measurement of LC50 acute toxicities for fathead minnows, done on site in the
plant effluent at the nuclear facility, showed a reduction in toxicity when TTA was replaced
by HRA.
BetzDearborn, Inc.
43
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Nalco Chemical
Company
Tektronix, Inc.
Designing an Environmentally Sensible Chlorine
Alternative (STABREX)
Industrial water treatment is necessary for energy conservation and to ensure a sustainable
global supply of freshwater. Water treatment is mostly about managing surface-fouling
processes. There are three surface-fouling processes to manage (microbial, scaling, corrosion)
and they occur simultaneously. Of these three, the microbial fouling process requires appli-
cation of the most potentially hazardous products in water treatment—far more chlorine is
used to control microbial fouling in an industrial water treatment compared to any other
chemical. An environmentally sensible chlorine alternative is needed because the gas is haz-
ardous, the liquid is not stable, chlorine is too volatile, free residuals do not efficiently control
fouling biofilms, combined residuals are not very effective, reactivity with scale and corrosion
inhibitors is counterproductive, and disinfection byproducts are toxic.
STABREX microorganism control chemical is a new stabilized liquid hypobromite prod-
uct designed to imitate the stabilized bromine antimicrobials produced naturally in the
human immune system. STABREX is the first biomimetic industrial biocide. It is chemical-
ly analogous to the antimicrobial product of the oxidative respiratory burst in eosinophils, a
type of mammalian white blood cell. These cells consume oxygen in a cellular process recent-
ly proven to produce stabilized bromine antimicrobials. In eosinophils, HOBr from the
enzymatically catalyzed oxidation of bromide with H2O2 immediately reacts with 2-
aminoethanesulfonic acid (taurine). The product of this stabilization reaction is a potent
antimicrobial, N-bromoaminoethanesulfonic acid and it is the design model for STABREX.
The design and performance benefits of STABREX Microorganism Control Chemical
have been proven in 100 billion gallons of successfully treated industrial water since intro-
duction in May 1997- The product is useful wherever industrial water is reused such as in
recirculating cooling water, in all sorts of light and heavy manufacturing processes, airwash-
ers, pasteurizers, and in hydrostatic sterilizers. STABREX has replaced 20 million pounds of
chlorine or its equivalent in the field, worldwide. Compared to chlorine, the new product is
more than 10 times less toxic, generates 50% less disinfection byproducts, is much more
effective in controlling microbial biofilms, is many orders of magnitude less volatile, is much
simpler to handle and feed, is 50% less reactive with other water treatment chemicals, and
degrades an order of magnitude less in storage or transport. STABREX works better, is safer,
and is easier to use than current chlorine alternatives.
Designing Safer Chemicals: Spitfire Ink
As the information age enters a significant period, a new paradigm is being introduced to
the printing industry. With the advancement of computer technology, the demand for
peripheral printing devices has accelerated. For the past 10 years, this growth industry has
been truly in its infancy. Various chemical systems have been employed with a multitude of
electronic and/or mechanical printing devices, primarily addressing office applications. The
computer-based printing devices, which consume large volumes of chemicals (inks, resins,
colorants, solvents, etc.) are rapidly progressing to the extent that traditional printing tech-
nologies are being challenged. One of these chemical systems is phase change ink. The many
attributes of phase change ink make it a viable contender for a leading position in the print-
ing industry to replace less environmentally friendly alternatives. Phase change ink, also
known as hot melt or solid ink, addresses many of the limitations of the ink and printing
processes associated with the well-defined, centuries old printing methods, (e.g., offset, flex-
ography, gravure, letterpress).
44
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To demonstrate the enormity of the opportunity, chemical development of phase change
inks has favorably addressed source reduction, pollution prevention, emission standards,
ground-water contamination, airborne particulates, waste abatement, worker and consumer
exposure, hazardous chemical reduction and nonreusable consumables. The traditional print-
ing techniques that often have significant worker and environmental liabilities can now be
replaced with modern technology sensitive to, and having an understanding of, complex
"green chemistry" issues. Tektronix is commercializing a four-color set of process shade, phase
change inks (Spitfire Ink) for use in color printers also manufactured by Tektronix. The
chemical design of Spitfire Inks started with consumer and manufacturing operator safety,
environmental concerns and the expected application performance. A retro-synthetic analy-
sis accounting for these primary "must haves" translated to the synthesis of new resins that
were water insoluble, required no volatile organic solvents (VOCs) to manufacture or use,
allowed for safe manufacturing, complied in "spirit and intent" with environmental regula-
tions and provided a flexible technology to a growing and expanding industry. These goals
were satisfied by foresighted design aimed at safer chemicals ultimately embodied in
Tektronix' Spitfire Ink.
Durable AMPS® Antimist Polymers for Aqueous Metal
Working Fluids
The generation and accumulation of metalworking fluids (MWF) mists in the plant envi-
ronment during metalworking production gives rise to worker health and safety concerns. It
is estimated that about 1.2 million workers are potentially exposed to MWTs annually. In
response to increasing worker health concerns from MWF mists, the United Auto Workers
Union has petitioned the Occupational Safety and Health Administration to lower the per-
missible exposure limit (PEL) of oil mists in the workplace from the current PEL of 5 to 0.5
mg/m3. The current mist control methods being used for mist exposure controls have draw-
backs. For instance, engineering mist controls based on machine enclosures and mist
collection are exorbitantly expensive to install and maintain. The second chemical mist con-
trol methods based on using high molecular weight polymers as antimist (AM) additives for
aqueous MWFs have found limited acceptability because AM polymers lose their perfor-
mance due to shear degradation, requiring frequent additions to maintain performance.
The development of durable AMPS® polymers at Lubrizol solves this problem. These
polymers suppress mist formation at the source by stabilizing the MWF against breaking up
into small droplets that get suspended in the plant environment as mist. The reduction in
mist minimizes worker exposure to MWF chemicals and other pollutants present in the mist,
creating a safer working environment. Because they are shear stable, the AMPS® polymers
provide long lasting mist reduction. The application and performance of the AMPS® poly-
mers were evaluated during field trials at small machine shops and large Ford manufacturing
plants. In a small machine shop field test, a one-time addition of 1,000 ppm AMPS® poly-
mer resulted in a stable 60% mist reduction. During large-scale plant trials at Ford Motor
Company, a one-time addition of 1,000 ppm AMPS® polymer resulted in a stable 40 to 60%
mist reduction for over two months in the plant environment. The worker response to
reduced mist levels during these trials was extremely positive. It was felt that after the poly-
mer addition, there was a distinct improvement in plant air quality, general improvement in
working conditions, and less slippery floors from oil mist deposits.
AMPS® polymers provide a low-cost method of suppression mist generation and exposure
control since they provide long lasting mist suppression at low (ppm) concentrations. These
polymers are less labor intensive to implement in the field since they disperse easily in the
MWF and do not require frequent addition. They are manufactured as aqueous solutions and
The Lubrizol
Corporation
45
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Akzo Nobel
U.S. Department of
Agriculture Forest
Service
Revlon Consumer
Products Corporation
do not contain any volatile organic compounds. Extensive sensory, inhalation, and dermal
toxicity tests have shown that AMPS® polymers exhibit a profile of minimal toxicity under
conditions of use. Waste-water treatment evaluations have shown that they do not affect the
waste treatability of aqueous MWFs.
A Durable Hydrodechlorination Catalyst for Selective
Conversion of CCU to CHCl$
In 1 987, the Montreal protocol was signed, which called for a freeze on the production
and use of chlorofluorocarbons at 1986 levels with subsequent reductions and complete elim-
ination by January 1, 1996. A similar ban applies to carbon tetrachloride, also due to
environmental concerns associated with ozone depletion, global warming, and ground-level
smog. However, in the production of methylene chloride and chloroform, carbon tetrachlo-
ride is produced as a byproduct. It is estimated that in the United States and Europe, there
are about 60,000 tons excess CCU produced per year. The disposal of this byproduct, CCU,
typically by incineration, has become an environmental challenge and major economic bur-
den to manufacturers of methylene chloride/chloroform.
Hydrodechlorination of carbon tetrachloride to chloroform is an attractive alternative to
the disposal of byproduct carbon tetrachloride by incineration. Until now, the catalytic con-
version of CCU to CHCIa has been problematic due to lack of catalyst, selectivity, poor
conversion efficiency, and catalyst deactivation. Akzo Nobel made the elegant discovery of
treating an aluminum oxide supported egg shell type platinum catalyst with an ammonium
chloride solution. This provides a remarkably durable catalyst, with high conversion of CCU
to CHC13 that resists deactivation for over 2,000 hours. In contrast, untreated catalysts were
rapidly deactivated with conversions dropping from 90 to 2% within one hour. The treated
catalyst provides a cost-effective, efficient method for the conversion of carbon tetrachloride
to chloroform. Akzo Nobel BU Base Chemicals is in the process of implementing this tech-
nology internally and might offer it for commercial licensing in the future.
Effluent-Free Process for Use of Oxygen in Place of
Chlorine Compounds in Wood-Pulp Bleaching
NOTE: This project is a partnership between the U.S. Department of Agriculture and
Prof. Craig Hill of Emory University. This entry was submitted by each party of the project
and therefore was judged in both the academic and industry categories. The project summa-
ry appears in the academic entries section on page 12.
ENVIROGLUVf": A Method for Decorating Glass with
Radiation Curable Environmentally Friendly Inks
Billions of products are sold in glass containers in our country every year. Most, if not all
of these glass containers are labeled in some fashion. Typically, decorative indicia is applied to
glass using paper labels, decals, or by a process known as applied ceramic labeling (ACL).
ACL involves first printing the glass with an ink composition that contains various heavy
metals such as lead, cadmium, chromium, and the like, then bonding the ink to the glass by
baking in a lehr oven at temperatures of 1,000 °F or more for several hours.
All of these processes have disadvantages. Paper labels are inexpensive, yet they are easily
removed if the container is exposed to water or abrasion. Decals are expensive and difficult
46
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to apply at the high line speeds that are required in the decoration of most commercial con-
tainers. In addition, decals are made from materials that are not biodegradable, which causes
serious problems in the recycling of glass containers that are decal decorated. The use and dis-
posal of the heavy metals used in ACL presents serious environmental concerns. Moreover,
the high-temperature lehr ovens required in ACL decorating use substantial amounts of ener-
gy and raise safety issues with respect to workers and plant facilities operating this equipment.
The inks used in ACL decorating also tend to contain high levels of volatile organic com-
pounds (VOCs) that generate undesirable emissions.
Envirogluv technology, developed by Revlon, fills the gap in the glass decorating industry
for a decorated glass container that is aesthetically pleasing, durable, and obtained in a cost-
effective, environmentally friendly, and energy-efficient manner. Envirogluv provides an
expensive look similar to that found with ACL, but without the undesirable health and envi-
ronmental concerns. Additionally, Envirogluv decorated glass containers are completely
recyclable.
The ink compositions used in the Envirogluv processes contain no heavy metals and min-
imal or no VOCs. All of the pigments used are organic and biodegradable. The Envirogluv
inks are cured directly on the glass by exposure to ultraviolet radiation, rather than by bak-
ing at high temperatures in lehr ovens. The elimination of lehr ovens from the glass
decorating process provides many safety and environmental benefits, such as reduced energy
consumption, reduced chance of worker injury such as burns or heat exposure, and more effi-
cient and economical use of plant space. Envirogluv is inexpensive on a unit cost basis,
making it a commercially viable alternative for glass decorators.
Environmentally Benign Antibacterial Agents
Many effective antibacterial agents for consumer and health care applications on textiles
and fibrous substrates are no longer available on the market or are restricted due to their dele-
terious environmental effects in stream and watershed pollution. Chlorinated phenols and
chlorinated bisphenols are coming under scrutiny because their structure is similar to that of
polychlorinated biphenyls (PCBs) or could potentially lead to the formation of the very toxic
substance dioxin. Tributyltin and related trialkyl tin oxides are also being restricted or close-
ly monitored because of their adverse effects on water sources. Thus, there is a need for new,
environmentally benign antibacterial agents to replace ones such as those described above.
Moreover, it would be useful if the new agents had chemistries compatible with bleaching
processes in the fiber and paper industries that increasingly utilize the environmentally
acceptable agent hydrogen peroxide in place of environmentally deleterious bleaching agents
such as hypochlorite and other chlorinating agents.
Such agents have been synthesized and patented. These new environmentally benign
antibacterial agents, magnesium hydroperoxyacetate (MHPA) and magnesium dihydroper-
oxide (MDHP), are prepared by heating aqueous solutions of the two reactants under
carefully controlled conditions to yield a water-dispersible product. These new compositions
have active oxygen or peroxide contents of 1 to 30%. These new compounds exhibit antibac-
terial activity against representative gram-positive bacteria (Staphylococcus aureus) and
gram-negative bacteria (KLebsiella pneumoniae), are hydrolytically stable at ambient tempera-
tures for extended periods (at least 60 days), and thermally stable below 350 °C.
Fixation of aqueous dispersions of these agents to a wide variety of fiber types and fabric
constructions has been demonstrated, as well as the long-term durability of these agents to
laundering to retain antibacterial activity. Because of the unique surface characteristics of cot-
ton fibers in woven fabrics, antibacterial activity (99-3% or greater reduction in growth)
Southern Regional
Research Center, U.S.
Department of
Agriculture
47
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United States Postal
Service
Polaroid Corporation
against representative gram-positive and gram-negative bacteria was observed even after 50
launderings. These agents have also been applied to a variety of cotton and wood-pulp cellu-
losic nonwovens. Thus, these agents have the additional benefit of being more suitable for
renewable fibers such as cotton and cellulosic fibers derived from wood pulp than the non-
renewable synthetic fibers (such as polyester and polypropylene). Moreover, since cellulosic
fibers are bleached with hydrogen peroxide, these agents have compatible chemistry with
prior purification processes. The agents themselves may also be used in other applications
(e.g., skin disorders, toothpastes, virus inactivation) yet to be evaluated.
Environmentally Benign Pressure Sensitive Adhesive
Program
Every year the U.S. Postal Service (USPS) sells about 42 billion stamps. These sales bring
in revenue of up to $7 billion. In all, the USPS spends about $200 million to produce about
50 billion stamps annually. Due to public demand, the USPS has issued different non-lick
(self-adhesive) stamp products. The removal of pressure sensitive adhesives (PSAs) from
recovered paper is a major problem facing the paper recycling industry. Because the USPS
currently purchases about 12 to 15% of domestic PSA production and produces a high per-
centage of self-adhesive stamps (82%), and due to the public demand for convenience as well
as hygienic considerations, environmental issues have to be addressed. With the development
of these new stamp products, concern has been raised by a certain segment of the industry
and by the general public about the environmental impact of PSA stamp products. Neither
the adhesive nor the release liner backing are repulpable or recyclable.
