United States
Environmental Protection
Agency
Pollution Prevention and
Toxics (7406)
EPA744-R-98-001
November 1 998
www.epa.gov/greenchemistry
The Presidential
Green Chemistry Challenge
Awards Program
Summary of 1998 Award
Entries and Recipients
Printed on paper that contains at least 20 percent postconsumer fiber.
-------
The Presidential Green Chemistry
Challenge Awards Program
Contents
Summary of 1998 Award Entries and Recipients 1
Awards 2
Academic Awards 2
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 27
Entries From Industry and Government 38
Index 70
-------
-------
The Presidential Green Chemistry
Challenge Awards Program
Summary of 1998 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 1998 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. Six projects that best met the scope of the program
and the criteria for judging were selected for 1998 awards and nationally recognized on
June 29, 1998.
This document provides summaries of the entries received for the 1998 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 1998
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.
-------
Academic Awards
Barry M. Trost,
Department of
Chemistry,
Stanford
University
The Development of the Concept of Atom Economy
The general area of chemical synthesis covers virtually all segments of the chemical indus-
try—oil refining, bulk or commodity chemicals, fine chemicals including agrochemicals,
flavors, fragrances etc., and pharmaceuticals. Economics generally dictates the feasibility
of processes that are "practical." A criterion that traditionally has not been explicitly
recognized relates to the total quantity of raw materials required for the process compared
to the quantity of product produced or, simply put, "how much of what you put into your
pot ends up in your product." In considering the question of what constitutes synthetic
efficiency, Professor Barry M. Trost has explicitly enunciated a new set of criteria by
which chemical processes should be evaluated. They fall under two categories—selectivity
and atom economy.
Selectivity and atom economy evolve from two basic considerations. First, the vast major-
ity of the synthetic organic chemicals in production derive from non-renewable resources.
It is self-evident that such resources should be used as sparingly as possible. Second, all waste
streams should be minimized. This requires employment of reactions that produce minimal
byproducts, either through the intrinsic stoichiometry of a reaction or as a result of mini-
mizing competing undesirable reactions, i.e., making reactions more selective.
The issues of selectivity can be categorized under four headings—chemoselectivity
(differentiation among various functional groups in a polyfunctional molecule), regioselec-
tivity (orientational control), diastereoselectivity (control of relative stereochemistry), and
enantioselectivity (control of absolute stereochemistry). These considerations have been read-
ily accepted by the chemical community at large. In approaching these goals, little attention
traditionally has been paid to the question of what is required. In too many cases, efforts to
achieve the goal of selectivity led to reactions requiring multiple components in stoichiomet-
ric quantities that are not incorporated in the product or reagents, thus intrinsically creating
significant amounts of byproducts. Consideration of how much of the reactants end up in
the product, i.e., atom economy, traditionally has been ignored. When Professor Trost's first
paper on atom economy appeared in the literature, the idea generally was not adopted by
both academia and industry. Many in industry, however, were practicing this concept with-
out explicitly enunciating it. Others in industry did not consideration the concept since it did
not appear to have any economic consequence. Today, all of the chemical industry explicitly
acknowledges the importance of atom economy.
Achieving the objectives of selectivity and atom economy encompass the entire spectrum
of chemical activities—from basic research to commercial processes. In enunciating these
principles, Professor Trost has set a challenge for those involved in basic research to create new
chemical processes that meet the objectives. Professor Trost's efforts to meet this challenge
involve the rational invention of new chemical reactions that are either simple additions or,
at most, produce low molecular weight innocuous byproducts. A major application of these
reactions is in the synthesis of fine chemicals and pharmaceuticals which in general utilize
very atom uneconomical reactions. Professor Trost's research involves catalysis, largely focused
on transition metal catalysis but also main group catalysis. The major purpose of his research
is to increase the toolbox of available reactions to serve these industries for problems they
encounter in the future. However, even today, there are applications for which such method-
ology may offer more efficient syntheses.
-------
Use of Microbes as Environmentally-Benign
Synthetic Catalysis
Fundamental change in chemical synthesis can be achieved by elaboration of new, envi-
ronmentally benign routes to existing chemicals. Alternatively, fundamental change can
follow from characterization and environmentally benign synthesis of chemicals that can
replace those chemicals currently manufactured by environmentally problematic routes.
Examples of these design principles are illustrated by the syntheses of adipic acid and cate-
chol developed by Dr. Karen M. Draths and Professor John W. Frost. The Draths-Frost
syntheses of adipic acid and catechol use biocatalysis and renewable feedstocks to create alter-
native synthetic routes to chemicals of major industrial importance. These syntheses rely on
the use of genetically manipulated microbes as synthetic catalysts. Nontoxic glucose is
employed as a starting material which, in turn, is derived from renewable carbohydrate feed-
stocks such as starch, hemicellulose, and cellulose. In addition, water is used as the primary
reaction solvent, and the generation of toxic intermediates and environment-damaging
byproducts is avoided.
In excess of 1.9 billion kg of adipic acid is produced annually and used in the manufac-
ture of nylon 66. Most commercial syntheses of adipic acid use benzene, derived from the
benzene/toluene/xylene (BTX) fraction of petroleum refining, as the starting material.
In addition, the last step in the current manufacture of adipic acid employs a nitric acid
oxidation resulting in the formation of nitrous oxide as a byproduct. Due to the massive scale
on which it is industrially synthesized, adipic acid manufacture has been estimated to account
for some 10 percent of the annual increase in atmospheric nitrous oxide levels. The Draths-
Frost synthesis of adipic acid begins with the conversion of glucose into cis,cis-muconic acid
using a single, genetically-engineered microbe expressing a biosynthetic pathway which does
not exist in nature. This novel biosynthetic pathway was assembled by isolating and ampli-
fying the expression of genes from different microbes including Klebsiella pneumoniae,
Acinetobacter calcoaceticus, and Escherichia colt. The cis,cis-muconic acid which accumulates
extracellularly is hydrogenated to afford adipic acid.
Yet another example of the Draths-Frost strategy for synthesizing industrial chemicals
using biocatalysis and renewable feedstocks is their synthesis of catechol. Approximately 21
million kg of catechol are produced globally each year. Catechol is an important chemical
building block used to synthesize flavors (e.g., vanillin, eugenol, isoeugenol), pharmaceuticals
(e.g., L-DOPA, adrenaline, papaverine), agrochemicals (e.g., carbofuran, propoxur) and
polymerization inhibitors and antioxidants (e.g., 4-t-butylcatechol, veratrol). Although some
catechol is distilled from coal tar, petroleum-derived benzene is the starting material for most
catechol production. The Draths-Frost synthesis of catechol uses a single, genetically engi-
neered microbe to catalyze the conversion of glucose into catechol which accumulates
extracellularly. As mentioned previously, plant-derived starch, hemicellulose, and cellulose
can serve as the renewable feedstocks from which glucose starting material is derived .
In contrast to the traditional syntheses of adipic acid and catechol, the Draths-Frost
syntheses are based on the use of renewable feedstocks, carbohydrate starting materials,
and microbial biocatalysis. As the world moves to national limits on carbon dioxide
emissions, each molecule of a chemical made from a carbohydrate may well be counted as a
credit due to the carbon dioxide which is fixed by plants to form the carbohydrate.
Biocatalysis using intact microbes also allows the Draths-Frost syntheses to utilize water as a
reaction solvent, near-ambient pressures, and temperatures that typically do not exceed
human body temperature.
Dr. Karen M.
Draths and
Professor
John W. Frost,
Department of
Chemistry,
Michigan State
University
-------
Small Business Award
PYROCOOL
Technologies,
Inc.
Technology for the Third Millennium: The Development
and Commercial Introduction of an Environmentally
Responsible Fire Extinguishment and Cooling Agent
Advances in chemical technology have greatly benefited firefighting in this century.
From the limitation of having only local water supplies at their disposal, firefighters have been
presented over the years with a wide variety of chemical agents, as additives or alternatives
to water, to assist them. These advances in chemical extinguishment agents, however,
have themselves created, in actual use, potential long term environmental and health prob-
lems which tend to outweigh their firefighting benefits. PYROCOOL Technologies, Inc
developed PYROCOOL EE.E (Fire Extinguishing Foam) as an alternative formulation of
highly biodegradable surfactants designed for use in very small quantities as a universal fire
extinguishment and cooling agent.
Halon gases, hailed as a tremendous advance when introduced, have since proven to be
particularly destructive to the ozone layer, having an ozone depletion potential (ODP) value
of 10-16 times that of common refrigerants. Aqueous film forming foams (AFFF's), devel-
oped by the U.S. Navy in the 1960's to combat pooled surface volatile hydrocarbon fires,
release both toxic hydrofluoric acid and fluorocarbons when used. The fluorosurfactants
compounds that make these agents so effective against certain types of fires render anaerobic
bacteria unable to metabolize their residue, often leading to contamination of ground water
supplies and failure of waste water treatment systems.
In 1993, PYROCOOL Technologies initiated a project to create a fire extinguishment
and cooling agent that would be effective in extinguishing fires and that would greatly reduce
the potential long-term environmental and health problems associated with traditionally used
products. To achieve this objective, it was first determined that the product (when finally
developed) would contain no glycol ethers or fluorosurfactants. In addition, it was decided
that the ultimate formulation must be an effective fire extinguishment and cooling agent
at very low mixing ratios. PYROCOOL F.E.F. is a formulation of highly biodegradable
nonionic surfactants, anionic surfactants, and amphoteric surfactants with a mixing ratio
(with water) of 0.4 percent. In initial fire tests at the world's largest fire-testing facility in
The Netherlands, PYROCOOL F.E.F. was demonstrated to be effective against a broad range
of combustibles.
Since its development in 1993, PYROCOOL F.E.F. has been employed successfully
against numerous fires both in America and abroad, and carries the distinction of extin-
guishing the last large oil tanker fire at sea (a fire estimated by Lloyd's of London to require
10 days to extinguish) on board the Nassia tanker in the Bosphorous Straits in just 12.5 min-
utes, saving 80 percent of the ship's cargo and preventing the spillage of 78,000 tons of crude
oil into the sea.
As demonstrated by the PYROCOOL F.E.F. technology, selective employment of rapid-
ly biodegradable substances dramatically enhances the effectiveness of simple water, while at
the same time eliminating the environmental and toxic impact of other traditionally used fire
extinguishment agents. Because PYROCOOL F.E.F. is mixed with water at only 0.4 percent,
an 87 to 93 percent reduction in product usage is realized compared to conventional extin-
guishment agents typically used at 3 to 6 percent. Fire affects all elements of industry and
society and no one is immune from its dangers. PYROCOOL F.E.F. provides an innovative,
highly effective, and 'green' alternative for firefighters.
-------
Alternative Synthetic Pathways Award
Elimination of Chlorine in the Synthesis of
4-Aminodiphenylamine: A New Process Which Utilizes
Nucleophilic Aromatic Substitution for Hydrogen
The development of new environmentally favorable routes for the production of chemi-
cal intermediates and products is an area of considerable interest to the chemical processing
industry. Recently, the use of chlorine in large scale chemical syntheses has come under
intense scrutiny. Solutia, Inc. (formerly Monsanto Chemical Company), one of the world's
largest producers of chlorinated aromatics, has funded research over the years to explore
alternative synthetic reactions for manufacturing processes that do not require the use of
chlorine. It was clear that replacing chlorine in a process would require the discovery of new
atomically efficient chemical reactions. Ultimately, it was Monsanto's goal to incorporate
fundamentally new chemical reactions into innovative processes that would focus on the
elimination of waste at the source. In view of these emerging requirements, Monsanto's
Rubber Chemicals Division (now Flexsys), in collaboration with Monsanto Corporate
Research, began to explore new routes to a variety of aromatic amines which would not rely
on the use of halogenated intermediates or reagents. Of particular interest was the identifica-
tion of novel synthetic strategies to 4-aminodiphenylamine (4-ADPA) a key intermediate in
the Rubber Chemicals family of antidegradants. The total world volume of antidegradants
based on 4-ADPA and related materials is approximately 300 million Ibs/year, of which
Flexsys is the worlds largest producer (Flexsys is a joint venture of Monsanto's and Akzo
Nobel's rubber chemicals operations)
Flexsys's current process to 4-ADPA is based on the chlorination of benzene. Since none
of the chlorine used in the process ultimately resides in the final product, the pounds of waste
generated in the process per pound of product produced from the process is highly unfavor-
able. A significant portion of the waste is in the form of an aqueous stream which contains
high levels of inorganic salts contaminated with organics that are difficult and expensive to
treat. Furthermore, the process also requires the storage and handling of large quantities of
chlorine gas. Flexsys found a solution to this problem in a class of reactions known as nucle-
ophilic aromatic substitution for hydrogen (NASH). Through a series of experiments
designed to probe the mechanism of NASH reactions, Flexsys realized a breakthrough in
understanding of this chemistry that has lead to the development of a new process to
4-ADPA that utilizes the base-promoted, direct coupling of aniline and nitrobenzene.
The environmental benefits of this process are significant and include a dramatic reduction
in waste generated. In comparison to the process traditionally used to synthesize 4-ADPA, the
Flexsys process generates 74 percent less organic waste, 99 percent less inorganic waste, 97 per-
cent less waste water. In global terms, if just 30 percent of the worlds capacity to produce
4-ADPA and related materials were converted to the Flexsys process, 74 million Ib/year less
chemical waste would be generated and 1.4 billion Ib/year less waste water would be generat-
ed. The discovery of the new route to 4-ADPA and the elucidation of the mechanism of the
reaction between aniline and nitrobenzene has been recognized throughout the scientific com-
munity as a breakthrough in the area of nucleophilic aromatic substitution chemistry.
This new process for the production of 4-ADPA has achieved the goal for which all green
chemistry endeavors strive, the elimination of waste at the source via the discovery of new
chemical reactions which can be implemented into innovative and environmentally safe
chemical processes.
Flexsys
America L.P.
-------
Argonne
National
Laboratory
Alternative Solvents/Reaction
Conditions Award
Novel Membrane-Based Process for Producing Lactate
Esters—Nontoxic Replacements for Halogenated and
Toxic Solvents
ANL has developed a process based on selective membranes that permits low-cost syn-
thesis of high-purity ethyl lactate and other lactate esters from carbohydrate feedstock. The
process requires little energy input, is highly efficient and selective, and eliminates the large
volumes of salt waste produced by conventional processes. Argonne's novel process uses per-
vaporation membranes and catalysts. In the process, ammonium lactate is thermally and
catalyticalry cracked to produce the acid, which, with the addition of alcohol, is converted to
the ester. The selective membranes pass the ammonia and water with high efficiency while
retaining the alcohol, acid, and ester. The ammonia is recovered and reused in the fermenta-
tion to make ammonium lactate, eliminating the formation of waste salt. The innovation
overcomes major technical hurdles that had made current production processes for lactate
esters technically and economically noncompetitive. The innovation will enable the replace-
ment of toxic solvents widely used by industry and consumers, expand the use of renewable
carbohydrate feedstocks, and reduce pollution and emissions.
Ethyl lactate has a good temperature performance range (boiling point: 154°C, melting
point: 40°C), is compatible with both aqueous and organic systems, is easily biodegradable, and
has been approved by the U.S. Food and Drug Administration for food. Lactate esters (pri-
marily ethyl lactate) can replace most halogenated solvents (including ozone-depleting CFCs,
carcinogenic methylene chloride, toxic ethylene glycol ethers, perchloroethylene, and chloro-
form) on a 1:1 basis. At current prices ($1.60-$2.00 per pound), the market for ethyl lactate is
about 20 million-pounds-per-year for a wide variety of specialty applications. The novel and
efficient ANL membrane process will reduce the selling price of ethyl lactate to $0.85-$ 1.00 per
pound and enable ethyl lactate to compete directly with petroleum-derived toxic solvents cur-
rently used. The favorable economics of the ANL membrane process therefore can lead to the
widespread substitution of petroleum-derived toxic solvents by ethyl lactate in electronics man-
ufacturing, paints and coatings, textiles, cleaners and degreasers, adhesives, printing, de-inking,
and many other industrial, commercial, and household applications. More than 80 percent of
the applications requiring the use of more than 3.8 million tons of solvents in the U.S. each year
are suitable for reformulation with environmentally friendly lactate esters.