The Environmentally Benign PSA Program was initiated by the USPS as part of its com-
mitment to develop stamps and postal products that do not adversely affect the environment.
The purpose of this program is to develop a PSA that is benign to the environment and is
able to meet the USPS requirements. This means that each component of the pressure sen-
sitive construction (i.e., the face stock, the adhesive layer, and the release liner backing) will
not only be able to perform to the USPS requirements for postage stamps, but will also pos-
sess those properties that are capable of being defined as environmentally benign. Once the
adhesive is developed, demonstrated, and implemented, the USPS intends to expand the use
of its application to other postal products.
The USPS takes a leadership role in addressing this complex problem because of popu-
larity and high visibility of PSA postage stamps. USPS is also one of the largest single PSA
materials purchasers. Identification and development of improved PSA materials to meet
stringent postage stamp performance requirements allows USPS to mandate use of these
materials for all postal products in future purchases and helps resolve contaminant issues in
recycling postal/consumer waste paper.
Environmentally Benign Supramolecular Assemblies of
Hydroquinones in Polaroid Instant Photography
NOTE: This project is a partnership between the Polaroid Corporation and Prof. John
Warner of the University of Massachusetts, Boston. This entry was submitted by each party
of the project and therefore was judged in both the academic and industry categories. The
project summary appears in the academic entries section on page 14.
48
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Environmentally Benign Synthesis of Monoglyceride
Mixtures Coupled with Enrichment by Supercritical
Fluid Fractionation
Supercritical fluid extraction (SFE, or fractionation, SFF), or, more recently, synthesis
under supercritical conditions, have attracted considerable attention as possible alternatives
to existing processes that employ organic solvents or catalysts requiring post reaction dispos-
al. Those methods utilizing carbon dioxide (CC^) have received the preponderance of
attention due to CCVs compatibility with the environment (i.e., toxicity, flammability). To
date, however, no one has demonstrated how CCh can be utilized in a series of processes
embodying synthesis, extraction, and/or fractionation, thereby creating an entire process or
plant that practices "green" chemistry from start to finish.
Studies conducted at the National Center for Agricultural Utilization Research have pro-
duced two alternative syntheses for producing monoglyceride-containing mixtures, via
glycerolysis, that employ CC^, either as a catalyst or extraction/reaction medium coupled
with enzymatic-based catalysis. The first synthesis uses carbon dioxide as a catalyst or trans-
port medium coupled with a lipase biocatalyst, to produce mixtures of varying
monoglyceride content. Further, the same carbon dioxide medium can then be used in a
sequential fashion to affect an enrichment of the synthesized glyceride mixtures to yield prod-
ucts having a monoglyceride content in excess of 90 weight% that have high value as
emulsifiers, lubrication aids, and food additives. Using carbon dioxide under pressure, metal-
based catalysts can be eliminated from the traditional batch, stirred reactor glycerolysis to
yield a product that is lighter in color, less odoriferous, and has a monoglyceride content
between 35 to 45 weight%, depending on botanical oil source.
Alternatively, the National Center for Agricultural Utilization Research has demonstrated
and patented a synthesis that uses CC^ in the supercritical state to dissolve vegetable-based
oils prior to transport over a supported enzyme catalyst to yield designer glyceride mixtures
having a variable monoglyceride content between 50 to 90 weight%. Finally, by coupling one
of the two CCh-based synthesis processes with a thermal gradient fractionation column, it is
possible to utilize a totally environmentally benign process for the production and enrich-
ment of high value oleochemicals from natural sources.
Environmentally Responsible Liquid Polymers
High molecular weight polymers based on acrylamide, produced either as a dry powder
or as water-in-oil emulsions, are commonly used as process aids and as water treatment agents
in various industries. In fact, about 200 million pounds of high molecular weight polymers
based on acrylamide, with an approximate market value of one billion dollars, are sold annu-
ally worldwide for such treatment. The powder form presents significant exposure hazards
and requires expending substantial energy during its manufacture as well as the end-use. The
emulsion form overcomes some of the limitations of the dry form. To produce these emul-
sions, however, large quantities of a "carrier" consisting of hydrocarbon solvents and
surfactants (30 to 40 weight% of the finished product) are required. This "carrier" plays no
active role other than to permit the polymers to be manufactured in liquid form and dis-
charging at the rate of about 90 million pounds per year into the environment as a "necessary
evil." To overcome these environmental and health hazards, Nalco introduced a new liquid
form of these polymers, manufactured through a unique dispersion polymerization process
using an aqueous salt solution as a reaction medium instead of oil and surfactants. These dis-
persions are completely water soluble and are very easily dissolved in water. They contain
National Center for
Agricultural Utilization
Research, U.S.
Department of
Agriculture
Nalco Chemical
Company
49
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almost zero volatile organic contents and eliminate the environmental and health hazards
associated with the respective emulsion and dry polymer forms.
U.S. Army Edge wood
Research,
Development, and
Engineering Center
Filter Leak Test Using Ozone-Benign Substances
Air purification filters operate by adsorbing impurities from flowing contaminated
streams onto high-surface-area microporous materials such as activated carbon. In order for
such a filter to operate properly, it must be packaged so that leak channels are eliminated.
Testing to ensure proper adsorbent material filling of manufactured filters is routine and has
traditionally been performed using substances such as chlorotrifluoromethane (CFC-11) and
dichlorodifluoromethane (CFC-12). It is now well known that small chlorocarbons, chlori-
nated fluorocarbons (CFCs), and certain bromine-containing fire-extinguishing materials
(halons) are detrimental to the environment because of their extreme environmental stabili-
ty in the lower atmosphere and their ability to release chlorine or bromine atoms upon
vacuum ultraviolet irradiation in the stratosphere. Chlorine and bromine atoms produced in
the stratosphere catalytically destroy ozone, thereby compromising the UV-protection the
stratospheric ozone provides.
With the advent of the Montreal Protocol eliminating production of ozone-depleting sub-
stances, the search for substitute materials for common items including air-conditioning and
fire extinguisher fluids has been intensive. Work at the U.S. Army Edgewood Research,
Development, and Engineering Center was directed at finding filter leak test materials that
were not destructive to earth's stratospheric ozone layer and capable of rapidly identifying fil-
ter assembly problems. Materials investigated included several hydrogenated fluorocarbons
(HFCs) of differing volatility. HFCs do not contain chlorine or bromine, which have been
implicated as potent stratospheric ozone destroyers. Two HFCs were identified as substitute
filter leak test vapors, 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-4310mee) for in-service
filters and 1,1,1,2-tetrafluoroethane (HFC-134a) for new filters. These materials have been
adopted by the U.S. Army to test the integrity of filters used to provide respiratory protec-
tion against chemical warfare agents.
ABB Power T&D
Company Inc.
Fully Biodegradable Vegetable Oil-Based Electrical
Insulating Fluid (BIOTEMP™)
The electrical industry uses millions of gallons of petroleum-based insulating fluids in
transformers and other electrical apparatus. These fluids have low biodegradability, and in
recent years, environmental concerns have been raised regarding the use of these fluids in
equipment located in housing areas, shopping centers, and major water-ways. Spillage of the
fluid by leaks and other means would contaminate the surrounding soil and water, posing a
threat to living organisms. A safer, environmentally friendly fluid has been sought by electri-
cal utilities.
To meet this challenge, ABB, a major worldwide electrical equipment manufacturer, ini-
tiated a R&D program in 1995- Agriculturally based oils were considered the best choice.
However, none of the vegetable oils commercially available were found to be suitable for
immediate use because of the presence of undesirable components, poor oxidation stability,
and high level of conducting impurities. The research project focused on 1) selection of a suit-
able base oil, 2) refining of the oil to electrical-grade purity, and 3) providing oxidation
stability for long-term use when exposed to air periodically.
High monounsaturated oils with more than 75% monounsaturated content were select-
ed. These oils are mostly high oleic oils derived from genetically modified oil seeds. They are
50
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inherently more stable than oils with significant di- and tri-unsaturate content. Further refin-
ing was achieved by the use of adsorbents derived from high-surface-area clays. Oxidation
stability was the hardest to achieve because many antioxidants that are available are also high-
ly conducting. A three-component system of antioxidants that would not significantly
increase the conductivity was developed by extensive testing. The level of additives is below
FDA regulatory limits, and these were food grade additives.
The newly developed fluid was tested extensively. The biodegradability was 97% or more,
comparable to pure vegetable oil. The fluid is stable at elevated temperatures due to high fire
point (above 300 °C), adding more safety. The beneficial environmental impact of the new
fluid, now commercially available, would be significant. For the first time in the last 100 years
of use of insulating fluids, a truly biodegradable fluid has been developed for use in electrical
apparatus with emphasis on environmental safety.
Green Card: A Biopolymer-Based and Environmentally
Conscious Printed Wiring Board Technology
Printed wiring boards (PWBs) have become ubiquitous in our society and are found in
an ever-expanding range of industrial and consumer products including computers, VCPvS,
cameras, and automobiles. The demand for PWBs is increasing rapidly—the world market
for PWBs has increased at an average rate of $2 billion per year since 1983 to a current value
of over $25 billion. PWBs are composites that are generally formed from an epoxy or novolac
resin coated on fiberglass or paper sheets that are laminated in multilayer stacks that are inter-
leaved with suitably patterned copper sheets. PWBs provide both the substrate for physically
attaching electrical components, as well as copper traces that provide electrical connectivity
between the components. Due to the use of highly crosslinked thermosetting resins, the lam-
inates form intractable composites that cannot be recycled by melting and reforming in the
same manner as thermoplastic polymers.
Of increasing concern is the manufacture and disposal of the more than 150 million
square meters of laminate that are produced globally each year. The resins currently in use for
PWB manufacture are generated entirely from petroleum-based stocks. Natural products,
especially if used in a form similar to that in which they occur in nature, generally take less
energy to produce than their petroleum-based counterparts, hence replacement of part or all
of the current raw materials could result in significant energy savings. Both energy and efflu-
ent (solid, liquid, or gaseous) reductions may be possible by choosing appropriate biobased
raw materials.
New resin compositions that incorporate wood or plant resources (available in commer-
cial quantities) were investigated. The technical objectives of this program culminated in the
development and optimization of the use of lignin—a waste byproduct of paper manufac-
ture—for the fabrication of several PWB demonstration vehicles to prove manufacturing
feasibility. Resins that included as much as 50 to 60 wt% lignin were formulated to meet the
primary requirements for printed circuit board physical and electrical properties. The utility
of lignin in epoxy-based resins was demonstrated for a range of current and advanced appli-
cations. Pilot scale manufacture of resin and laminates using these formulations was
accomplished on standard manufacturing equipment using current processing techniques
and chemicals. In addition, the lignin/epoxy formulations have financial incentives that
increase their desirability due to the inexpensive nature of lignin as a raw material.
A lifecycle analysis was performed, showing that the environmental benefits of a lignin-
based resin system included reductions in energy usage, solid wastes, air and waterborne
emissions, and "greenhouse gases" such as CO2 from petroleum based sources, methane, and
T.J. Watson Research
Center, IBM
Corporation
51
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Solutia Inc.
nitrogen oxides. Due to the lower energy requirements for production of natural raw mate-
rials, fuel usage for resin production can be cut by up to 40% by converting from standard
epoxies to lignin-based resins. Lignin resins can be cast from ketone/alcohol or ketone/propy-
lene glycol methyl ether acetate solvents, which would reduce the usage of methyl ethyl
ketone (a SARA listed chemical) and acetone in PWB manufacture. Disposal concerns are
also reduced, as incineration will produce reduced levels of greenhouse gases, and boards sub-
mitted to compost/landfill will have increased opportunity for biodegradation due to fungi
potentially present in that environment that can break down lignin.
Greenhouse Gases: From Waste to Product
About 5 billion pounds of adipic acid are manufactured worldwide each year. In the
United States alone, approximately 3 billion pounds of adipic acid are produced every year.
Adipic acid is used in the manufacture of a large number of consumer products, including
nylon for carpets, apparel, industrial fabrics, and also for urethanes, plasticizers, and food
additives. Essentially all adipic acid is manufactured today by a three-step process starting
with benzene: the benzene is hydrogenated to cyclohexane, the cyclohexane is oxidized with
air to a mixture of cyclohexanol and cyclohexanone (KA oil), and the KA oil is oxidized to
adipic acid using nitric acid as the oxidant. Waste generation is a serious environmental issue
with the traditional processes used to make adipic acid: the oxidation processes produce large
amounts of nitrous oxide and organic wastes that must be disposed of or destroyed. For
example, with the current technology, the production of 5 billion pounds of adipic acid also
results in the production of 2 billion pounds of nitrous oxide. Nitrous oxide is a known
greenhouse gas with a global warming potential 300 times greater than carbon dioxide and
is also a suspected ozone depleter. It has been estimated that release of nitrous oxide from
adipic acid manufacture accounts for 10% of the annual releases of manmade nitrous oxide
into the atmosphere worldwide.
As part of Solutia's program to search worldwide for new technologies to reduce or elim-
inate waste from its operations, the company initiated a partnership with Boreskov Institute
of Catalysis in Novosibirsk, Siberia, to develop an alternative method for manufacturing
adipic acid. This new process recycles the nitrous oxide waste gas and uses it as a raw mater-
ial in the production of phenol. This eliminates either the direct release of this greenhouse gas
into the atmosphere or the use of expensive, energy-intensive CCh greenhouse gas producing
abatement processes. At the same time, the yield of phenol from Solutia's new technology is
very high. Furthermore, since the cost of this alternative method of producing adipic acid is
lower than the commercial method traditionally used by the chemical industry, the process
is both environmentally and economically sustainable.
A pilot plant demonstrating the process on a continuous basis was started at Solutia's
Pensacola Technology Center in May 1996. The unit has operated successfully since startup
and provided the data currently being used in design of the full-scale commercial plant. The
new plant will utilize all of Solutia's nitrous oxide (250 million pounds per year) to produce
more than 300 million pounds per year of phenol. This revolutionary process represents the
first major breakthrough in the production of phenol in more than 50 years. The new effi-
cient process saves energy and eliminates the emission of massive amounts of greenhouse
gases, while greatly reducing the production of organic wastes.
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Hydrofluoroethers (HFEs)—The Right Balance of
Properties
Research on hydrofluoroethers started in 1994, and the first commercial compound came
to the marketplace in 1996. The "design" of the hydro fluoroethers provides a balance of prop-
erties that make them excellent substitutes for ozone depleting compounds.
3M formed a technical team in the early 1990s to find a substitute for ozone depleting
substances (ODSs) (CFCs and HCFCs). In addition to addressing the issue of ozone deple-
tion, the team also set criteria for candidate molecules on the basis of flammability, toxicity,
photochemical reactivity (potential for smog formation), and global warming potential. The
3M team investigated the performance, health, and environmental attributes of more than
100 compounds before the invention of HFEs. HFEs did not require the team to compro-
mise on any of its desired qualities for an ODS replacement. HFEs do not deplete the ozone
layer, do not contribute to photochemical smog, are very low in toxicity, are nonflammable
and have very low GWPs.
The first commercial product for the HFE program was HFE-7100. HFE-7100
^FgOCHs) was brought to market in 1996 and was followed by HFE-7200
(C4F9OCH2CH3) in 1997- Both of these compounds are approved for use under EPA's
Significant New Alternatives Policy Program (SNAP) for solvent cleaning, aerosol, and heat
transfer applications. EPA also declared these materials as VOC exempt on August 25, 1997-
The acute and subchronic toxicity of HFE-7100 has been thoroughly investigated. An eval-
uation of this data by the American Industrial Hygiene Association Workplace Environment
Exposure Limit Committee yielded an exposure guideline of 750 ppm. The exceptional low
toxicity of HFEs make them unique in a marketplace that has traditionally had to compro-
mise on the toxicity of available alternatives.
Hydrogen Sulfide Elimination from the Substances Not
Precipitated by H2$ Test
Mallinckrodt Baker has developed a method that eliminates hydrogen sulfide from the
substances not precipitated by H2$ test. The existing method uses hazardous hydrogen sul-
fide, takes about 5 hours to perform, and is precise only for combined alkali results. The new
method is safer (does not use hazardous reagents), takes only 30 minutes to perform, and is
accurate for individual element determinations.
Imation No Process Plates
Although the principles of lithography were first applied to printing in 1796, aluminum
plates precoated with photoactive polymers did not enter volume production until the 1950s.
Availability of these presensitized plates fueled rapid growth in the lithographic printing
industry due to superior print performance and economy. When a conventional presensitized
plate is exposed to ultraviolet radiation through a contact masking film, formation of ink
receptive image areas is initiated. These plates then require wet development to activate the
printing surface, most often using a mechanical processor that also rinses the plates. Many
developers contain hazardous solvents. Developer solutions saturate with dissolved coating
compounds, including toxins and heavy metals. Total U.S. printing plate consumption in the
year 2000 is expected to reach 68 million square yards. Wet processing of this total volume
will consume over one million gallons of aqueous developer, based upon typical depletion
rates. Depleted solutions containing coating solids require disposal at hazardous waste sites in
3M Center
Mallinckrodt Baker, Inc.
Imation Corporation
53
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The Geon Company
many regions of the United States. In addition, more than 1.2 billion gallons of rinse water
would become part of the waste stream.
Recognizing the environmental costs of the total waste stream, Imation launched an
intensive Research and Development effort to commercialize plates requiring no wet chemi-
cal processing of any kind. Today, this no process technology provides a superior printing
plate, without wet processing, under the trademark name "Imation™ No Process Plates."
Demand for the technology is growing rapidly across the printing industry. Imation™ No
Process Plates employ photoactive polymers that form printing surfaces without wet chemi-
cal processing. When the plate is exposed to ultraviolet radiation through a masking film,
formation of ink receptive areas is initiated, but activation takes place on press under action
of the ink/water emulsion during the normal plate roll up process. This technology is applic-
able across the printing industry, from general commercial lithographic printing to forms,
packaging, and newsprint operations. Environmental benefits available to the industry are
truly significant and valuable because pollution is prevented through source reduction. When
Imation™ No Process Plates are used along with Imation's DryView™ imagesetting films,
even greater waste reductions are possible. If 68 million square yards of DryView™ film were
used to image plates, an additional 2.4 million gallons of film developer, 4.1 million gallons
of fixer, and 675 million gallons of rinse waste could be eliminated from the waste stream.
Increased Utilization of Raw Materials in the
Production of Vinyl Chloride Monomer
Commercial catalytic oxidation processes have been adapted for disposal of organic sol-
vents, ground-water pollutants, synthetic co-products, incinerator flue exhaust, and
automotive exhausts. In the large-scale catalytic oxidation of chlorinated hydrocarbons, fuel
value is typically recovered as steam and chlorine is recovered as HC1 and/or Cb. Various
approaches are disclosed in the patent and scientific literature. Studies of the deactivation of
commercial catalysts over long-term exposure of streams of chlorinated and nonchlorinated
hydrocarbons found that during long-term use the reaction temperature needed to be
increased in order to maintain high conversion rates and reduce catalyst deactivation. In com-
mercial scale catalytic oxidation of chlorinated materials, the maximum operating
temperatures are limited by the optimal temperature range for the chosen catalyst as well as
the corrosion resistance inherent in the metals used for the equipment. For example, certain
economical nickel alloy steels undergo catastrophic corrosion in the presence of HC1 at or
above 530 °C. Increasing the operating temperature of the reaction approaching 530 °C will
lead to higher corrosion rates. It would therefore be desirable from an economic standpoint
to maintain very high conversion of 99% or higher of feedstocks over long periods of time
without risking increased rates of corrosion.
Geon developed Catoxid™ as a catalytic process for the recovery of chlorine and energy
from chlorinated organic materials. Typically, such materials are co-products of the produc-
tion of useful chemicals such as vinyl chloride monomer (VCM), or other chlorinated and
nonchlorinated products. The recovery is accomplished by catalytically reacting the
organochlorines and an oxygen containing gas such as air to produce hydrogen chloride
(HC1), carbon dioxide (CC^), and water in a fluidized bed reactor. No additional fuel is
required to sustain the exothermic reaction, and the chemical energy of the materials is recov-
ered as steam. The HC1 produced is fed directly to an oxychlorination reactor and recovered
as 1,2-dichloroethane (EDC). The EDC is subsequently converted to VCM and ultimately
PVC. The Catoxid111 process thus reduces the amount of chlorine required to produce a spe-
cific amount of the desired product VCM, and also reduces the fuel requirements of the
54
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production facility. Unlike incineration, which is the only acceptable alternative, the
Catoxid™ process has no vents to the atmosphere. In addition, since no aqueous hydrochlo-
ric acid is generated (as is usually the case for incinerators), there is no need to utilize caustic
or limestone to neutralize the acid. The Catoxid™ process was developed for the
EDC/VCM/PVC industry and is directly applicable to many technologies used to produce
VCM.
An Innovative Process for the Manufacture of
Caprolactam from Postconsumer Nylon 6 Carpet and
Other Nylon 6 Waste Articles
A proprietary depolymerization and purification process developed by Allied Signal and
DSM Chemicals North America converts an alternative feedstock, postconsumer nylon 6
carpet, to high-quality caprolactam, the monomer for nylon 6. The innovative technology is
presently being commercialized through a manufacturing joint venture, Evergreen Nylon
Recycling LLC, in Augusta, Georgia.
It is estimated that in 1996, more than 1.3 billion pounds of postconsumer nylon 6 car-
pet was disposed of via landfilling or incineration. At full production, approximately 20% of
this waste stream, or 230 million pounds per year of waste carpet, will be diverted from land-
fills and converted into 100 million pounds of caprolactam at the Evergreen facility. The
recovered caprolactam is polymerized into nylon 6 polymer and used in such critical appli-
cations as carpet fibers and engineering resins, demonstrating that quality products can be
regenerated from waste carpet sources indefinitely. Additional environmental benefits include
reduced oil dependency of 700,000 barrels per year, reduced energy consumption of 4.49
Btus, and reduced global warming gas emissions (67% CC^ and 100% N2O).
To secure the required supply of postconsumer nylon 6 carpets, Allied Signal created an
infrastructure to collect, sort, and deliver waste nylon 6 carpet to the commercial facility in
Augusta, Georgia. The infrastructure, together with the breakthrough depolymerization tech-
nology, has resulted in a recycling process that is both economical and environmentally
beneficial. Landfill diversion, energy savings, and reduced greenhouse gas emissions are exam-
ples of the environmental benefits.
In Situ Chemical Stabilization of Lead-Based Paint
Waste from Abrasive Blasting
A team of researchers from the U.S. Army Construction Engineering Research
Laboratories (USACERL) and the TDJ Group developed, demonstrated, and patented an
innovative technology for the removal of lead-based paint from structures at a significant cost
savings compared to traditional methods. The engineered abrasive combines a traditional
abrasive media with a calcium silicate-based material (commercially known as Blastox™)
which chemically stabilizes the lead in the residual abrasive blast waste. The stabilized waste
will not show the toxicity characteristic for lead (EPA Method 1311, Toxicity Characteristic
Leaching Procedure) and can be disposed as a nonhazardous waste at a much lower cost (up
to 30% savings on total project costs for potential DOD-wide savings of $5 billion). The
method enjoys the same high production rate of traditional abrasive blasting and requires no
equipment modification. The key technological breakthrough combines a traditional abra-
sive media (such as silica sand or coal slag) with a calcium silicate-based material (CaO at 65
wt%, SiCh at 22 wt%) which chemically stabilizes the lead in the residual waste. The chem-
Allied Signal Inc.
U.S. Army Construction
Engineering Research
Laboratories
55
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U.S. Bureau of
Engraving
Mobil Oil Corporation
ically stabilized lead-containing waste will not leach lead at a rate greater than 5 pprn and will
not be characterized as hazardous waste.
ISOMET: Development of an Alternative Solvent
The U.S. Bureau of Engraving and Printing, the world's largest security manufacturing
establishment, produces currency, postage stamps, revenue stamps, naturalization certificates,
U.S. savings bonds, and other government securities and documents. Until 1991, Typewash,
a solvent mixture, was used by the Bureau for cleaning typographic seals and serial numbers
of the COPE-Pack (overprinting presses) and for cleaning of sleeves of postage stamp press-
es. Typewash is a solvent mixture composed of methylene chloride (55%), toluene (25%),
and acetone (20%). The use of Typewash was no longer in compliance with the District of
Columbia Environmental Law and the Federal Air Toxic Law. An alternative solvent, Isomet,
was designed and developed to replace Typewash. Isomet is a mixture of isoparaffmic hydro-
carbon (55%), propylene glycol monomethyl ether (10%), and isopropyl alcohol (35%).
Isomet is less toxic, less polluting, and environmentally friendly. Isomet was found to be
acceptable in the areas of (1) cleaning ability, (2) solvent evaporation rate, (3) solvent odor,
(4) environmental and safety compliance, and (5) cost. Thus, a solvent discharged at the rate
of 7,500 gallons per year was made environmentally friendly. The performance of Isomet is
excellent and it has been used for cleaning all postage stamp and overprinting presses in the
Bureau.
Membrane Separation in Solvent Lube Dewaxing
Mobil Oil Corporation and W R. Grace have developed a pioneering technology that sig-
nificantly reduces the impact of the solvent refining of lubricants on the environment. The
membrane-based process provides greater lubricant selectivity and reduces waste generation
while simultaneously decreasing emissions of volatile organic compounds and greenhouse
gases.
The use of membranes to facilitate the solvent dewaxing of lubricants represents the first
significant, environmentally focused improvement in this technology in over 40 years. In
conventional lube dewaxing, a lube oil/solvent mixture is generated as part of the process.
The solvent is removed from this mixture by distillation to isolate the lube oil product. The
solvents are then cooled and refrigerated to the desired process temperature before being recy-
cled to the process. The improved process uses a proprietary polymeric membrane material
developed by WR. Grace to separate up to 50% of the dewaxing solvents from the lube
oil/solvent mixture. Consequently, the spirally wound membranes significantly reduce ener-
gy consumption by minimizing the need for energy-intensive distillation, cooling, and
refrigeration.
As a result, a single commercial facility could reduce fuel oil consumption by 36,000
bbl/yr. This equates to a reduction in greenhouse gas emissions of about 20,000 tons/yr for
each plant in which the technology is installed. The same plant would reduce cooling water
use by nearly 4 million gal/day, or about 1.5 billion gal/year. The use of membranes allows
more solvent to be recirculated in the dewaxing operation, which in turn leads to higher
lubricant yields and a reduction in the amount of undesirable byproducts generated in the
process. The higher process yields reduce by about 5% the volume of crude oil required to
produce a given volume of lube oil. For a world-scale plant, this equates to a savings of about
2 million barrels of crude oil per year. Finally, the loss of dewaxing solvents, which are volatile
organic materials, into the environment could be decreased by 50 to 200 tons/yr per plant
depending on the age and mechanical condition of the dewaxing equipment. This results
56
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from a reduction in the number of pieces of equipment required to refine a given volume of
lube oil.
This technology was first implemented commercially at Mobil's Beaumont, Texas, refin-
ery. It can be easily retrofitted into existing plants or incorporated into new plant designs and
is currently available for license.
Metabolic Engineering of Crops for Commercial
Production of Biodegradable Plastics
Poly(hydroxyalkanoates) (PHAs) are a class of polymers accumulated by numerous bac-
terial species as carbon and energy reserves. These polymers have thermoplastic properties
that make them attractive as biodegradable alternatives to petrochemical plastics. One poly-
mer of this class, poly(S-hydroxybutyrate-co-S-hydroxyvalerate) (PHBV) is currently
produced by fermentation of the bacterium Ralstonia eutropha; however, the process is not
economically competitive with polymer production from petrochemicals. PHA production
in green plants promises much lower costs, but producing polymer with the appropriate
monomer composition is problematic.
The goal of Monsanto is to produce PHBV by transferring the R. eutropha biosynthesis
pathway to plants and modifying the plant's intermediary metabolism to generate the appro-
priate metabolic precursors for copolymer synthesis. Metabolic engineering of Arabidopsis
and Brassica to redirect intracellular pools of both short-chain fatty acids and amino acids
resulted in the production of PHBV. This process required transformation of plants with four
separate transgenes, and a novel application of one endogenous plant enzyme.
This technology provides a novel biosynthetic route to plastic using atmospheric CC>2 as
the carbon source and sunlight as energy. The project is intended to utilize green technology
from cradle to grave. The energy for polymer extraction and processing will ultimately be
provided by the residual biomass derived from the polymer production crop. Key environ-
mental benefits include utilization of atmospheric CCh (rather than petroleum) as a chemical
feedstock, reduced combustion of fossil fuels for polymer production, and reduced con-
sumption of landfill space because the polymer is biodegradable (compostable). Additionally,
economic benefits to the agricultural sector will be associated with production of the new or
modified crop.