The ANL process has been patented for producing esters from all fermentation-derived
organic acids and their salts. Organic acids and their esters, at the purity achieved by this
process, offer great potential as intermediates for synthesizing polymers, biodegradable plas-
tics, oxygenated chemicals (e.g., propylene glycol and acrylic acid), and specialty products.
By improving purity and lowering costs, the ANL process promises to make fermentation-
derived organic acids an economically viable alterative to many chemicals and products
derived from petroleum feedstocks.
A U.S. patent on this technology has been allowed, and international patents have been
filed. NTEC, Inc. has licensed the technology for lactate esters and provided the resources for
a pilot-scale demonstration of the integrated process at ANL. The pilot-scale demonstration
has produced a high-purity ethyl lactate product that meets or exceeds all the process perfor-
mance objectives. A 10 million pounds-per-year demonstration plant is being planned for
early 1999, followed by a 100 million pounds-per-year full-scale plant.
-------
Designing Safer Chemicals Award
Invention and Commercialization of a New Chemical
Family of Insecticides Exemplified by CONFIRM"
Selective Caterpillar Control Agent and the
Related Selective Insect Control Agents MACH 2™
and INTREPID™
The value of crops destroyed worldwide by insects exceeds tens of billions of dollars. Over
the past fifty years, only a handful of classes of insecticides have been discovered to combat
this destruction. Rohm and Haas Company has discovered a new class of chemistry, the
diacylhydrazines, that offers farmers, consumers and society a safer, effective technology
for insect control in turf and a variety of agronomic crops. One member of this family,
CONFIRM™, is a breakthrough in caterpillar control. It is chemically, biologically, and
mechanistically novel. It effectively and selectively controls important caterpillar pests in
agriculture without posing significant risk to the applicator, the consumer, and the ecosys-
tem. It will replace many older, less effective, more hazardous insecticides and has been
classified by EPA as a Reduced Risk Pesticide.
CONFIRM™ controls target insects through an entirely new and inherently safer mode
of action than current insecticides. The products acts by strongly mimicking a natural sub-
stance found within the insect's body called 20-hydroxy ecdysone, which is the natural
"trigger" that induces molting and regulates development in insects. Because of this
"ecdysonoid" mode of action, CONFIRM™ powerfully disrupt the molting process in target
insects, causing them to stop feeding shortly after exposure and to die soon thereafter.
Since 20-hydroxy ecdysone neither occurs nor has any biological function in most
nonanthropods, CONFIRM™ is inherently safer than other insecticides to a wide range
of non-target organisms such as mammals, birds, earthworms, plants, and various aquatic
organisms. CONFIRM™ is also remarkably safe to a wide range of key beneficial, predatory,
and parasitic insects such as honeybees, lady beetles, parasitic wasps, predatory bugs, beetles,
flies and lacewings, as well as other predatory arthropods such as spiders and predatory mites.
Because of this unusual level of safety, the use of these products will not create an outbreak
of target or secondary pests due to destruction of key natural predators/parasites in the local
ecosystem. This should reduce the need for repeat applications of additional insecticides and
reduce the overall chemical "load" on both the target crop and the local environment.
CONFIRM™ has low toxicity to mammals by ingestion, inhalation and/or topical appli-
cation and has been shown to be completely non-oncogenic, non-mutagenic, and without
adverse reproductive effects. Because of its high apparent safety and their relatively low use
rates, CONFIRM™ poses no significant hazard to the applicator or the food chain and does
not present a significant spill hazard. CONFIRM™ has proven to be an outstanding tool for
control of caterpillar pests in many integrated pest management (IPM) and resistance
management situations. All of these attributes make CONFIRM™ among the safest, most
selective, and most useful insect control agent ever discovered.
Rohm and Haas
Company
-------
Professor Michael R.
Ladisch, Laboratory of
Renewable Resources
Engineering and
Department of
Agricultural and
Biological Engineering,
Purdue University
Dr. Rakesh Govind and
Rajit Singh, Department
of Chemical Engineering,
University of Cincinnati
Entries from Academia
Biobased Adsorbents 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. An
installation at the Johns Hopkins School of Medicine processes 300,000 cubic feet of air per
minute (cfm) for a laboratory facility that requires 10 air changes per hour using all outdoor
air. A desiccant wheel system using an inorganic adsorbent was proposed due to its energy
efficiency and was installed at a cost of $3 million in 1991. After 4 years of monitoring its
operation, the Director of Maintenance Operations reported energy savings of $650,000 per
year over a conventional heating and air conditioning system.
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 percent 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
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 and are given the abbreviation—biobased. Unlike silica gels and other inorganic adsor-
bents, 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 systems for residential as well as commercial uses.
Bioconversion of Carbon Dioxide into
Organic Feedstocks
It has been established that emissions of carbon dioxide gas is responsible for about half
of the increase in global warming. Efforts to decrease the consumption of fossil fuel are lim-
ited by increasing human population and industrialization and the fact that alternatives to
fossil fuel 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 regards, a unique bioprocess has been developed
which is capable of converting waste carbon dioxide gas into algae, which is subsequently
fermented 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 require anaerobic conditions,
which requires that carbon dioxide gas has to be separated from oxygen and is an expensive
-------
process; unlike algae, photo tropic 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, Tetraselmis Suecica, has been used successfully in a photobioreactor using light
emitting dioded (LEDs) with a specific wavelength of 680 nm and a gas residence time of a
few seconds. More than 98 percent removal efficiency of carbon dioxide gas from typical coal
fired power plant stack gases was achieved experiementally at 3 seconds gas residence time at
ambient temperature and pressure. The algae was separated form the aqueous phase by set-
tling 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 percent to
acetic acid and 89 percent to methane gas. Catalytic conversion of methane gas to methanol
and other organic feedstocks has been established in the literature. Thus, this process offers
several advantages: bioconversion of waste carbon dioxide gas to useful organic feedstocks at
ambient temperature 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 sides and acetic acid can be manufactured at less than
half the current costs of manufacturing acetic acid from natural gas or crude oil resources.
Biotechnological Routes to 'Tailored' Polymeric Products
of Environmental and Industrial Importance
Biodegradable polymers are attracting much public and industrial interest since they
represent an important strategy to ease current problems in solid waste disposal. The surfac-
tant and emulsifier industry in the U.S., for example, has grown nearly 300 percent during
the last decade. In 1989, the U.S. production was estimated to be 15-5 billion pounds
and the value of U.S. shipments in 1989 was approximately $3.7 billion. Many of the
applications of surfactants and emulsifiers either involve human contact or release into the
environment. Therefore, there is a critical need for a new generation of low toxicity fully
biodegradable products.
The work of Richard A. Gross at the University of Massachusetts Lowell on emulsion
analogs, y-poly(glutamic acid) and the preparation of low molecular weight polyester-poly-
etheylene glycol diblocks have provided important new products from microbial syntheses.
These products meet the need for biodegradability and low toxicity and, therefore, provide
considerable human health and environmental benefits. Microbial polymerizations offer the
potential for the discovery of important new routes to polymers and materials from renew-
able resources that involve all aqueous, green chemical routes. A critical problem limiting the
utility of such methods, however, is the inability to control product structural variables that
ultimately determine functional properties. The work of Professor Gross has led to the devel-
opment of a family of technologies which has demonstrated unprecedented levels of control
for nonribosomal mediated microbial polymerizations. Lipoheteropolysaccharides have been
prepared from renewable resources, and innovative methods were developed to control the
product's fatty acid structure and the degree of substitution. This has led to a diverse family
of new biodegradable bioemulsifiers that have wide applicability for the stabilization of
oil/water emulsions in cleaning and degreasing formulations, biocosmetics, green coating
technologies, and bio remediation of organic pollutants.