This project is one of the first and most complex attempts to metabolically engineer green
plants to produce novel chemicals. Agriculture already provides a large number of chemical
raw materials for industry, including sugars, oils, fibers, and many small molecules. The
power of this new technology lies in the ability to manipulate plant metabolism, thereby cre-
ating new pathways leading to new products. Therefore, this project serves both the specific
aim of PHBV production in plants, and opens the use of green plants as factories for the com-
mercial, environmentally sustainable production of biodegradable plastics.
Minimizing Environmental Emissions by Using
Different Solvents in Manufacturing Processes
Solvent selection is an important aspect of chemical process development. Two well-
known solvent effects are their influence on the desired reaction kinetics, and potential to
minimize the effects of hazardous undesired reactions through dilution and heat absorption
as solvent is vaporized.
Monsanto Company
Eastman Kodak
Company
57
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Nalco Chemical
Company
Recent testing of energetic chemicals has demonstrated that the chemistry and kinetics of
their undesired decomposition reactions are also significantly altered by solvents. Eastman
Kodak has successfully applied this knowledge to the process safety element of process devel-
opment by systematically evaluating potential solvents for their effectiveness in minimizing
the potential environmental impacts of accidental process upsets. For example, the batch size
of an existing process had been very restricted because of the potential severity of a thermal
runaway. Research on chemistry/solvent-specific decomposition data was utilized to select
candidate replacement solvents that would minimize environmental hazards. A cooperative
effort by safety engineers and development chemists ensued, resulting in a final process that
entirely eliminated the possibility of loss of containment due to a thermal runaway. The end
result of this work is that a new tool is available to help chemists and chemical engineers
develop inherently safer chemical processes.
Historically, changing a process in order to mitigate a potential hazard has been accom-
plished through drastic changes in process conditions, process chemistry, or through
equipment modifications, all of which require significant capital and resources. It is demon-
strated by example that the application of recent investigations into the effect of solvents on
the decomposition kinetics of energetic chemicals can be leveraged to substantially decrease
the potential environmental impact of thermal runaways in production-scale equipment. The
technology described has the potential for broad application in chemical manufacturing
processes that make or use thermally unstable materials.
Nalco Fuel Tech NOxOUT^ Process
Nalco Fuel Tech develops and markets air pollution control technologies worldwide.
Their flagship technology, NOxOUT®, reduces harmful nitric oxide emissions of stationary
combustion sources to yield nitrogen gas and water, leaving no disposal solids. Nitrogen oxide
(NOx), the pollutant targeted in NOxOUT® technologies, is a "primary" pollutant, and
reducing it directly reduces acid rain, particulate matter less than 2.5 microns in diameter,
and greenhouse gases and mitigates nitrogen eutrophication sensitive watersheds. NOx also
is a precursor in the formation of ground-level ozone that, along with NOx, is one of EPA's
six criteria pollutants. More than 100 million of our nation's citizens and many more global
inhabitants live in areas that are classified "nonattainment for ozone," [i.e., ambient air ozone
levels exceed 120 parts-per-billion (ppb)]. High ozone levels are linked to many forms of res-
piratory problems, leading EPA to promulgate the new National Ambient Air Quality
Standard of 0.080 ppm for an 8 hour period to adequately protect human health and wel-
fare. The NOxOUT® process meets today's environmental challenges by using less toxic
chemistry, reducing or eliminating toxic releases to the environment, converting wastes to
more environmentally acceptable discharges, and reducing energy consumption. The
NOxOUT® process provides an economical solution for complying with the stringent regu-
latory requirements for NOx reduction from fuel combustion sources. NOxOUT® can
reduce NOx emissions by 75% compared to the 20 to 50% reduction from existing treat-
ment.
The NOxOUT® process is being used commercially. It can be used on new combustion
units for small industrial units to large utility installations, or it can be retrofitted to existing
units. The environmental benefits are significant NOx reduction, elimination of byproduct
disposal, toxic use elimination of Superfund Amendment and Reauthorization Act Title III
chemicals, and increased energy efficiency.
58
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Nalco LAZON Technology
The U.S. paper industry suffers more than $1 billion per year in lost production alone
due to biological contamination problems. Nalco LAZON Technology gives papermakers a
new integrated approach that allows them to improve control of microorganisms with sig-
nificantly lower environmental impact. This technology is a unique bundling of innovations
that includes a synergistic biocide combination, two new monitoring technologies, and spe-
cialized feed equipment. The primary component of LAZON Technology is the chemistry, a
combination of the nonhalogen oxidant peracetic acid and a standard organic biocontrol
agent, which together provide antimicrobial activity that is far greater than expected from the
individual components. Improved microbiological control is demonstrated with the Nalco
BIOWATCH™ Optical Fouling Monitor. Minimal or no environmental impact is assured
by Nalco's BIOWATCH TRA-CIDE® system, which rapidly measures biocide toxicity and
microbial ATP onsite. Finally, a specially designed chemical feed system and Nalco's PORTA-
FEED® returnable container complete the program. This interlocking network of novel
technology decreases biocide use, measures product performance and residual toxicity, and
minimizes the chances of accidental biocide release during transportation or product feed.
This Nalco technology is a complete program that improves safety, increases energy conser-
vation, reduces operating costs, and minimizes point source release.
Nalco Chemical
Company
Nalco NALMET® Heavy Metal Removal Technology
Stricter NPDES discharge limits for effluent metals impact both metal and nonmetal
industries. The parts-per-billion (ppb) limits for heavy metals removal cannot be met by tra-
ditional metal precipitation processes. Membrane processes such as ion exchange,
ultrafiltration, and reverse osmosis are historically recommended for metal removal. They
require significant capital investment and still require pretreatment of these waste streams. A
chemical removal process that can reduce metals to acceptable NPDES levels represents an
important new technology for industrial waste treatment. Nalco has developed NALMET®,
a patented program for metal removal. This low-toxicity technology includes a liquid poly-
mer containing a metal chelating functional group that simultaneously precipitates metals
and clarifies the waste stream, all in one product. It also includes an automated chemical feed
system with patented sensor technology to guarantee standard treatment. The program allows
customers to have their NALMET®-generated sludge reclaimed by our partner company. The
benefits of the NALMET® program are that sludge volumes are reduced 25 to 90%, product
overfeed is reduced, environmental releases of treatment chemical are reduced, a less toxic
treatment chemical is used, and customers consistently meet ppb metals discharge limits.
Through Nalco's integrated, innovative approach, our customers achieve pollution preven-
tion. Cradle-to-grave environmental management is achieved with environmental toxicity
reduction.
Nalco Chemical
Company
Nalco PORTA-FEED®
During the 1980s, disposal of chemical residue and its containers was a potential human
health and environmental risk for chemical users and the public. In 1985, Nalco developed
the PORTA-FEED® Advanced Chemical Handling System for chemical applications world-
wide. It is the largest private fleet of returnable containers in the world at a capital cost of
$240 million. These 105,000 units are owned, monitored, maintained, and cleaned by Nalco
as a cradle-to-grave risk management process. The program consists of the units, a comput-
erized tracking system, a zero defect delivery system, and a systematic maintenance and
Nalco Chemical
Company
59
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cleaning program. This pollution prevention program has prevented the disposal of over 3
million drums and 30 million pounds of chemical waste. In 1985, 33% of our annual sales
($659 million) were shipped in 500,000 nonreturnable drums. Fifteen percent of 1996 annu-
al sales ($1.3 billion) were shipped in nonreturnable drums. By the year 2000, we expect to
have eliminated the disposal concerns from 10 million drums and 100 million pounds of
chemical waste worldwide. The system benefits are reduction of human and environmental
risk from transportation to disposal, reduced chemical inventory, and renewable resource
implementation.
Nalco Chemical
Company
Nalco TRASAR Technology
From tracing to tagging to product performance monitoring, Nalco impacts the way the
world manages water. Using monitoring approaches, customers are provided with a window
into their water systems, helping them detect and control chemical feed, reduce pollution at
its source, conserve energy, and prevent unintended environmental releases. The first
approach adds low levels of inert fluorescent "trace" to water treatment products. The tracer
allows controlled chemical application instantaneously and automatically. Chemical treat-
ment reductions of 20 to 30% have resulted from this process. The second approach involves
direct, automatic detection of a fluorescence tagged treatment chemical. The chemical's pres-
ence can be detected in systems where low-level detection was not possible, correlating
variations in treatment consumption with variations in the water system's operation. The final
approach tracks the resulting product performance, such as corrosion protection or foam
elimination in the process system, allowing further refinement of chemical dosing. These
technologies provide wide-ranging benefits: less consumption and more effective use of
industrial water, reduced chemical use, energy conservation, measurement of the fate of
chemical additives, detection of industrial and biocide treatment for enhanced risk manage-
ment, and minimization of environmental release. These applications provide a complete
cradle-to-grave approach to water management.
Albright & Wilson
Americas Inc.
A New Environmentally Friendly Corrosion Inhibitor
for Industrial Cooling Systems
The U.S. industrial water treatment market for corrosion inhibitors is 50 million pounds
per year, growing at 5 to 7% annually. There are more than 500,000 individual use sites in
this industry category. Exposure to corrosion inhibitors is thus a major concern.
Conventional corrosion inhibitors used for the control of corrosion in industrial cooling sys-
tems are either hazardous to the environment or have other drawbacks, such as instability in
the presence of oxidizing biocides, limiting their applicability. A new, all-organic corrosion
inhibitor, Bricorr® 288, a phosphonocarboxylate mixture, has been discovered and patented.
Bricorr® 288 is a highly effective corrosion inhibitor with wide applicability to industrial
cooling systems. Bricorr® 288 has an environmental profile permitting, in many instances,
discharge of treated water directly into rivers without any adverse effects. In many cases, the
recommended treatment level is at least an order of magnitude below that which would be
toxic to fish. Bricorr® 288 is also extremely water soluble and, therefore, will not bioaccu-
mulate; this represents a much reduced risk to higher life forms. Additionally, the
manufacture of Bricorr® 288 is via a new, patented aqueous route that does not use toxic sol-
vents. The process is inherently 'clean' in that it does not produce any discharges to water or
air, nor any byproducts. Bricorr® 288 also has excellent handling characteristics due to its low
mammalian toxicity helping to improve safety, particularly when used by those with minimal
experience handling industrial chemicals.
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New Organic Corrosion Inhibitors Help Replace Toxic
Heavy Metals and Reduce Solvent Emissions
The coatings industry in the United States has had to focus their efforts to develop prod-
ucts that are compliant with an ever expanding set of federal, state, and local regulations, all
designed to reduce or eliminate materials that pose a threat to either human health and safe-
ty or more broadly, environmental safety. The Irgacor family of organic corrosion inhibitors
was designed and developed specifically to replace the standard anticorrosive pigments that
are based on heavy metals such as lead, chrome, zinc, strontium, and barium. These heavy
metals are classified as being harmful to humans and/or the environment. In addition to tox-
icity generally associated with heavy metal-based anticorrosive pigments, they are not
particularly effective in low volatile organic content (VOC) waterborne coatings due to
incompatibility.
Irgacor organic corrosion inhibitors are heavy metal free. They offer effective replacements
for heavy metal-based products and can produce commercially viable waterborne and high
solids solvent-based coatings. Replacement of all conventional corrosion inhibitors by these
organic corrosion inhibitors could result in a potential overall annual source reduction of
heavy metal-based inhibitors of approximately 11.0 million pounds (4.2 million pounds
chromate based, 3-9 million pounds zinc/nonchromate, 3-0 million pounds barium borates
and silicates). Irgacor corrosion inhibitors are typically used at levels (based on total solids) of
0.5 to 4% compared to 10 to 20% or more for anticorrosive pigments. The volume of Irgacor
necessary to replace the 11.0 million pounds therefore will only be 2.0 million pounds. In
addition, if Irgacor can further stimulate the replacement of solvent-based systems with
waterborne coatings in the maintenance, auto refmish, and marine markets by 20%, the
annual volume of VOCs being emitted to the atmosphere would be reduced by 6.7 million
pounds (8.0 million pounds to 1.3 million pounds). Irgacor organic corrosion inhibitors pro-
vide both long-term anticorrosive properties as well as excellent protection against flash rust.
This provides the coatings industry with effective materials to further the development of
waterborne coatings as replacements for solvent-based, higher VOC products.
New Technology Converts Waste to Valuable
Intermediates
Methylchlorosilanes, intermediates for the growing silicone industry, are produced by the
reaction of elemental silicon with methyl chloride in a fluidized bed reactor. As with most
chemical processes, conversion of reactants to products is not 100%; and while the percent-
age of waste is small for this process, these waste streams become more significant as the
production volume of this industry continues to grow.
A significant fraction of the wastes produced by this "direct process" reaction are high-
boiling methylchlorodisilanes that have been disposed of in the past by quenching them to
form a nonhazardous landfillable material. In pursuit of reducing wastes and recovering value
from the fed raw materials, Dow Corning has developed a process that provides for the con-
version of these waste materials into valuable monosilanes by reacting the
methylchlorodisilanes with hydrogen gas to form methylhydrogenchlorosilanes. Thus not
only are the wastes associated with the production of chlorosilanes reduced, but the value of
the raw materials are recovered as intermediates important to a wide range of siloxane prod-
ucts.
Ciba Specialty
Chemicals Corporation
Dow Corning
Corporation
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Akzo Nobel
Roche Colorado
Corporation
Once this new technology is implemented in Dow Coming's basic silicone plants, total
cost savings will be $3 million per year. This number can be expected to rise significantly as
the production capacity of these plants increase.
Next Generation Fire-Resistant Fluids
Triaryl phosphate esters constitute a major industrial product category for fire-resistant
hydraulic fluid and lubricant applications. Tertiary butylphenyl phosphate (TBPP) esters, a
more specific class in this category, have a growing share of these markets due to their greater
stability and lower toxicity compared to phosphate esters derived from naturally occurring
cresols and xylenols. Current production methods yield TBPP esters with 10 to 45% tri-
phenyl phosphate, a less stable component and a known esterase enzyme inhibitor that also
is known to degrade the hydrolytic stability crucial for hydraulic fluid and lubricant applica-
tions.
Two synthetic approaches were developed to produce TBPP esters in high yield with less
than 5% triphenyl phosphate. Both use commercially available raw materials and existing
technology for production. The processes do not adversely impact environmental emissions
or effluents. Most importantly, these new TBPP esters will be cost-effective to produce, given
the performance advantages they bring to the marketplace.
These next generation TBPP esters are more stable and less hazardous for many applica-
tions reducing environmental concerns about recycling and disposal, as well as reducing
potential worker exposure hazards with much lower esterase inhibition properties. A patent
has been filed on these TBPP esters and on the methods to manufacture them. Plans are in
place to implement production of these novel products in 1999-
A Novel and Efficient Process for the Production of
Cytovene®, A Potent Antiviral Agent
The design, development, and implementation of environmentally friendly processes for
the large-scale production of pharmaceutical products is one of the most challenging aspects
of business operations in the pharmaceutical industry. Significant efforts toward developing
new and efficient synthetic processes for the preparation of Cytovene®, a potent antiviral
agent for the treatment of cytomegalovirus (CMV) retinitis infections in immunocompro-
mised patients, have been made since the discovery of Cytovene® in 1980. Patients who are
particularly at risk for developing CMV include those with AIDS and patients who are trans-
plant recipients. In the early 1990s, Roche Colorado Corporation developed the first
commercially viable process for the production of Cytovene®. In 1993, chemists at Roche's
Boulder Technology Center developed a novel commercial process for the manufacture of
Cytovene®, which at the time had an estimated commercial demand of about 50 metric tons
per year.
The Guanine TriEster Process (GTE), which was registered with the FDA as the current
manufacturing process for the world's supply of Cytovene®, achieved several environmental
and economic goals through technology-based designs for pollution prevention. These
achievements include a reduction in the number of chemical processing and isolation steps
from six to two steps, a reduction in the number of reagents and intermediates from 22 to
11, recovery and reuse of three out of four major reagents, a reduction in the number and
quantities of byproducts and waste generated, doubling of the processing throughput of the
process, and at the same time, an increase in the overall yield of the product by more than
25%.
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The new GTE Process for the commercial production of Cytovene® clearly demonstrat-
ed the successful implementation of the general principles of green chemistry The
development of environmentally friendly syntheses—including the development of alterna-
tive syntheses utilizing nonhazardous and nontoxic feedstocks, reagents, and solvents,
elimination of waste at the source, and elimination of the production of toxic waste and
byproducts—established a new and innovative technology for a general and efficient method
for the preparation of Cytovene and other potent antiviral agents for the treatment of CMV
retinitis and AIDS-related diseases.
Oxidizer Scrubber Project
NASA, in conjunction with the previous Engineering Support Contract contractor, I-
NET, and the current contractor, Dynacs Engineering Co., Inc., has developed an innovative
process that converts hypergolic oxidizer waste to a fertilizer used by Kennedy Space Center
(KSC). The Toxic Vapor Detection (TVD) Laboratory of the KSC has demonstrated that the
efficiency of the oxidizer scrubbers can be increased, a hazardous waste stream can be avoid-
ed, the operating cost of the process can be lowered, and fertilizer purchases can be reduced.
Hypergolic propellants are used in spacecraft such as the Space Shuttle, Titan IV, Delta II,
and other vehicles and payloads launched at KSC and Cape Canaveral Air Station (CCAS).
Fueling and deservicing spacecraft constitute the bulk of operations in which environmental
emissions of NOx occur. Monoethylhydrazine, nitrogen tetroxide, and hydrazine are the
main propellants of concern. The scrubber liquor waste generated by the oxidizer scrubbers
(approximately 311,000 pounds per year) is the second largest waste stream at KSC. The
waste disposal cost for this oxidizer scrubber liquor is approximately $0.227 per pound, or
$70,600 a year.
With the new process change, the scrubber liquor waste stream at KSC and CCAS will
be converted to a high-grade fertilizer, which will be applied to citrus groves. The process
reacts nitrogen tetroxide with 1% hydrogen peroxide and potassium hydroxide to produce
potassium nitrate, which is a major ingredient in commercial fertilizers. This process avoids
the generation of hazardous wastes, which occurs when sodium hydroxide is used as the
scrubber liquor. In addition, the new scrubber liquor is more efficient in capturing nitrogen
tetroxide than when sodium hydroxide is used. For example, when the new and existing
scrubber liquors were compared under the same test conditions, the efficiencies were
improved from 72.6 to 98.7% and 98.3 to 99-99% for the new scrubber liquor. Therefore,
the emissions from the scrubber were 10 to 200 times lower for the new scrubber liquor than
the emissions from the sodium hydroxide scrubber liquor. This new chemical change has
eliminated the second largest hazardous waste stream at KSC and developed a new scrubber
liquor, which is approved for application as fertilizer to the lawns and citrus groves at KSC.
The cost savings with this new system amount to approximately $80,000 per year.
Oxygenation of Hydrocarbons by Photocatalysis: A
Green Alternative
The chemical industry is a significant component of the domestic economy, generating
well over $250 billion in sales and a trade surplus exceeding $15 billion in each of the last
five years. The industry is also a major source of industrial waste and is the dominant source
of hazardous waste in the United States. The costs of handling, treating, and disposing of
wastes generated annually in the United States has reached 2.2% of gross domestic product
and continues to rise.
Dynacs Engineering
Co., Inc., Kennedy
Space Center
National Risk
Management Research
Laboratory, U.S.
Environmental
Protection Agency
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The chemical manufacturing industry generates more than 1.5 billion tons of hazardous
waste and 9 billion tons of nonhazardous waste annually. Roughly half of the releases and
transfers of chemicals reported through the Toxics Release Inventory and 80 to 90% of haz-
ardous waste generation reported through the Resource Conservation and Recovery Act are
due to chemical manufacturing. Organic chemicals constitute the largest source of the toxic
releases. Many of these releases can be minimized by improving the conventional house-
keeping methods and pollution prevention techniques. Some of these techniques include
better management of material and energy, more efficient process control, optimizing process
conditions, and recycling and reusing waste and byproducts. However, cleaner production
methods can be achieved by adopting "green synthetic" methods.
In recent years, there has been considerable work aimed at utilizing semiconductors pho-
tocatalysts for a variety of applications. High-value oxygenated organic compounds have been
successfully synthesized from linear and cyclic hydrocarbons by a low-temperature photocat-
alytic oxidation using the semiconductor material titanium dioxide (TiC^). Various
hydrocarbons were partially oxygenated in both aqueous and gaseous phase reactors using
ultraviolet light and titanium dioxide at mild conditions. The conversions and selectivities
obtained for the partial oxidation of hydrocarbons have been comparable to those achieved
with the conventional method.
Vapor phase photocatalytic oxidation of toluene with air, using a continuous reactor at
160 °C and 27 mW/cm2 irradiation, resulted in 12% conversion per pass to benzaldehyde
and benzole acid, with a 95% selectivity to benzaldehyde. Gas phase oxidation of cyclohexa-
ne achieved up to 6% conversion per pass, and the major products obtained were
cyclohexanol and cyclohexanone, with no detectable formation of CCh. The gas phase pho-
tocatalytic reactors eliminated the separation step involved with liquid solvents and catalyst
slurry mixtures, and minimized the adsorption of products to the catalyst.
Initial life-cycle analysis studies have shown that this technology has the potential to
reduce water contaminations and eliminate the use of toxic metal catalysts and solvents.
Light-induced catalysis expands the possibilities of using molecular oxygen in partial oxida-
tion reactions that are now being conducted with far more expensive polluting oxidants. This
technology also promises the potential of visible light-induced chemistry for commercially
important syntheses. Furthermore, the high selectivity and mild conditions achieved with
photochemical routes will be especially attractive for the manufacturing of fine chemicals.
National Risk
Management Research
Laboratory, U.S.
Environmental
Protection Agency
PARIS II Solvent Design Software
There is a great need to replace solvents used in industry whose continued use presents
environmental difficulties, such as worker health concerns and environmental impacts such
as ozone depletion and environmental toxicity To address this need, a research program has
been underway to create the solvent design software PARIS II (Program for Assisting the
Replacement of Industrial Solvents, Version 2). PARIS II designs solvents by matching the
physical properties and behavior of undesirable solvents to that of environmentally better
replacements. The theory embodied in PARIS II is based on the observation that the math-
ematical expressions governing solvent behavior are universal, and that the identity of the
solvent is represented by coefficients (e.g., viscosity, diffusivity, activity coefficients). It is,
therefore, possible to design entirely new replacement solvents by mapping one solvent into
another using these coefficients, and the resulting replacement will mimic the behavior of the
original solvent irrespective of intended application. PARIS II embodies a sophisticated algo-
rithm using property prediction and phase equilibrium calculations to design mixtures with
specific properties and behavior. These properties include general, dynamic, and equilibrium
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properties, environmental requirements (i.e., a VOC index and an environmental index), and
performance and safety requirements. The result is general and robust solvent design soft-
ware.
It is worth emphasizing that PARIS II is capable of not only designing solvents that mimic
the behavior of another solvent, but it can actually design solvents with improved techno-
logical and environmental properties over the existing solvent. The reason is that the
algorithm allows one to actually request a solvent with, for example, 10% lower viscosity,
20% higher density, or 50% lower vapor pressure. This is most useful when the replacement
solvent is a mixture so that different components can be added and the composition adjust-
ed by the software. With the PARIS II algorithm, improving environmental performance is
automatic because the algorithm looks for solvents with environmental indexes as close to
zero as possible. Improving the technological performance of the solvent, however, is at the
discretion of the user.
PVC Replacement Technology
Phthalates and chlorine, two components of PVC products, are among the synthetic
chemicals that environmental activists claim are interfering with the hormone system in ani-
mals and humans. In addition, when PVC is manufactured or combusted, dioxins are formed
as byproducts. Many countries, including Germany, Australia, Denmark and Sweden, are
taking actions to restrict the use of and manufacture of PVC. Today, there is a new breed of
polymer catalysts that allow, during the course of polymerization, the production of polymers
with unique product characteristics. These characteristics make it possible for polyolefins to
enter and compete in new markets hitherto not seen. These catalysts are called metallocenes
and essentially allow polymer properties to be tailor-made during reactor polymerization.
The basic challenge of the product replacement (vinyl flooring) program was to develop
a system that could combine the excellent physical properties of metallocene polyolefins with
the unique processing characteristics of PVC. For instance, a patented chlorine-free floor cov-
ering was developed showing that a metallocene based polyolefm utilizing selected
nonvolatile monomers goes beyond the conventional melt processing procedure and allows
processing on conventional PVC manufacturing equipment. Unlike plastisol, where the
"cure" is due to the solubilization of the plasticizers, the final polyolefm product contains no
dissolved liquid and results in a multiphase polymer system. This same system can be utilized
in a wide array of applications and manufacturing processes, and offers environmental and
product performance improvements.
The use of metallocene polyolefins is important for two distinct reasons. The most obvi-
ous is the inherently superior physical properties relative to conventional polyolefins. The
second is directly associated with their chemical structure. Their unique polymerization
process results in each polymer chain having a terminal double bond. This double bond can
participate in the free radical polymerization of the liquid monomers (methacrylate and aery-
late). The copolymers that result will contain both olefmic and acrylic segments. Such
combined polymers will act as compatibilizers for the two polymeric phases. This compati-
bilization will play a major role in several characteristic functions of various applications.
Chemecol, L.L.C., Forbo
International, and
McDonough Braungart
Design Chemistry,
L.L.C.
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M.A. Hanna Color—
Technical Center
DuPont Company
Reducing VOC Emissions by Eliminating Painting and
Labeling Operations with a New Color Laser Marking
System for Plastic Parts
Decorating, marking, or coding plastic parts can be a challenge. Many plastics require sur-
face treatments before paint will adhere. In certain environments, printed marks lack
durability and may require a protective topcoat. Self-adhesive labels, another option, pose
similar durability problems coupled with high scrap rates. A new technology to mark plastic
parts in color with a laser has been developed by M.A. Hanna Color. This technology offers
dramatic improvements in the ability of processors and end users to permanently mark a wide
range of plastic parts using a broad color palette. The technology is expected to replace a sig-
nificant portion of plastic printing and adhesive label decorating/coding operations in most
major market segments. The results will be significant reduction in VOC emissions (via elim-
ination of solvents in ink production, usage, and cleanup), enhanced recyclability of scrap
plastic parts (unlike labels, there is no effect on melt reprocessability), and reduced liability
on critical components, where safety warning labels often scrape or fall off the part.
Compared to earlier first-generation laser marking of plastics, the new technology offers
greater contrast between mark and background, applicability to most major classes of ther-
moplastics and some thermosets (since custom-additive packages and manipulation of laser
energy rather than base resin reformulation is used), the ability to move beyond what was
essentially a monochrome palette, and reduction in potential thermal damage to the wall-
stock of the part, since the new technology does not work by pyrolization. Speed, flexibility,
and economics are further benefits. Based on figures supplied by the Commerce Department
and Rauche Guide to the U.S. Ink Industry, total solvent usage associated with inks for the
plastics industry amounts to 22.4 million pounds (11,200 tons) annually, conservatively
assuming an average solvent content of 30%. M.A. Hanna Color estimates that within the
first two years of use, the new color laser marking technology could effectively replace approx-
imately 10% of the plastics decorating processes that involve inks. Within ten years, this
figure could rise to 50%. Meeting the 10% projection would eliminate approximately 1,120
tons (2.24 million pounds) of VOC emissions from the production of plastic parts in the
U.S. annually.
Reduction of Carbon Tetrachloride Emission at the
Source by Development of a New Catalyst
Phosgene is an important intermediate in the synthesis of polycarbonate plastics, high-
performance polymers, agrichemical intermediates, and urethane foams. Current global
production is about 10 billion pounds per year. Although the process chemistry is selective,
the byproduct carbon tetrachloride, CCU, is generated at a rate of 300 to 500 parts per mil-
lion, amounting to 5 million pounds per year globally. Since carbon tetrachloride is a
carcinogen, an ozone depleting chemical, and a greenhouse gas, it was necessary to reduce or
eliminate this undesirable byproduct.
A DuPont team discovered a new catalyst that was produced in Siberia, Russia. After
much laboratory work, it was decided to try a plant test, a scale-up of greater than 250,000
times. The catalyst was purchased, shipped from Siberia, and implemented in less than one
year after the start of the program. After one and a half years of commercial production, the
new catalyst has consistently demonstrated high phosgene production rates and achieved a
90% reduction in the level of carbon tetrachloride generation (to less than 50 ppm, appar-
ently a new global record). By conceptualizing, identifying, testing, securing from Russia, and
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implementing a novel phosgene production catalyst (well within the proposed 18 month
deadline), the team saved the business a cost of $2 million associated with the installation of
a new abatement furnace, which would have been the only other alternative. Furthermore,
the resulting need for fewer catalyst changes in the reactor, as well as the prevention of main-
tenance costs that would have been associated with the abatement furnace, will save
approximately an additional $400,000 per year. The catalyst technology is being offered for
license globally, which could reduce emissions of CCLj by up to 5 million pounds per year.