A second technology area has used polyethylene glycols to regulate microbial polyester
molecular weight, repeat unit composition, and alter repeat unit sequence distribution.
Furthermore, this strategy can be used to form microbial polyester-polyethylene glycol
Professor Richard A.
Gross, Department
of Chemistry,
University of
Massachusetts, Lowell
-------
Dr. Chhiu-Tsu Lin,
Department of
Chemistry and
Biochemistry, Northern
Illinois University
Professor Eric J.
Beckman, Chemical
Engineering
Department, University
of Pittsburgh
10
diblock copolymers. It is now possible to consider the in-vivo preparation of synthetic-nat-
ural diblocks. This technology has therefore created a number of opportunities for the
preparation of completely biodegradable interfacial agents for blends, the termination of
chains with reactive end-groups for coupling pharmacologically active molecules, and the
engineering of surfactant molecules. A third technology area has been the development of
new fermentation routes to anionic y-poly (glutamic acid) from renewable resources such as
glucose, y-poly (glutamic acid) has the potential to replace millions of pounds of anionic
polymers such as polyacrylic acid, which is nonbiodegradable and persistent in nature.
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 multi-step 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
Mongomery 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 multi-step coating
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 pre-dispersed
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 ofCO2-Soluble Ligands for Affinity
Extraction Using CO2
Carbon dioxide has elicited significant interest among the academic and industrial com-
munity over the previous decade in that it exhibits properties which render it a relatively
"green" solvent. Carbon dioxide is an inexpensive, non-toxic solvent whose use in chemical
processes is not limited by either FDA or EPA regulations. Use of CC>2 in extractions from
water (or in biphasic reaction systems) is particularly advantageous in that, unlike the analo-
gous situation using conventional organic solvents, one needn't worry about contamination
of the aqueous phase when using CC>2. Unfortunately, because CC>2 is a low dielectric fluid,
extraction of polar materials from aqueous solution using CC>2 has been heretofore techni-
cally infeasible.
The work of Professor Eric J. Beckman at the University of Pittsburgh has shown that
design and use of highly CCVsoluble ligands allows one to employ carbon dioxide in extrac-
-------
tions of polar materials from water which were previously thought to be untenable. Using flu-
oroether-functional affinity ligands, for example, Professor Beckman has shown that one can
extract proteins from aqueous solution into CC>2 with retention of activity following recov-
ery by depressurization. Analogous chelating agents have been used to extract metals into
CC>2 as well. While initial work has targeted primarily extractions, the described CC>2 solu-
ble ligands can also be used to solubilize catalysts in CC>2 (enzymes
and metals are examples) for use in carrying out reactions either in CC>2 or in CC>2 water
biphasic mixtures.
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
management 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 process-
es 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 mor-
tar 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. While the technology to reuse rubber tires into cement system yields value-added
infrastructural material, it eliminates the imminent threat of health hazard and explosion
potential because of the flammable nature of rubber tires.
The Determination of Alternative Solvents
Quantifying and Qualifying Green Chemistries
in Industrial Surface Cleaning
The Massachusetts Toxics Use Reduction Institute (TURI) was established by the state
legislature with the passage of the Toxics Use Reduction Act (TURA) of 1989. TURI is a
multi-disciplinary research, education, and technical support center at the University of
Massachusetts, Lowell created to promote reduction in the use of toxic chemicals and/or the
generation of toxic byproducts in Massachusetts industry and commerce. Because tradition-
al organic and chlorinated solvents have known serious health and environmental effects,
Dr. Dharmaraj
Raghavan, Department
of Chemistry, Howard
University
Carole LeBlanc,
The Massachusetts
Toxics Use Reduction
Institute, University of
Massachusetts, Lowell
11
-------
Professor Terrence J.
Collins, Department of
Chemistry, Carnegie
Mellon University
Dr. Jon D. Stewart,
Department of
Chemistry, University
of Florida
TURI maintains a Surface Cleaning Laboratory (SCL) with the capability to evaluate the
effectiveness of different cleaning chemistries and equipment on a variety of substrates and
contaminants. The objective of the Lab is to develop and promote safer alternatives to
hazardous cleaning solvents. In this way, the Lab practices input substitution, one of six
program-defined toxics use reduction (TUR) techniques. The Laboratory is designed with a
special focus on aqueous/semi-aqueous cleaners and state-of the-art surface cleanliness analy-
ses. In full operation since 1994, SCL has served a wide range of businesses, including the
electronics, metalworking, automotive, plastics, and paper and pulp sectors. The Institute's
comprehensive appraisal of the tests conducted thus far will assist other companies with
solvent substitution in many applications throughout the nation and the world.
Efficient, Selective, Totally Chlorine Free (TCP) Wood
Pulp Bleaching Technology
The Pulp and Paper Industry is the eighth largest industry in the United States. In 1991,
the value of shipments from the U.S. paper and allied products industry was $129 billion.
The 1994 global capacity of bleached pulp for paper making was 93.3 million tons; 58.7
millions tons was produced in the United States. Oxidative bleaching is essential for remov-
ing residual lignin from the pulp to produce bright white fiber. Dominant U.S. bleaching
technologies have employed chlorine-based oxidants since the inception of the industry.
Today, approximately 40 million tons of chlorine is produced annually; ca. 17 percent is used
in paper making. The annual U.S. chlorine dioxide production has been estimated to be
more than 105 metric tons.
In recent decades the environmental significance of chlorine-based bleaching has become
well-recognized. Chlorine-containing organics are produced as byproducts of widely-prac-
ticed bleaching technologies, some of which are highly toxic. November 14, 1997, EPA
signed a Cluster Rule requiring the industry to reduce chlorinated organics production.
Enormous incentive exists to find cost-effective totally chlorine free (TCP) methodologies for
bleaching pulp that meet environmental, health, and industrial needs. Professor Terrance J.
Collins at Carnegie Mellon University has developed robust ligands that support iron cata-
lysts for peroxide activation. This PFC technology is remarkable in possessing significant
environmental and technological advantages. PFC catalyst lifetimes can be controlled in an
unprecedented fashion because deep understanding has been achieved concerning how the
catalyst ligands degrade upon oxidation and how such degradation can be blocked. The PFC
catalysts consist of nontoxic elements. At micromolar concentrations, they activate peroxide
efficiently for pulp bleaching from 0 to 90°C in water from neutral to basic pH; bleaching
performance is best at room temperature, but remains excellent at 50°C. The all-important
selectivity for lignin over cellulose oxidation is greater with the PFC technology than any
existing TCP technology.
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
12
-------
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 yeast 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
phamaceutical end-products, it is imperative to consider the development of effective carbon-
carbon bond forming reactions in aqueous media. The work of Dr. Leo A. Paquette at the
Ohio State University demonstrates not only that the counter-intuitive 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.
Environmentally Benign Solvent-Free
Chemical Processing
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 NaIO4-silica, 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.
Dr. Leo A. Paquette,
Department of
Chemistry, The Ohio
State University
Dr. Rajender S. Varma,
Texas Regional
Institute for
Environmental Studies,
Sam Houston State
University
13
-------
Professor John C.
Warner, Department
of Chemistry,
University of
Massachusetts, Boston
Polaroid Corporation
Dr. Douglas C. Knipple,
Department of
Entomology, Cornell
University
Environmentally Benign Supramolecular Assemblies of
Hydroquinones in Polaroid Instant Photography
The work of Professor John C. Warner at the University of Massachusetts, Boston represents
the first example of supramolecular synthesis in a manufacturing system for pollution preven-
tion. 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 generation, 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 can-
didate 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 pre-
vention, 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 aqueous dispersing techniques.
In Vivo Synthesis ofLepidopteran 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 agricul-
ture 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 animal
disease vectors, the development of insecticide resistance in insect pest populations and the envi-
ronmental damage caused by insecticides were quickly recognized as serious drawbacks to their
use. Today the environmental and human health effects associated with the manufacture and
use of insecticides for pest control are widely recognized. These include the following: 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 envi-
ronment 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 effectiveness and
selectivity depend upon high chemical and stereo-specific purity, making them expensive to
synthesize. The latter factor has limited their commercial success versus conventional insecti-
cides. 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 insecticide 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 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 lat-
14
-------
ter goal will significantly improve the economic competitiveness of existing pheromone prod-
ucts, and could provide the basis for the expansion of this promising insect control
technology into other markets.
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 devel-
opment 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 by-products, 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 reaction mixture to come close to
its boiling point. Such reactions can be completed on several hundred grams scale in a few min-
utes. Larger scale synthesis should be possible by using commercial microwave equipment used
by the food industry.
The elimination or reduction of the use of organic solvents, and the purer products formed,
lead to reduced chemical waste (such as, organic solvents for reactions and recrystallization,
chromatographic material for purification, etc.). To demonstrate 'atom economy (more prod-
ucts 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 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 nitra-
tion method can be accomplished by irradiating with microwaves, have observed mild
acceleration of chemoenzymatic reactions under low intensity microwave irradiation, 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 synthesis and thus make the devel-
opment 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 method-
ologies that reduce or eliminate the use or generation of feedstocks, products, byproducts, 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 incor-
porated 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 average), new methods for determining physical
properties; milder and safer alternative reaction conditions; alternative benign solvents; and differ-
Dr. Ajay K. Bose,
Stevens Institute of
Technology
Dr. Mono M. Singh,
National Microscale
Chemistry Center,
Merrimack College
15
-------
ent synthetic pathways, often employing catalytic and other environmentally safe techniques. The
National Microscale Chemistry Center was established at Merrimack College in 1993. The cen-
ter offers workshops, training and other related support to teachers and industrial chemists in
microscale chemistry techniques. Currently, more than 2000 institutions in the United States
have, either fully or partly, adopted this approach. NMC2 is also the lead site of an international
consortium promoting the microscale/Green Chemistry revolution.
Craig L. Hill,
Department of
Chemistry, Emory
University
Ira A. Weinstock, USDA
Forest Service, Forest
Products Laboratory
A New Catalytic Biomimetic Technology to Convert
Wood to Paper Without Pollution
A completely new approach to the delignification of wood or wood pulpcomposites 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 selec-
tive 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, that
imparts strength to trees and paper, and lignin, that 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, and not C>2, have been the dominant oxidants. While
decades of optimization have led to highly selective delignification (minimally damaged cel-
lulose), these man-made technologies produce waste streams that contain environmentally
deletarious 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^C^) 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 biometric approach uses versatile, nontoxic, and inexpensive inorganic
clusters known as polyoxometalates (POMs) in two steps. The first step involves delignifica-
tion 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 catalyzes the com-
plete conversion (mineralization) of the dissolved lignin fragments to CO2 and HjO. 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 elim-
inates 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.
16
-------
A Non-Toxic Liquid Metal Composition for Use as a
Mercury Substitute
Mercury is used extensively in switches and sensors; yet, mercury is toxic to humans and
animals. In addition to being an excellent conductor of electricity, mercury, unlike any other
metal known, remains fluid throughout a wide temperature range which encompasses 0°C.
Another important physical attribute of mercury is that it has significant surface tension
which means that it does not wet glass, metal, or polymer surfaces. Because of these proper-
ties, mercury is found in numerous commercial products such as automobiles, thermostats,
steam irons, pumps, computers, and even tennis shoes. In each of these cases, mercury func-
tions as a liquid electrical switch. Discarded consumer items which contain mercury have
become an environmental hazard. Several states have banned new products that contain mer-
cury. Since billions of mercury switches are made each year worldwide, a nontoxic
replacement for mercury appears highly desirable.
At Virginia Tech, a gallium-based alloy containing indium, zinc, and copper has been
identified. The alloy conducts electricity, freezes below 0°C, and exhibits high surface tension.
In other words, this material which looks and acts like mercury does not contain a single toxic
element. The alloy can conduct both AC and DC current, exhibits a solidification tempera-
ture near -10°C, possesses a very high boiling point and very low vapor pressure, and has
similar flow characteristics to mercury. Both glass- and metal-housing switches have been
found to be highly acceptable with the nonmercury material after extensive testing. In addi-
tion to the environmental advantages, nonmercury switches and sensors can replace mercury
switches and sornsors without modifying existing technology. In fact, the methodology for
fabrication of nonmercury switches and sensors would be identical to that currently being use
with toxic mercury. Mercury also is used in temperature sensors, pressure activated switches,
pumps and filters, slip rings, liquid mirror telescopes, fluid unions, dental amalgam, and in
medical devices such as sphygmomanometers and bougies. The nonmercury described here-
in also can serve as a substitute for elemental mercury in many of these applications.
Novel Applications of Polymer Composite from
Renewable Materials
Metal corrosion costs the United States about 4.2 percent 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 of the surface
involves paint stripping and application of a fresh paint coating. Traditional stripping meth-
ods employ 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 percent of the waste by
biological or chemical degradation of the spent media. The degradation of solid media waste
(based on renewable polymer) results in the production of speciality solvents which 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
Professor Larry T.
Taylor, Department of
Chemistry, Virginia
Tech
Virginia Tech
Intellectual Properties
Dr. Dharmaraj
Raghavan, Department
of Chemistry, Howard
University
17
-------
Dr. Jimmy E. Antia
and Dr. Rakesh Govind,
Department of Chemical
Engineering, University
of Cincinnati
Dr. Bala Subramaniam,
Department of
Chemical and
Petroleum Engineering,
University of Kansas
a worldwide market approaching $1 billion, annually. Membranes have found wide applica-
tion in the industries, the separation industry remains the most important segment. 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 work-
ing crew to carncinogenic solvents during the preparation of membranes. To address these
concerns, Dr. Raghavan has designed a compatablizer based polymer composite, where the
major component is renewable polymeric material and the minor component is nondegrad-
able synthetic polymer. The technology is based on the degadability of the renewable polymer
in protic solvent/enzymic system, and the ability to formulate a porous microstructure of syn-
thetic polymer. The degradation of the renewable polymer results in the production of
chemicals which are environmentally safe and can be used in the synthesis of renewable
polymer.
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. It has been shown that in-situ
coatings of zeolites on monoliths substrates, maximizes the effectiveness of the "shape-selec-
tive" aspects of zeolite catalysis. 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 hydrocarbons 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. Main
technical advantages of monolith reactors is low pressure drop, improved performance due to
less plugging and channeling, and high surface area per unit volume of reactor. The technol-
ogy 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 (C^-C^) into gasoline
compounds (Cy-Cg). Alkylates constitute roughly 15 percent 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 environ-
mentally-safer alternatives to liquid acids. However, solid-acid catalysts deactivate rapidly due
to coke retention in the pores. In gas-phase media, the heavy coke precursors (such as olefinic
oligomers) are poorly soluble. In liquid phase reaction media, the transport of coke precur-
sors out of the catalyst pores is severely restricted resulting in their readsorption and
transformation to consolidated coke. The work of Dr. Bala Subramanian 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 sol-
18
-------
vent, 1-butene/isobutane alkylation was performed at supercritical conditions resulting in vir-
tually steady alkylate (trimethylpentanes and dimethylhexanes) production in a fixed-bed
reactor on solid acid catalysts (HY zeolite, sulfated zirconia and Nafion) for several days. The
carbon dioxide-based supercritical process thus offers an environmentally safer alternative to
conventional alkylation by eliminating a major technological barrier impeding the applica-
tion of solid acid catalysts in alkylation practice.
Novel Waste Minimization Approach: Production of
Carbon-Based Catalyst or Sorbent from 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 also been
increasing due to a greater percent of the global population being served by sewer lines and
an increasing 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 minimalization and recycling at wastewater
treatment facilities.
An innovative process was developed by the Department of Chemical and Environmental
Engineering at the Illinois Institute of Technology to convert biosolids produced at waste-
water treatment facilities primarily to carbons with a wide range of applications as adsorbents
or catalysts. The feedstock for the process was biosolids produced at the Spring Brook Water
Reclamation Center, in Naperville, Illinois. The results of the laboratory study showed that
biosolids can be effectively and economically converted to a carbon-based catalyst or sorbent
with relatively high surface area and small pores with a rather wide pore size distribution. The
total surface area, surface structure, and pore size distribution were effectively controlled by
varying chemical activation processes and heat treatment methods. The characteristics of the
produced carbons were evaluated using N2-BET (Brunauer, Emmett, and Teller) gas adsor-
ber and X-ray diffraction. This study demonstrates the effective conversion of waste from
wastewater treatment processes to a useful carbon-based catalyst or sorbent, and at the same
time, replaces fossil fuels in the production of activated carbon.