The Removal of Oxides of Nitrogen (NOx) by In Situ
Addition of Hydrogen Peroxide to a Metal Dissolving
Process
The removal of oxides of nitrogen (NOx) by in situ addition of hydrogen peroxide to a
metal dissolving process was developed by Mallinckrodt Inc. Salts are produced by dissolving
metals in nitric acid. 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
NOx emissions from the dissolving process. The literature states NOx is required to catalyze
the dissolution reaction. This theory was challenged; Mallinckrodt Inc. proposed to oxidize
the NOx back to nitric acid by adding hydrogen peroxide directly to the process, thus com-
pletely eliminating NOx emissions. This proposal was demonstrated in the laboratory. Next,
two trial runs using this technology were completed. In both cases the formation of NOx was
completely eliminated. Based on the information from the trial runs, manufacturing, with
help from research and development, designed a hydrogen peroxide addition process, which
was successfully introduced. The new process has eliminated the generation of 30 tons per
year of NOx while at the same time reducing nitric acid usage by approximately 109 tons per
year. Also, 13 million gallons per year of scrubber waste water were eliminated since the
scrubber is no longer needed.
Replacement of Asbestos in the Diaphragm Cell Process
for Manufacture of Chlorine and Caustic Soda
PPG has developed the Tephram® nonasbestos diaphragm for use in diaphragm electrol-
ysis cells for the production of chlorine and caustic soda (NaOH). Approximately 75% of the
chlorine and caustic soda produced in the United States is made by the electrolysis of salt
brine in diaphragm electrolysis cells. In these cells, salt dissolved in water is supplied as ana-
lyte to an electrolysis cell consisting of an anode, cathode, and a diaphragm. The Tephram8
diaphragm uses nonhazardous materials to replace asbestos, reducing complexity in the safe
handling of raw materials and in the disposal of diaphragm materials at the end of their use-
ful lives. The Tephram® diaphragm is not only easier to handle safely and is more
environmentally friendly, it also lasts longer than does asbestos and operates with greater
energy efficiency. These advantages of greater durability and efficiency combine to reduce
expenditure of cell renewal labor and consumption of both materials and energy.
Mallinckrodt Inc.
PPG Industries, Inc.
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Viasystems Technology
Corporation
Dow Polymers LLC,
Cargill Dow Polymers
LLC
Solder Waste Reduction Environmental Project
One operation in the manufacturing process of printed wiring boards (PWBs), Hot Air
Solder Leveling (HASL), applies solder to the copper circuits on the PWB as a solderability
preservative for subsequent component assembly operations at customer locations. As the
PWB passes through the molten solder in the HASL process, some copper dissolves from the
PWB into the solder bath. The maximum allowable copper contamination level in solder for
PWB applications is 0.30%. To maintain the solder bath below the maximum copper cont-
amination level, a fraction (1/3) of the solder bath was routinely removed from the process
and replaced with fresh solder. This spent solder, due to its lead (Pb) content, was classified
as a hazardous waste.
In 1991, 372,800 pounds of solder hazardous waste was generated at Viasystems Corp.'s
Richmond facility from the process for disposal. This was reduced to 261,720 pounds in
1992 through optimization of process parameters to minimize the copper dissolution rate.
Although this was a significant waste stream reduction, this level of hazardous waste genera-
tion was still unacceptable from an environmental and cost standpoint. In addition, the
required bailout of spent solder created productivity and process control issues within the
process.
In 1993, a specific waste minimization project was undertaken to further reduce the sol-
der hazardous waste generation in the HASL process. An online solder skimmer device was
developed that allows preferential removal of the copper from the HASL solder. The solder
skimmer functions by continuously circulating a small portion of the solder from the HASL
solder pot (480 °F) through the skimmer, which is maintained at a temperature 100 degrees
lower (380 °F), then returning it to the main solder pot. A portable solder pot was developed
to work in conjunction with the solder skimmer to eliminate solder waste generation when
routine maintenance was performed. As a result of this solder waste minimization project,
solder dross hazardous waste shipments were reduced from 261,720 pounds in 1992 to
29,920 pounds in 1996. The solder waste generation was reduced from 199 pounds in 1993
to 31 pounds in 1996 on a per 1,000 panels processed basis. An overall waste reduction of
over 80% was achieved. The reduction of solder waste also resulted in fresh solder cost sav-
ings of over $250,000 per year. There are now more than 50 solder skimmer devices in use
on HASL processes throughout the world.
Solvent-Free Process to Produce Biodegradable Polylactic
Acid Polymers
Polyactic acid (PLA) is a highly versatile biodegradable polyester derived from 100%
renewable resources that offers great promise as a replacement for petrochemical-based plas-
tics in a wide range of commodity applications. The environmental benefits of PLA have long
been appreciated. However, the commercial viability of PLA has been limited by high pro-
duction costs leading to resin prices above $2/lb. Yet PLA may well be considered the
"sleeping giant" of biodegradable, renewable-resource based polymers.
Cargill Dow Polymers, in conjunction with its parent companies, has developed a novel
solvent-free process for the production of lactide and polylactic acid (PLA). This process
allows the manufacture of an environmentally friendly, biodegradable polymer that is posi-
tioned to effectively compete with petrochemical-based, commodity plastics. PLA is made in
a multistep process from lactic acid, a fermentation product derived from 100% renewable
resources. First, aqueous lactic acid undergoes a condensation polymerization to produce low
molecular weight PLA pre-polymer. Next, PLA pre-polymer is thermally depolymerized into
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a mixture of L- and meso-lactide diastereomers, lactic acid, and water. The lactide isomers are
isolated with high purity by a patented vacuum distillation process. Finally, PLA high poly-
mer is produced via a tin-catalyzed, ring-opening polymerization of lactide in the melt.
The advantage of this new synthetic process is that costly and environmentally unfriend-
ly solvent purification steps for lactide and PLA are completely avoided. Another
environmental benefit of PLA is the fact that it could be 100% recyclable once the commer-
cial volume warrants its own collection system. Articles produced from PLA can be
conveniently hydrolyzed with water back to lactic acid quantitatively and reused in the
process. Additionally, one of the unique features of PLA is its ability to rapidly biodegrade.
Furthermore, PLA is a low-impact greenhouse gas polymer since the CCh generated during
its biodegradation is exactly balanced by CC^ taken from the atmosphere by renewable
resource feedstocks. Petrochemical-based polymers contribute to the VOC emission and
greenhouse warming problem when they are incinerated. For every ton of petrochemical-
based polymer that is incinerated, more than 3-7 tons of CC^ are emitted to the atmosphere.
This process has been in operation for more than a year at a semiworks facility in Savage,
Minnesota, the world's largest PLA plant having a capacity of 8 MM Ib/yr. A planned 250
million pound commercial PLA plant, with a targeted PLA price of $0.50/lb, has the poten-
tial to eliminate up to 1 billion pounds of CC^ emissions annually if the product replaces
disposable hydrocarbon products that are incinerated. The combination of versatile produc-
tion capability and advantaged economics, while simultaneously practicing sound green
chemistry, uniquely positions EcoPLA™ brand polymers to be competitive with petrochem-
ical-based plastics in a variety of commodity applications.
Solvent-Free Semiconductors Manufacturing Process
The U.S. semiconductor industry utilizes over 300 million pounds of solvents and other
chemicals annually in the manufacturing of computer chips. In addition to the costs of ini-
tial purchase of these chemicals, the industry must bear the cost burden of waste disposal of
these hazardous and polluting chemicals. Ultimately the consumer must pay for these costs
when purchasing a new computer or any other product (e.g., cellular phone) which utilizes
these chips.
The major uses for solvent cleans in the industry are for Post Metal Etch (the application
here) and for Post Via Etch. These are known as "back-end" processes in the industry.
Approximately equal consumption is for each application; metal alone would total 125 mil-
lion pounds annually. This is equivalent to 18 million gallons of solvent used annually in the
U.S. territory. It is estimated that the Conexant Systems, Inc. facility uses approximately
20,000 gallons per year for solvents related to post-metal stripping applications. Purchased at
$40 per gallon (not including waste disposal costs), this is a cost of $800,000 annually.
A new generic process for accomplishing the above objectives was developed by ULVAC
Technologies, Inc. that incorporates plasma chemical processing to replace hazardous, costly,
and polluting wet solvents in the manufacture of metallized patterns on silicon wafers. This
process is adapted to the specific chemistry of the manufacturing process for each semicon-
ductor manufacturer. Initial experiments established the process adjustments to obtain
satisfactory performance with the Conexant Systems, Inc. 0.25u metal product. This includ-
ed testing for electrical performance, inspecting all process steps for cleanliness and stability,
confirming that corrosion will not be a problem, and generally verifying that overall device
performance is satisfactory. The result has been a new multilevel metal-manufacturing line
that incorporates no solvents.
Conexant Systems,
Incorporated, ULVAC
Technologies, Inc.
69
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Union Carbide
Corporation
Sequa Chemicals, Inc.
Splittable Surfactants
Union Carbide has developed a new class of surfactants, splittable surfactants, which pro-
vide a substantial reduction in emulsified organics discharged in waste-water streams from
industry. Splittable surfactants exhibit superior end-use performance, compared to current
waste-treatable surfactants and other proposed treatments, which have not gained widespread
use due to performance limitations. Waste streams containing splittable surfactants are quick-
ly, easily, thoroughly, and irreversibly "split" and deactivated, via a chemical trigger, into
non-surface active components, allowing rapid separation of oily waste from the water
stream. A more concentrated oily waste is generated, facilitating either incineration for fuel
value (industrial laundry applications), isolation for recycling (metal working fluids), or direct
use (isolating lanolin from wool scouring). Before splitting and deactivation, Splittable
Surfactants have an environmental profile comparable to conventional nonionic surfactants.
Upon deactivation, both the hydrophilic and hydrophobic components biodegrade rapidly,
and the hydrophilic component remaining in the waste water is essentially nontoxic to aquat-
ic life. Splittable Surfactant technology represents the first industry partnership under the
EPA's Environmental Technology Initiative for Chemicals, and EPA has recognized these
products as "a significant innovation in surfactant chemistry, one that greatly reduces risk to
the aquatic environment," with its Recognition of Achievement in Pollution Prevention.
Starch Graft Polymers as Phenolic Resin Extenders
Starch graft polymers are derived from modified starch and conventional vinyl and acrylic
monomers. While starch graft polymers have been known previously, a technology developed
by Sequa Chemicals overcame rheological problems associated with prior products and
afforded a convenient, fluid latex-like form. Drawing on glyoxal-based paper coating tech-
nology, these new starch graft polymers also utilized a novel nonformaldehyde cross-linking
system. This new technology was initially used as a replacement for conventional latex poly-
mers made with N-methylol acrylamide (which is a source of formaldehyde emissions) as the
cross-linking system. Applications were as binders for fiberglass and polyester nonwoven mat.
This provided a binder system that eliminated formaldehyde emissions and maintained good
performance and reasonable economics.
These starch graft emulsion polymers are water-based, nontoxic and nonirritating. Recent
work has examined the use of these starch graft polymers as extenders for phenol-formalde-
hyde (PF) resins. An aqueous PF resin typically contains approximately 2% free
formaldehyde. Approximately 1 billion pounds of aqueous PF resins are sold in the United
States each year. That adds up to approximately 20 million pounds of free formaldehyde
emitted to the environment and workplace each year. It has been found that starch graft poly-
mer products not only decrease formaldehyde emissions greatly, but also work synergistically
with PF resins. Optimum performance is near the midpoint of composition. Such synergis-
tic performance has not previously been observed with conventional latex emulsion
polymers. Performance properties such as tensile strength, burst, and stiffness are improved
over either the PF resin or the starch graft alone. Extending PF resins proportionally lowers
the residual unreacted phenol in the final products. Proportional reductions of formaldehyde
emissions have been measured, and a scavenging effect has been noted in testing designed to
evaluate exposure to workers handling treated substrate. This technology is now sold com-
mercially in tank truck quantities and its benefits are being promoted in various industries.
70
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Stepan Company PA Lites Polyol
Stepan Company's Polyester Polyol product, manufactured using the Phthalic Anhydride
Process Light Ends (PA Lites), uses a previously categorized waste as a raw material in its man-
ufacture, thereby eliminating the material's disposal via incineration. This Polyester Polyol is
the basic raw material for the manufacture of various types of insulating wallboard used in
the home construction and commercial building industry By substituting traditional raw
materials with PA Lites, Stepan Company is providing the construction industry and con-
sumer with a cost-effective alternative to traditional building construction products.
Benefits from this product substitution go beyond the elimination of a waste requiring
disposal. With its substitution as a raw material, it has reduced the requirement for phthalic
anhydride, the traditional raw material for the polyol product, and the air emissions associ-
ated with its manufacture. As part of the development of this process, the distillation
operation in the phthalic anhydride facility was also improved. An estimated 350 tons per
year of organic waste material has been eliminated with the development and implementa-
tion of this technology. This not only represents a significant reduction in waste requiring
disposal by incineration, but also the air emissions associated with these processes. Since this
previously categorized waste material is now used on site to produce Polyester Polyol, poten-
tial exposure to the general public during offsite transportation to disposal facilities has been
eliminated.
This project resulted in two economic benefits. The first is the savings associated with the
transportation and disposal via fuel blending for energy recovery. On an annual basis the
expected saving is $200,000. The second economic benefit is the raw material savings due to
the replacement of the Pure PA with the PA Lites material on a pound for pound basis. This
results in additional savings of $20,000 annually.
Stepanfoam® Water-Blown Polyurethane Foam HCFC-
Free, Environmentally Friendly, Rigid Polyurethane
Foam
Stepan Company's STEPANFOAM® Water-Blown Polyurethane Foam is a product in
which CFCs and HCFCs are replaced with water as the blowing agent in rigid polyurethane
foam. Historically, polyurethane foams used in insulating applications incorporated
Trichlorofluoroethane (CFC-11), or more recently 1,1-Dichloro-l-fluoroethane (HCFC-
l4lb), as the blowing agent. CFCs and HCFCs have been demonstrated to play a role in the
depletion of the earth's stratospheric ozone layer and to contribute to global warming.
Traditional rigid polyurethane foam products have the potential to release CFCs and HCFCs
into the environment during formulation, manufacture, use, and disposal. The replacement
of these compounds with water as an innocuous blowing agent eliminates the requirement
for these environmentally unfriendly compounds and the resultant emissions to the environ-
ment. Throughout the 1990s, Stepan Company has remained committed to the
development of a lower cost, technologically advanced polyurethane foam that replaces envi-
ronmentally unfriendly and potentially hazardous blowing agents with water. Stepan's
Research and Development Department and Business Teams have partnered with our cus-
tomers throughout the development and continued application of this product to promote
its use as a viable alternative to CFCs and HCFCs.
Stepan Company
Stepan Company
71
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Antelman Technologies,
Ltd.