Orphan Chemical Recycling Program
In April of 1993, the Department of Environmental Health and Safety at Bowling Green
State University initiated a program to transfer orphan laboratory chemicals to nonuniversi-
ty academic institutions primarily within Wood County, Ohio (note: an orphan chemical is
one that is still useful but unwanted by those having them). In 1994, the program gained the
participation of an area hazardous waste management company. This joint effort has allowed
the program not only to move beyond the boundaries of Wood County, but also to include
small business and industry in the recycling effort. The program, which is free of charge, has
now seen participation from 30 academic institutions and 52 small business, industry, and
governmental facilities throughout Ohio as well as from other states. Since April of 1993, the
program has transferred over 3,500 pounds of solids and 1,100 gallons of liquids to "needy"
institutions and facilities. These transactions have resulted in cost savings between $330,000
and $405,000.
Dr. Nasrin R. Khalili,
Hamid Arastoopour,
and Laura Walhof,
Department of
Chemical and
Environmental
Engineering, Illinois
Institute of Technology
Bowling Green
State University
19
-------
James P. Rybarczyk,
Department of
Chemistry, Ball State
University
Dr. Michael F. Doherty,
Dr. Michael F. Malone,
Department of
Chemical Engineering,
University of
Massachusetts,
Amherst
Dr. Stephen Thompson,
The Center for Science,
Mathematics and
Technology Education,
Colorado State
University
Premature Degradation of Coolant Oil in the
Machining of Magnesium in the Automobile Industry
The research of James P. Rybarczyk at Ball State University is concentrated on a funda-
mental chemical study to increase the longevity of a water-based coolant, cutting oil emulsion
used in the machining and manufacture of magnesium cases for the automotive industry.
Water-based emulsions have virtually replaced the more toxic organic solvent-based ones, but
the difficulty of water-based ones in magnesium applications involves the dissolution/reac-
tion of the machined magnesium fines with water, producing hydrogen gas and dissolved
magnesium ions. These Mg+2 ions then interact with the emulsion, breaking the oil/water
emulsion and splitting out the oil, creating scale deposits of magnesium carbonate, magne-
sium greases, and the virtual disintegration of both the coolant and cutting properties. This
necessitates a changing of the coolant systems at a frequency of 1.5 to 2 months, as opposed
to a theoretical 24 months. This high frequency of replacement/disposal results in a signifi-
cant workload cost, monetary cost, and above all, environmental cost. Rybarczyk's research
established the causes of the premature breakdown of the emulsion and provided seven rec-
ommendations for chemical and/or physical process modifications. The study focussed on
the fragility of the emulsion and on the control of pH at basic levels to minimize the water
dissolution of magnesium. The study showed an increase of better than 16 times in the life-
time of the emulsion from these recommendations. The industry has currently implemented
three of the recommendations, with hopefully more to follow, resulting in a 2 times to 3
times increase in emulsion lifetime.
Reactive Distillation Technology to Reduce Waste
at the Source
Mixtures are azeotropic if they can be distilled (or condensed) without a change of com-
position. The existence of azeo tropes in multicomponent mixtures in the absence of chemical
reactions is well understood phenomenologically and theoretically. Azeotropes place a funda-
mental limit on the compositions attainable in mixtures by fractional distillation, but they
can in some cases be 'broken by carrying out chemical reaction and separation simultane-
ously rather than sequentially. Here, Dr. Michael F. Doherty and Dr. Michael F. Malone at
the University of Massachusetts, Amherst report the discovery of a boiling state of constant
composition and temperature in a mixture of acetic acid, isopropanol, isopropyl acetate, and
water that is simultaneously in both reaction and phase equilibrium. This project confirmed
earlier theoretical predictions by the senior author and others of the existence of reactive
azeotropes that would allow combined reaction and distillation without a change in compo-
sition. This hybrid combination is also known as "catalytic" or "reactive" distillation. The
technology is broadly applicable as the basis for innovative process designs
to improve yields and productivity and eliminate or reduce by-product formation.
The researchers built a working apparatus to prove the value of reactive distillation at
higher pressures and assessed the feasibility of making dimethyl ether by reactive distillation
from methanol.
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
20
-------
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 provides a realistic approach to green chemistry and allows academic
institutions to institutionalize lasting behavioral changes. SSC provides an easy to implement,
affordable, and wide application remedy to a real environmental management problem face
by most college and university chemistry programs.
Source Reduction Through Mass Integration:
Mass Exchange Network Synthesis
Mass Integration, and in particular Mass Exchange Network (MEN) synthesis, represents
a set of systematic and general methods for the design of networks that increase the mass effi-
ciency of manufacturing processes. Dr. Vasilios Manousiouthakis at the University of
California Los Angeles has conceived of these design methods in an effort to provide novel,
powerful and versatile tools, for engineers that wish to pursue source reduction and waste
minimization. The goal of this project has been the development of the Mass Integration
methodology and its industrial application. The general formulation of the design problem,
allows the incorporation of any possible network and any mass exchange operation, includ-
ing that of distillation. It also permits use of the method in both a grassroots and a retrofit
design setting. Mass Integration's power and flexibility, have led to its wide applicability.
Several academic and industrial mass integration application are being reported and a multi-
million dollar mass integration industry is coming into its own. In collaboration with M.W.
Kellogg, Dr. Manusiouthakis has recently applied his design method on a phenol manufac-
turing facility. The resulting process design demonstrated a 17 percent reduction in
freshwater use and a 50 percent reduction in waste phenol.
Successful Development of Recombinant
Xylose-Fermenting Saccharomyces Yeasts Capable
of Effectively Co-Fermenting Glucose and Xylose
from Renewable Cellulosic Biomass to Ethanol as
Clean Transportation Biofuel
Ethanol is an effective, environmentally friendly, nonfossil, transportation biofuel that
produces far less pollution than gasoline, contributes essentially no net carbon dioxide to
the atmosphere, and eases the threat of global warming. Furthermore, ethanol can be
produced from plentiful, domestic, renewable, cellulosic biomass feedstocks. This reduces
our nation's dependency on imported oil, protects its energy security, and reduces our trade
deficit. However, a major obstacle in this process is that cellulosic biomass contains two major
sugar molecules, glucose and xylose. Saccharamomyces yeasts, traditionally used and still the
only microorganisms currently used for large scale industrial production of ethanol from
glucose, are unable to ferment xylose to ethanol, making the use of the safest, most effective
Dr. Vasilios
Manousiouthakis,
Department of
Chemical Engineering,
University of California
Los Angeles
Dr. Nancy W. Y. Ho,
Laboratory of
Renewable Resources
Engineering, Purdue
University
21
-------
Professor James B.
Hendrickson,
Department of
Chemistry, Brandeis
University
22
Saccharamomyces yeasts for conversion of biomass to ethanol economically infeasible.
Furthermore, there are no other natural microorganisms that can ferment both glucose and
xylose with reasonable efficiency.
After many years of dedicated research efforts, Dr. Nancy W. Y. Ho at Purdue University
achieved a historic breakthrough in the development of genetically engineered
Saccharomyces yeasts that can effectively ferment both major sugars (glucose and xylose)
present in cellulosic biomass to ethanol. Her work has made it possible to use the most safe,
effective, user friendly Saccharamomyces to ferment sugars from cellulosic biomass to ethanol
to be used as the environmentally friendly transportation fuel. This was accomplished by
cloning multiple copies of genes encoding three key enzymes for metabolizing xylose in
yeasts. These genes were modified so that they were able to produce the desired enzymes
in yeasts in the presence of glucose and/or xylose. This allows yeasts
to effectively co-ferment glucose and xylose simultaneously to ethanol. The current best
xylose-fermenting Saccharamomyces yeasts can ferment glucose and xylose efficiently and cost-
effectively for industry to produce ethanol from cellulosic biomass. More effective yeasts that
will ferment xylose faster and will also be able to produce other high-valued byproducts can
still be developed.
The SYNGEN Program for Generation of
Alternative Syntheses
Thousands of organic chemicals are synthesized annually on an industrial scale, and their
manufacture can often lead to environmental problems. If alternative syntheses that create
fewer hazardous wastes and less pollution could be found, a number of these problems could
be solved. No one would claim that the synthesis routes currently in use are the only ones
possible, or even that they know them to be the best routes. Indeed it is easy to show that the
number of possible synthesis routes to target molecules of even modest complexity is usual-
ly enormous. However, organic chemistry has traditionally not provided any logical protocol
for the systematic design of synthesis routes to any target molecule. If there were such a pro-
tocol, other routes to any industrial synthesis target could be systematically explored, and
their relative impacts on the environment examined. Although a number of computer pro-
grams have been written, few have come out of their academic sources into the world of
chemical industry for practical use, and essentially none have been viewed there as successful.
The SYNGEN program developed by Professor James B. Hendrickson at Brandeis
University is different from the others in conception and practice. It aims at surveying all pos-
sibilities and reduces the vast number of these possibilities quickly and stringently to focus on
only the shortest and cheapest routes following a criterion of economy. It is self-consistent
and not interactive, and so avoids skewing the results to favor operator's preconceptions. On
this base it now adds evaluation of environmental hazards to the best routes selected. Earlier
version of SYNGEN were also not successful in the practical world, partly because chemists
did no fully understand its logic and also because the program too often generated reactions
which the chemists regarded as chemically unworkable. To clarify the logic for chemists, the
program first focuses on the criteria of the target skeleton from available starting skeletons.
then it presents the ideal synthesis—of construction reactions only, to create the target just by
sequential constructions uniting these starting skeletons. Finally the digital basis rigorously
but compactly defines all possible molecular structures and their reactions. This basis allows
the new SYNGEN program to propose all the short alternative syntheses of any product from
real starting materials in terms both of their cost and their environmental impact. This makes
possible for the first time an unbiased collection of real benign synthesis routes for the
production of commercial chemicals. With this tool we can truly explore alternatives for
green chemistry.
-------
Synthetic Methodology 'Without Reagents'. Commercial
Manufacture oflnositols and Other 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
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.
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 non-toxic precursors, and minimizing
energy consumption. Professor Weimer and his students have demonstrated model ceramic
synthesis systems which 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.
Waste Biomass Utilization in the Production of a
Biodegradable Road Deicer
The effective utilization of biomass 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
Dr. Tomas Hudlicky,
Department of
Chemistry, University
of Florida
Professor Alan W.
Weimer, Department of
Chemical Engineering,
University of Colorado
Alexander P. Mathews,
Department of Civil
Engineering, Kansas
State University
23
-------
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 percent lactose and 0.1
percent to 0.8 percent lactic acid. About 50 percent 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 ener-
gy utilization.
The work of Alexander P. 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. Bulk of this expenditure is on the application of chemical deicers, principally
sodium chloride. 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 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 environmental damage
by contaminating water supplies and soils.
The main objectives of the work of Mathews were to examine the use of biomass wastes
in the production of deicers, calcium magnesium acetate (CMA), and calcium magnesium
propionate (CMP). A novel two-stage fermentation process was developed to utilize and con-
vert inexpensive substrates such as whey permeate to acetic and propionic acids for use in the
production of the deicer. The two-stage process has a substrate conversion efficiency of about
90 percent compared to 53 percent 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
which can be used in the production of CMA/CMP deicer).
Dr. Claudia Lage
Nassaralla, Department
of Metallurgical and
Materials Engineering,
Michigan Technological
University
Waste Reduction and Recycling of Magnesite-Chrome
Refractory into the Steelmaking Process
The primary objectives of the work of Dr. Claudia Lage Nassaralla at Michigan
Technology 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 tempera-
ture 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 detrimen-
tal 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 &2O3. 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 ppni must be
treated before disposal.
The technology that is currently being developed by Dr. Nassaralla has the potential to
minimize the formation of Cr6+ by carefully controlling the brickmaking and Steelmaking
24
-------
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 installa-
tion of additional equipment will be necessary. The waste material can be treated onsite, 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 elec-
tric 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 conversion to chromium metal, di- and triva-lent chromium
will avoid contamination of the environment by possible leaching of Cr6+ after dumping.
Water as Solvent for Chemical and Material Syntheses
Rather than sacrificing one or the other, to synchronize the advancement of science and
technology and 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 non-toxic, non-explosive, non-flammable, as well as the basis and bear-
er 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 syn-
theses have been carried out in organic solvents. At Tulane, Professor Chao-Jun Li has
developed various synthetic methodologies by using water as solvent. By using these method-
ologies he has synthesized biologically important natural products, novel electronic and
optical materials, and nano-carbon materials. In most cases, the studies have the dual advan-
tages 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.
Water borne 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 EPAs 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
Professor Chao-Jun Li,
Department of
Chemistry, Tulane
University
Dr. David E. Nikles,
Department of
Chemistry, University
of Alabama
25
-------
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.
26
-------
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
service ware, and packagings. Mater-Bi™ is a product technology which offers enormous
advantages for dealing with the problems of solid waste disposal. Disposal of conventional
plastic products, which constitute the largest share of disposable products, have a significant
negative impact on the environment. Typically, disposable products are landfilled and rapid-
ly diminish landfill capacity. Being compostable, disposable products made of Mater-Bi™
are fully recyclable. Biodegradable food serviceware, for example, presents a significant oppor-
tunity for reducing the volume of the solid waste stream. In 1994, nearly 39 billion pieces
of disposable 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. Other new and significant applications for biodegradables are being developed
for medical products, textiles, etc. Such products can be transformed into much needed
composts and soil amendments for agricultural and horticultural use. Mater-Bi™ resin used
for films and sheets is made of starch and a polymer, polycaprolactone. Biodegradation
time is between 20 and 45 days in composting conditions. Mater-Bi™ resin used for dimen-
sionally 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 Pesticide 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, fertilizers, etc. (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.
BIOCORP, Inc.
Burch Company
27
-------
EOSystems, Inc.
Biofine, Incorporated
CerOx Process Technology for Non-Thermal Destruction
of Organic Hazardous Wastes
EOSystems, Inc. has commercialized the CerOx (Cerium Oxidation) process for destroy-
ing hazardous organic waste streams. The process converts toxic wastes into CO2 and water.
The unique process 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 gen-
erator. Seven sizes of systems have been designed to meet the needs of various customers
ranging from 300 pounds of destruction per day to over three tons per day. The CerOx
process is an electrochemical 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 scalability of the CerOx Process allows it to be placed onsite for destruction of haz-
ardous 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 meth-
ods such as incineration and molten metal pyrolysis.
Conversion of Low-Cost Biomass Wastes to Levulinic
Acid and Derivatives
Biofine, Incorporated of Waltham, Massachusetts, has patented a process to convert cel-
lulosic biomass into levulinic acid (LA) using high-temperature, dilute-acid hydrolysis, and is
manufacturing LA at a demonstration plant in New York State. The process is economical
even without tipping fees for the feedstock. The product, a promising chemical building
block, is made with low-cost and abundant waste feedstocks such as papermill sludge. Wet
feedstocks can be used without drying, thereby saving energy. LAs niche markets provide
excellent small-scale opportunities, and large-scale opportunities will open up as the price of
this highly versatile chemical intermediate lowers. LA's worldwide market is about one mil-
lion pounds per year at a price of $4 to 6/lb. Large-scale commercial 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 diphenolic acid that sell for $2.00/lb or less. Eventually, Biofine
hopes to build larger plants to convert 1,000 dry ton/day of feedstock into $0.04 to 0.05/lb
LA for conversion into economical fuel additives. The worldwide commercial market for LA
and its derivatives could someday reach one trillion Ibs/yr. Large-scale plant opportunities are
being assessed for several locations in the United States and worldwide.