Superior Replacement for Chlorine in Water Treatment
Chlorine is today the most commonly used product for the treatment of industrial and
recreational water. Its use, however, has been accompanied by a host of personal complaints
and environmental risks. Chlorinated waters often find their way into natural waterways,
destroying the organisms that sustain the food chain of aquatic life. Environmental interac-
tions have been shown to facilitate the evolution of highly carcinogenic chloramines that find
their way into the food chains of higher animals and humans. Sildate® provides a practical
remedy to an environmental dilemma — how to sanitize water without using chlorine or
other halogens, such as bromine.
Sildate® is an entirely new, nontoxic, environmentally friendly, complete water treatment
system which is virucidal, bactericidal, and algicidal in parts per million. Each molecule of
Sildate® is a single molecular diamagnetic semiconducting crystal that kills hazardous germs
by direct electrocution and chelation rather than conventional poisoning. Because of this
action modality, it is totally nontoxic to higher life forms. The Sildate® monomolecular device
is a unique, inexpensive, patented, marketed product that effectively fills a significant public
health need without the serious environmental problems associated with other products now
in use. It is safe to humans, wildlife, pets, aquatic creatures, and to the earth's environment.
Bayer Corporation,
Bayer AG (Germany)
Two-Component Water borne Polyurethane Coatings
Two-component solvent borne polyurethanes have long been considered in many appli-
cation areas the benchmark for high-performance coatings systems. The attributes that make
these systems so attractive are fast cure under ambient or bake conditions, high-gloss and mir-
ror-like finishes, hardness or flexibility as desired, chemical and solvent resistance, and
excellent weathering when aliphatic polyisocyanates are used. But the traditional carrier has
been organic solvent which, upon cure, is freed into the environment as VOC and hazardous
air pollutants (HAPs) material. Use of high-solids systems ameliorates this problem but does
not go far enough.
Aqueous polyurethane dispersions (PUDs) can impart the properties of polyurethane
coatings from a waterborne system containing less organic solvent. They are fully reacted,
high-molecular weight polyurethanes, which are most commonly ionically modified for
water dispersibility. Because of low levels of crosslinking, chemical and solvent resistance is
generally not equivalent to films based on two-component solvent borne polyurethane.
Additionally, manufacturing procedures used for polyurethane dispersions frequently dictate
inclusion of cosolvent.
Bayer's introduction in 1992 of high-quality two-component (2K) polyurethane coatings
using water as the carrier amazed the coatings industry because, at that point, it was consid-
ered that 2K polyurethanes required scrupulous protection from water. Developing
waterborne formulations that produce films equivalent to solvent borne counterparts was not
a trivial matter. It was accomplished with the invention of water dispersible polyisocyanates
and much work to develop practical formulations for a variety of market areas. New spray
equipment has been developed that makes implementation of this environmentally friendly
coating simple and inexpensive. The work done on the 2K waterborne polyurethanes over
the past several years has resulted in a technology that provides several health and environ-
mental benefits. VOCs are reduced by 50 to 90%, and HAPs by 50 to 99%. The amount of
chemical byproducts evolution from films in interior applications is also reduced. In the
United States, 2K waterborne coatings are now being sold into such market areas as indus-
trial finishing, wood finishing, floor coatings, military coatings, and automotive interiors.
72
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Use of Solid Catalysts in Pollution Prevention in the
Nitration of Aromatic Compounds
Nitration reactions of aromatic substrates are important for the industrial production of
a wide variety of essential chemicals, chemical and pharmaceutical intermediates, and explo-
sives. The most widely used practical nitrating agents are mixtures of concentrated nitric and
sulfuric acids. These homogenous systems are very corrosive and present serious environ-
mental problems caused by spent acid disposal. This traditional nitration process is a
notoriously unselective reaction resulting in statistical distribution of ortho, meta, and para
substituted nitro isomer products. Also, this process requires an aqueous washing stage to
remove oxidized byproducts that result in a waste stream that is environmentally unsuitable
and costly to treat.
Therefore, there is a great need for a new nitration method that can overcome problems
associated with the current mixed-acid nitration process widely used in the industry. An
attractive nitration process has been developed to provide para-nitro isomer with high regio-
selectivity in alkyl and halo benzenes under mild conditions using concentrated nitric acid
and a solid catalyst. Several aromatic substrates were nitrated using industrial grade nitric acid
as the nitrating agent and commonly available, cheap zeolite solid acid catalyst to yield com-
mercially valuable para-nitro isomer in good yield. The increase in the regioselectivity of the
commercially more desirable para-isomer is due to the shape selective characteristics exerted
by the solid catalyst.
This process has a number of practical advantages: significant improvements in regiose-
lectivity favoring para-isomer in aromatic substitution in good yields, ease of separation and
recovery of products, and low cost. The solid catalyst can be easily regenerated and reused by
recalcination. It represents an attractive method for the clean synthesis of a range of nitroaro-
matic compounds. For example, this process eliminates the formation of unwanted
meta-nitrotoluene isomer and other byproducts in the production of 2,4,6-trinitrotoluene
(TNT) thus preventing the Red Water pollution problem. Regioselective formation of com-
mercially more desirable p-nitro isomer has unique applications in the polyurethane and dye
industry. In this respect, the polyurethane division of Bayer Corporation is currently evaluat-
ing this technology to implement in their polyurethane and dye production facilities.
Vegetable Oil Based Printing Inks and Their
Environmental Advantages
The current United States market for news inks is greater than 500 million pounds, for
sheetfed inks is greater than 100 million pounds, and for heatset inks greater than 400 mil-
lion pounds. Conventional printing inks used in these applications are multicomponent
systems comprising a hydrocarbon and/or alkyd resin, a hydrocarbon solvent, a pigment, and
optional additives. The large amount of petrochemical resins and solvents, used in these for-
mulations, are presenting environmental problems and pollution during the production and
disposal of these inks. In recent years, the industry has been able to substitute soybean oil for
a portion of the petroleum fraction, although news ink can contain as little as 40% vegetable
oil (including soybean oil), sheetfed ink as little as 20% vegetable oil, and heatset ink as lit-
tle as 7% vegetable oil of total formula weight.
In comparison to the formulas, the USDA developed news, sheetfed, and heatset litho-
graphic inks, by using vehicles consisting of 100% soy or other vegetable oils, eliminating all
petroleum products from the ink formulations. Ink vehicles were prepared by the polymer-
ization of vegetable oils. By controlling the polymerization conditions, the desired viscosity,
U. S. Army Armament
Research,
Development, &
Engineering Center
National Center for
Agricultural Utilization
Research, U.S.
Department of
Agriculture
73
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Dow Corning
Corporation
Supratech Systems Inc.
74
color and molecular weight could be achieved for a variety of vegetable oils having a broad
range of iodine value and fatty acid composition. These vehicles were used to formulate news
inks in four primary colors (black, cyan, magenta, and yellow).
For sheetfed and heatset ink vehicles, heat polymerized vegetable oil was mixed with
monoester of an unsaturated fatty acid or a blend of unsaturated fatty acid monoesters. In the
formulation of the vehicle, unmodified vegetable oil was used as a third component. Esters
were incorporated at a relatively low level—on the order of about 0.5 to 3-0% by weight of
the vehicle. Heat polymerized and unmodified oil constitutes the major fraction of the vehi-
cle, and thereby primarily is responsible for the theological properties of the formulated ink.
Physical properties (i.e., viscosity, tack, drying time, printability) and performance of
these inks meet or exceed the industry standards. Biodegradation and volatile organic chem-
ical tests once again showed the superiority of our inks over commercial inks.
Volatile Methyl Siloxanes: Environmentally Sound
Solvent Systems
Linear Volatile Methyl Siloxanes (VMS) are a class of mild solvents having an unusual
combination of environmentally benign qualities. They are low in toxicity, make little con-
tribution to global warming, do not contribute to urban ozone pollution, and do not attack
the stratospheric ozone layer. They do not accumulate in the atmosphere, but rather are
rapidly transformed to naturally found species, and they have received SNAP approval and
VOC exemption from the EPA.
VMS solvency can be tailored to specific applications by use of cosolvents and surfactants.
Eleven U.S. patents, 26 new azeotropes, 5 commercial solvents, and several formulated prod-
ucts have resulted. The underlying phenomena related to their use to replace less benign
solvents in coating formulations or to remove particulates, oils, fluxes, and aqueous contam-
inants have been extensively studied. Their mild but selectable solvency, environmental
benignancy, and odorless character commend them for many uses. Highly purified grades
leave no surface residue, and many of their applications require such purities. They have
potential value for precision Water Displacement Drying during the many aqueous process-
ing steps of Flat Panel Display and semiconductor manufacturing.
Water Washable Flexo Photopolymer Plate "Flexceed"
and Washout System
Flexography (Flexo) is a method of direct rotary printing that uses resilient relief image
plates and the fastest growing printing process in the world. The conventional flexo pho-
topolymer plates can be washed out only by using organic solvents to make relief images.
Concerns for solvent use include the emission of VOCs, flammability because of lower flash
point, hazardous waste, and influence on human health. Flexo photopolymer plate
"Flexceed" is designed to be washed out by water to eliminate the use of any organic solvents.
Both "Flexceed" plate and its washout system are designed as a total system to make treat-
ment of its washout solution pass waste management regulations at reasonable cost using a
user-friendly concept. The newly developed washout system can provide wider latitude for
developing new types of "Flexceed" plate, which can satisfy the requirements of new flexo
market segments for "Flexceed," while maintaining this environmental benefit. It has been
positively demonstrated that the total "Flexceed" system is acceptable for each market seg-
ment of flexo printing industry due to not only print performances but also economic
benefits as compared with the conventional solvent washout flexo photopolymer plate sys-
tems.
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Zero Effluent Photographic Processing in the Printing
Industry
In its pre-press operations, the printing industry consumes about 1.5 billion square feet
of silver halide photographic film annually. Processing the film consumes enormous amounts
of water and chemicals and produces an equally large amount of liquid waste that is primar-
ily disposed of in POTWs. The process also produces millions of waste plastic containers.
Virtually none of this material is recycled and the environmental burden is very large. Some
400 million gallons of fresh water is consumed each year and, after washing contaminant
from the processed film, is sent to local POTWs for treatment. In addition to that, 15 mil-
lion gallons of photographic developer containing thousands of tons of noxious chemicals
like hydroquinone are similarly dumped on the POTWs. Further, 15 million gallons of pho-
tographic fixer containing high levels of ammonia and silver are also sent to the POTWs for
treatment. Although some of the silver is removed by various processes, these are not very effi-
cient and recovery of this precious metal is only on the order of 50%. The limited
environmental efforts have been directed primarily at silver recovery because of the value of
the silver, or, where water prices are high, to reduction in wash water use.
The wastes generated in the pre-press printing industry are complex and require a coor-
dinated effort to eliminate them. The Dupont DuCare™ Photochemical Film Processing
System is such a coordinated effort. It attacks the largest volume piece of the problem, the
wash water, by developing novel technology that reduces the amount of wash water required
by 99% and completely eliminates the wash water effluent by sending used wash water into
the fixer. The DuCare™ system includes a novel, recyclable developer based on erythorbic
acid instead of hydroquinone in a process that allows about 75% of returned developer to be
used in making fresh recycled developer. The DuCare™ system also includes a recycled fixer.
Although the technology used is not new, it is made much more effective and efficient than
in the past. The fixer is returned to a central recycling center, much like the developer is,
where the silver is recovered with an efficiency of 99%. In addition, the analytical capability
and control at a recycling center allow about 90% of the returned fixer to be used in making
fresh recycled fixer. The net effect of this coordinated approach would virtually eliminate the
liquid waste generated if it was applied across the industry. Fresh water savings would be over
395 million gallons annually. No liquid waste would be sent to POTWs. All liquids would
be returned for recycling. Those that could not be recycled would be disposed of at com-
mercial, licensed TSDFs. Packaging waste would drop significantly. The efficient recycling
and reuse of the spent chemical stream would eliminate the need for thousands of tons of raw
materials as well.
E.I. duPont de Nemours
& Co., Inc.
75
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Index
Award winners are indicated with *.
3M Center
Hydrofluoroethers (HFEs) —The Right Balance of Properties 53
ABB Power T&D Company Inc.
Fully Biodegradable Vegetable Oil-Based Electrical
Insulating Fluid (BIOTEMP™) 50
Akzo Nobel
A Durable Hydrodechlorination Catalyst for
Selective Conversion ofCCh to CHCls 46
Next Generation Fire-Resistant Fluids 62
Albany Research Center, U.S. Department of Energy
Chloride-Free Processing of Aluminum Scrap 42
Albright & Wilson Americas, Inc.
A New Environmentally Friendly Corrosion
Inhibitor for Industrial Cooling Systems 60
Allied Signal Inc.
An Innovative Process for the Manufacture of Caprolactam from Postconsumer Nylon
6 Carpet and Other Nylon 6 Waste Articles 55
Almaden Research Center, IBM Corporation
The Chemical Kinetics Program 41
American Air Liquid
Air Liquid PFC Recycle Process 39
American Society for Testing & Materials (ASTM)
Analysis of Liquid Hazardous Waste for Heavy Metals by Energy-Dispersive X-Ray
Fluorescence (EDXRF) Spectrometry 39
AMSOIL Incorporated
Waste Oil Source Reduction Through Extended Oil Service Life 35
Anderson Chemical Company
Total Impact Program—An Environmentally Preferable Program for Laundry . . . 35
Antelman Technologies, Ltd.
Superior Replacement for Chlorine in Water Treatment 72
Antia, Jimmy E. and Govind, Rakesh, Department of Chemical
Engineering, University of Cincinnati
Novel In-Situ Zeolite Coatings in Monoliths 19
Argonne National Laboratory
Clean Diesel Breakthrough: Simultaneous Decrease in Emissions of Both Particulates
and Oxides of Nitrogen During Combustion 42
Arkenol, Holdings, L.L.C.
Sugars from Lignocellulosic Materials for the Production of
Bio-Based Fuels and Chemicals 35
BAT Technologies Inc.
Primer for Anti-Fouling Paint 34
76
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Bayer Corporation, Bayer AG (Germany)
Two-Component Waterborne Polyurethane Coatings 72
Beckman, Eric J., Chemical Engineering Department, University of
Pittsburgh
Generation of Hydrogen Peroxide in Carbon Dioxide 15
Metal Extraction and Recovery Using Carbon Dioxide 17
Bergbreiter, David E., Department of Chemistry, Texas A&M University
Use of Soluble Polymers to Recover Catalysts and to Control Catalytic Reactions. . 24
BetzDearborn, Inc.
Designing an Environmentally Friendly Copper Corrosion
Inhibitor for Cooling Systems 43
BIOCORP, Inc.
Biodegradable Thermoplastic Material. 28
Biofine, Incorporated
*Conversion of Low-Cost Biomass Wastes to Levulinic Acid and Derivatives 4
Bose, Ajay K., Stevens Institute of Technology
Microwave-Induced Organic Reaction Enhancement (MORE)
Chemistry for Eco-Friendly Synthesis 17
Burch Company
Burch Apparatus and Method for Selectively Treating Vegetation to
Reduce Pesticides and Fertilizer Use, Eliminate the Release of Certain
Toxins to the Environment, Reduce Pesticide Runoff, and Reduce the
Potential of Worker Exposure to Toxic Substances 28
Burlington Chemical Company
Development of a Practical Model and Process to Systematically
Reduce the Environmental Impact of Chemicals Utilized by the
Textile and Related Industries 30
CerOx Corporation
CerOx Process Technology for Non-Thermal
Destruction of Organic Hazardous Wastes 29
Chemecol, L.L.C., Forbo International, and McDonough Braungart Design
Chemistry, L.L.C.
PVC Replacement Technology 65
Ciba Specialty Chemicals Corporation
Ashless Friction Modifier!Antioxidant for Lubricants 40
New Organic Corrosion Inhibitors Help Replace Toxic Heavy
Metals and Reduce Solvent Emissions 61
Collins, Terry, Carnegie Mellon University
*TAML™ Oxidant Activators: General Activation of
Hydrogen Peroxide for Green Chemistry 3
Conexant Systems, Incorporated, ULVAC Technologies, Inc.
Solvent-Free Semiconductors Manufacturing Process 69
Cussler, E.L., University of Minnesota
Pollution Preventing Lithographic Inks 21
77
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Dow AgroSciences LLC
*Spinosad, A New Natural Product for Insect Control 7
Dow Corning Corporation
New Technology Converts Waste to Valuable Intermediates 61
Volatile Methyl Siloxanes: Environmentally Sound Solvent Systems 74
Dow Polymers LLC, Cargill Dow Polymers LLC
Solvent-Free Process to Produce Biodegradable Polylactic Acid Polymers 68
DuPont Company
Reduction of Carbon Tetrachloride Emission at the
Source by Development of a New Catalyst 66
Dynacs Engineering Co., Inc., Kennedy Space Center
Oxidizer Scrubber Project 63
Eastman Kodak Company
Minimizing Environmental Emissions by Using
Different Solvents in Manufacturing Processes 57
E.I. duPont de Nemours & Co., Inc.
Zero Effluent Photographic Processing in the Printing Industry 75
Environmental Technology and Education Center, Inc. (ETEC)
High Energy Efficiency, Environmentally Friendly Refrigerants 31
Fish, Richard H., Lawrence Berkeley National Laboratory,
University of California
Fluorous Biphasic Catalysis: A New Paradigm for the Separation of Homogeneous
Catalysts from Their Reaction Substrates and Products, as Demonstrated in Alkane
andAlkene Oxidation Chemistry 14
Freeman, Harold S., Ciba-Giegy Professor of Dyestuff Chemistry,
North Carolina State University
Synthetic Dyes Based on Toxicological Considerations 23
The Geon Company
Increased Utilization of Raw Materials in the
Production of Vinyl Chloride Monomer 54
Govind, Rakesh and Singh, Rajit, Department of Chemical Engineering,
University of Cincinnati
Bioconversion of Carbon Dioxide into Organic Feedstocks 9
Hauser, Inc.
Paclitaxel Process Improvements 33
Hill, Craig L., Department of Chemistry, Emory University and Weinstock,
Ira A., USDA Forest Service, Forest Products Laboratory
Effluent-Free Process for Use of Oxygen in Place of Chlorine Compounds in Wood-
pulp Bleaching 12
Ho, Nancy W.Y., Laboratory of Renewable Resources Engineering,
Purdue University
Successful Development of Hazard-Free, User-Friendly Genetically Engineered
Microorganisms for Effective Production of Environmentally Friendly Chemicals from
Renewable Biomass using Green Chemical Methodologies 22
78
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Hudlicky, Tomas, Department of Chemistry, University of Florida
Toward Synthetic Methodology "Without Reagents"
Increased "Effective Mass Yield" for Pharmaceuticals by
Tandem Enzymatic and Electrochemical Oxidations and Reductions 23
Imation Corporation
Imation No Process Plates 53
IMC-Agrico Company
AGROTAIN -(n-butyl) Thiophosphoric Triamide 38
International Metalizing Corporation
Nontoxic Antifouling 33
lonEdge Corporation
Zero-Waste Dry Plating of Cadmium 36
Khalili, Nasrin R., Arastoopour, Hamid and Walhof, Laura, Department of
Chemical and Environmental Engineering, Illinois Institute of Technology
A Novel Waste Minimization Approach: Production of Carbon-Based Catalyst or
Sorbentfrom Biosolids 20
KM Limited Inc.
The LCAPIXModule Software: Combining Life Cycle Assessment with Activity Based
Costing to Assist in Preservation of the Global Environment and Sustained Economic
Growth 31
Knipple, Douglas C, Department of Entomology, Cornell University
In Vivo Synthesis of Lepidopteran Pheromone Precursors in Saccharomyces Cereviseae:
An Economical Process for the Production of Effective, Nontoxic, Environmentally
Safe Insect Control Products 16
Ladisch, Michael R., Laboratory of Renewable Resources Engineering and
Department of Agricultural and Biological Engineering, Purdue
University
Biobased Adsorbents for Desiccant Coolers 8
Li, Chao-Jun, Department of Chemistry, Tulane University
Water as Solvent for Chemical and Material Syntheses 27
Lilly Research Laboratories
*Practical Application of a Biocatalyst in Pharmaceutical Manufacturing 5
Lin, Chhiu-Tsu, Department of Chemistry and Biochemistry, Northern
Illinois University
Chrome-Free Single-Step In Situ Phosphatizing Coatings 10
The Lubrizol Corporation
Durable AMPS* Antimist Polymers for Aqueous Metal Working Fluids 45
Lynd, Lee R., Department of Engineering, Dartmouth College
Overcoming the Recalcitrance ofCellulosic Biomass and Envisioning the Role of
Biomass in a Sustainable World 21
M.A. Hanna Color—Technical Center
Reducing VOC Emissions by Eliminating Painting and Labeling Operations with a
New Color Laser Marking System for Plastic Parts 66
Mallinckrodt Inc.
The Removal of Oxides of Nitrogen (NOx) by In Situ Addition of Hydrogen Peroxide
to a Metal Dissolving Process 67
79
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Mallinckrodt Baker, Inc.
Hydrogen Sulfide Elimination from the Substances Not Precipitated by H2S Test . 53
Mathews, Alexander P., Department of Civil Engineering, Kansas State
University
Waste Biomass Utilization in the Production of a Biodegradable Road Deicer ... 25
Matyjaszewski, Krzysztof, Department of Chemistry,
Carnegie Mellon University
Atom Transfer Radical Polymerization 8
Mobil Oil Corporation
Membrane Separation in Solvent Lube Dewaxing 56
Moller, Gregory, Holm Research Center, University of Idaho
Effects of the Corrosion of Elemental Iron on Heavy Metal
Contamination from Pyrite Oxidation 12
Monsanto Company
Metabolic Engineering of Crops for
Commercial Production of Biodegradable Plastics 57
Morton International, Inc.
ADVAFLEXIU Organic Stabilizer 38
Nalco Chemical Company
Designing an Environmentally Sensible Chlorine Alternative (STABREX) 44
Environmentally Responsible Liquid Polymers 49
Nalco Fuel Tech NOxOUT* Process 58
Nalco LAZON Technology 59
Nalco NALMET* Heavy Metal Removal Technology 59
Nalco PORTA-FEED® 59
Nalco TRASAR Technology 60
*Water Based Liquid Dispersion Polymers 6
Nassaralla, Claudia Lage, Department of Metallurgical and Materials
Engineering, Michigan Technological University
Waste Reduction and Recycling of Magnesite-Chrome
Refractory into the Steelmaking Process 26
National Center for Agricultural Utilization Research,
U.S. Department of Agriculture
Environmentally Benign Synthesis of Monoglyceride Mixtures Coupled with
Enrichment by Supercritical Fluid Fractionation 49
Vegetable Oil Based Printing Inks and Their Environmental Advantages 73
National Risk Management Research Laboratory,
U.S. Environmental Protection Agency
Oxygenation of Hydrocarbons by Photocatalysis: A Green Alternative 63
PARIS II Solvent Design Software 64
Nextec Applications, Inc.
Solventless Process for Improving Fabric Performance Properties 34
80
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Nikles, David E., Department of Chemistry, University of Alabama
Waterborne Coating Formulations for Video Tape Manufacture 27
Novon International
Natural Recycling of Plastics Through Chemical And Biological Degradation. . . . 32
Pacific Northwest National Laboratory
Biocatalytic and Biomimetic Process for the Synthesis of Nitroaromatic Intermediates
and Destruction of Nitrocompounds, Including Explosives 40
Paquette, Leo A., Department of Chemistry, The Ohio State University
Environmental Advantages Offered by Indium-Promoted Carbon-Carbon Bond-
Forming Reactions in Water 13
Peretti, Steven W., Department of Chemical Engineering,
North Carolina State University
Biosynthetic Production ofp-Hydroxybenzoate Improves Regiospecificity and
Minimizes Byproduct Generation 9
PPG Industries, Inc.
Replacement of Asbestos in the Diaphragm Cell Process for Manufacture of Chlorine
and Caustic Soda 67
Radiance Services Company
The Radiance Process: A Quantum Leap in Green Chemistry 34
Raghavan, Dharmaraj, Department of Chemistry, Howard University
Design of Rubberized Concrete From Recycled Rubber Tires 11
Novel Applications of Polymer Composite from Renewable Materials 18
Revlon Consumer Products Corporation
ENVIROGLUV™: A Method for Decorating Glass with Radiation Curable
Environmentally Friendly Inks 46
Robbat, Albert Jr., Chemistry Department, Tufts University
Cheminfomatics: Faster, Better, Cheaper Chemical Analysis Software 10
Roche Colorado Corporation
A Novel and Efficient Process for the Production ofCytovene®,
A Potent Antiviral Agent 62
Rogers, Robin D., Department of Chemistry and Director, Center for
Green Manufacturing, The University of Alabama
Green Separation Science and Technology: Using Environmentally
Benign Polymers to Replace VOCs in Industrial Scale Liquid/Liquid or
Chromatographic Separations 16
Rowe, H. Alan, Department of Chemistry/Center for Materials Research,
Norfolk State University
New Reducing Sugar Assay 18
SaLUT Inc.
Chemically Modified Crumb Rubber Asphalt 29
Sequa Chemicals, Inc.
Starch Graft Polymers as Phenolic Resin Extenders 70
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Singh, Mono M., National Microscale Chemistry Center,
Merrimack College
National Microscale Chemistry Center:
The Leader in Worldwide Implementation of Microscale Technology 18
Solutia Inc.
Greenhouse Gases: From Waste to Product 52
Solvent Kleene Inc.
Non-Hazardous Degreaser that Degreases as Efficiently as Trichloroethane and
Outperforms Aqueous Products 32
Southern Regional Research Center, U.S. Department of Agriculture
Environmentally Benign Antibacterial Agents 47
Stepan Company
Stepan Company PA Lites Polyol. 71
Stepanfoam Water-Blown Polyurethane Foam HCFC-Free, Environmentally Friendly,
Rigid Polyurethane Foam 71
Stewart, Jon D., Department of Chemistry, University of Florida
Engineered Baker's Yeast as a Means to Incorporate Biocatalysis Early in Process
Design: Application to the Asymmetric Baeyer-Villiger Oxidation 13
Subramaniam, Bala, Department of Chemical and Petroleum
Engineering, University of Kansas
A Novel Solid-Acid Catalyzed 1-Butene/Isobutane Alkylation Process 20
Supratech Systems Inc.
Water Washable Flexo Photopolymer Plate "Flexceed" and Washout System 74
Synovec, Robert E., Department of Chemistry, University of Washington
Novel Chemical Analysis Technologies by Water Liquid Chromatography, Raman
Spectroscopy, and High Speed Gas Chromatography 19
Synthon Corporation
Development and Commercialization of High-Value Chemical Intermediates from
Starch and Lactose 29
Tanko, James M., Department of Chemistry,
Virginia Polytechnic Institute and State University
Green Chemistry Through the Use of Supercritical Fluids and Free Radicals 15
TechMatch, Incorporated
N-Methylmorpholine-N-Oxide (NMMO): A Novel, Non-Toxic Solvent for Cellulose
as Source Reduction in the Production of Textile Fibers 32
Tektronix, Inc.
Designing Safer Chemicals: Spitfire Ink 44
Thompson, Stephen, The Center for Science, Mathematics and
Technology Education, Colorado State University
Small Scale Chemistry: Pollution Prevention in
Inorganic Chemistry Instruction Program 22
T.J. Watson Research Center, IBM Corporation
Green Card: A Biopolymer-Based and Environmentally Conscious Printed Wiring
Board Technology 51
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U. S. Army Armament Research, Development, & Engineering Center
Use of Solid Catalysts in Pollution Prevention in the Nitration of
Aromatic Compounds 73
U.S. Army Construction Engineering Research Laboratories
In Situ Chemical Stabilization of Lead-Based Paint Waste from Abrasive Blasting 55
U.S. Army Edgewood Research, Development, and Engineering Center
Filter Leak Test Using Ozone-Benign Substances 50
U.S. Bureau of Engraving
ISOMET: Development of an Alternative Solvent 56
United States Postal Service
Environmentally Benign Pressure Sensitive Adhesive Program 48
Union Carbide Corporation
Splittable Surfactants 70
Varma, Rajender S., Texas Regional Institute for Environmental Studies,
Sam Houston State University
Solvent-Free Chemical Synthesis 22
Viasystems Technology Corporation
Solder Waste Reduction Environmental Project 68
Warner, John C, Department of Chemistry, University of Massachusetts,
Boston; Polaroid Corporation
Environmentally Benign Supramolecular Assemblies of Hydro quinones in
Polaroid Instant Photography 14
Washington State Department of Ecology
Washington State Pollution Prevention, Health, and Safety Initiative in Academic
Chemistry Laboratories 25
Weimer, Alan W., Department of Chemical Engineering,
University of Colorado
Vibrating Fluidized Bed Combustion Nitridation Processing Using
Concentrated Solar Energy 24
Wong, Chi-Huey, Ernest W. Hahn Professor of Chemistry,
The Scripps Research Institute
Enzymes in Large-Scale Organic Synthesis 14
Wool, Richard P., University of Delaware
Affordable Composites from Renewable Sources (ACRES) 8
Zyvax Incorporated
The Zyvax "Watershield" Mold Release 37
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