28
-------
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
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) near 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.
Synthon Corporation
29
-------
NICCA U.S.A., Inc.
Environmental
Technology and
Education Center, Inc.
(ETEC)
Heavy Metals Free, Non-Formaldehyde Fixing Agent for
Direct and Fiber Reactive Dyes
Generally, a textile fixing agent is a cationic polymer, which forms a resin film covering
the surface of the fiber and adheres to it. This action causes the many cationic groups in the
molecule of the polymer to bond with the dye anions in the fabric to block the hydrophilic
groups of the dye, thereby forming insoluble salts. Once completed, this process allows the
dye to be retained in the fabric, preserving the intended color shade through the normal
washing processes. The cationic charges in these types of polymers is often supplied by the
positive charge of heavy metal ions such as zinc. It was NICCA's strong commitment to the
environment and recognition of the value of such green chemistry that led to the develop-
ment of NEOFIX® E-l 17. NEOFIX® E-l 17 is a heavy metals free, nonformaldehyde based
fixing agent for direct and fiber reactive dyes. It significantly improves wash fastness of cellu-
losic fabrics and their blends. Unlike many fixing agents of this nature, NEOFIX® E-l 17
adds the extra benefit of helping its users comply with environmental and safety regulations
by removing occupational and environmentally hazardous compounds.
High Energy Efficiency, Environmentally
Friendly Refrigerants
For several decades chlorofiuorocarbons (CFCs) were the most widely used refrigerant
working fluids because of their nonflammability low toxicity low cost, and reasonably high
performance. Because CFCs have been implicated in stratospheric ozone depletion, their pro-
duction worldwide was stopped at the end of 1995 under the provisions of the Montreal
Protocol as amended in Copenhagen in 1992. The phaseout of CFCs and HCFCs and
increasing concern about greenhouse gases create the urgent need for nontoxic, nonflamma-
ble, environmentally safe refrigerants with high capacity and energy efficiency.
Dr. Jonathan Nimitz, President of ETEC, and his co-inventor Lance Lankford, have dis-
covered an improved family of refrigerants based on blends containing trifiuoromethyl iodide
(CF3I). The refrigerants are nonflammable, have zero ozone-depletion potential (ODP), low
global warming potentials (GWPs) and total equivalent warming impacts (TEWIs), relative-
ly low toxicity, and are more energy efficient than R-134a and R-22. Dr. Nimitz and Mr.
Lankford have formed a joint venture with the Dole Food Company, called Ikon, Inc., to
support testing and commercialization of the refrigerants. The first blend, Ikon A, has been
demonstrated for over two years in Dole Food Company refrigerated transport containers,
with excellent results. Ikon A has been approved for use under EPA's Significant New
Alternatives Policy (SNAP) program for automotive use. In a project for NASA Kennedy
Space Center (KSC), a formulation capable of higher capacity at lower operating tempera-
tures, Ikon B, was developed. Demonstration in a 1.5 ton commercial water chiller unit gave
approximately 17 percent higher energy efficiency for Ikon B versus R-134a. Testing in the
vapor compression loop at Oak Ridge National Laboratory showed approximately 25 percent
higher energy efficiency for Ikon B versus R-22. Demonstration of Ikon B will continue in
KSC chiller units.
30
-------
MRA-D, A New Wastewater Treatment Process
A breakthrough has been made in the technology of treating metal bearing wastes. Great
Western Chemical Company's MRA-D (Metal Removal Additive) Series of chemistries
allows for an improvement in the methods of printed circuit waste treatment. The most
unique feature of the MRA-D process is that is achieves very low effluent metal levels while
producing a compact, nearly dry metallic sludge high in metal content. Since the MRA-D
process produces sludge of such unusually high metals, it may be suitable for sale as a prod-
uct, rather than disposed of as a waste like other conventional industry methods. The
MRA-D process allows for true recycling of concentrated sludge from the waste of printed
circuit board facilities to finally be achieved. Printed circuit board facilities will manufacture
printed circuit boards as well as copper concentrates.
N-Methylmorpholine-N-Oxide (NMMO): a Novel,
Non-toxic, Reusable 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 strong base to produce a xanthate complex. Carbon disulfide is highly flammable and
toxic to humans as well as being a green house gas. Further, to produce fibers the xanthate
must be regenerated by extrusion into an acid coagulating bath where it decomposes and pro-
duces polluting by-products 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, but 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
Great Western
Chemical Company
TechMatch,
Incorporated
Novon International
31
-------
International
Metal izing Corporation
Solvent Kleene Inc.
Mauser, Inc.
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.
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 non toxic 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.
Non-Hazardous 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 non-hazardous cleaners have been introduced as alternatives, but few
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.
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 anti-cancer compound paclitaxel from ^few trees.
The implementation of Hauser's ozonolysis technology in the isolation of paclitaxel
32
-------
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 anti-cancer 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 percent decrease in the cost of man-
ufacturing paclitaxel.
The FIX Module Software: Combining Life Cycle
Assessment with Activity Based Costing to Preserve
the Global Environment
The project undertaken by KM Limited was successful in developing the first commer-
cially available software package tool—the LCAPIX module—to simultaneously allow the
user to perform both Activity Based Costing (ABC) and Life Cycle Assessment (LCA). By
using an industrial engineering approach employing drivers and driver values, the model and
relational database provides for a unique combination of two strategies which complement
and enhance the implementation of an Environmental Management Strategy (EMS). This
approach has strong appeal to those involved in any manufacturing sector—the point source
for more than 50 percent of "undesirable effluents" affecting our global climate.
This software tool has been used to compare different products, processes, and service for
not only their environmental burden potential (using different valuation techniques—i.e.,
selected weighted emphasis on global warming, ozone depletion, acid rain, deforestation, bio-
diversity), but also to understand how different techniques can be used to diminish these
burdens while improving internal, external, unseen, or unknown "hidden" costs. The soft-
ware tool, therefore, is multifunctional, in that it provides for inexpensive, rapid, simple, LCA
strategic or environmental comparisons of any product, process, or service; allows for addi-
tion and access of general "valuation" databases to perform environmental burden analysis
based on various methodologies; performs LCA and ABC simultaneously, not only for imple-
menting and effective EMS, but also to ensure future efficiency and profitability by detailed
cost analysis; converts LCA impact analysis information into a suitable form; allows each
LCA stage (inventory, analysis-valuation, improvement) to be performed independently;
builds a process hierarchy inventory of industrial systems, calculates process substance
amounts, and determines the process substance Environmental Load Units; and reduces con-
ventional time approaches (weeks or months) once a single process inventory is completed
(several independent calculations or "cases" can be determined in the analysis stage within
hours).
KM Limited Inc.
33
-------
Radiance Services
Company
Rynex Holdings, Ltd.
The Radiance Process: A Quantum Leap
in Green Chemistry
The Radiance Process is a novel dry non-toxic enabling technology for surface cleaning.
It employs the quantum mechanical effects of laser light in combination with an inert gas,
ordinarily nitrogen, to clean surfaces. In industries such as semiconductors, photomasks, hard
disks, flat panel displays, optics, automotive, and aerospace, current cleaning technology pre-
sents a real environmental management problem because of the lavish use of fresh water and
toxic chemicals. In semiconductor manufacturing the primary cleaning technique is the RCA
wet process. This is washing wafers in solutions of hydrochloric acid, hydrogen peroxide, and
ammonium hydroxide, rinsing in deionized water, and drying with isopropyl alcohol. The
wet cleaning process accounts for most of the 3 to 6 million gallons of water a typical semi-
conductor manufacturing facility uses each day.
The Radiance Process provides a cost-effective remedy to real environmental management
problems by replacing chemicals and water with light and an inert gas. The Process is inex-
pensive and adaptable to many manufacturing products, such as computer chips, hard disks,
flat panel displays, night vision goggles, and tire molds. Radiance is working with Motorola,
the Defense Department's Microelectronics Research Laboratory, and EPA's National Risk
Management Laboratory to demonstrate the Process, and expects to enter into up to six joint
development projects in 1998. Semiconductor International called Radiance a "break-
through." Advancing Microelectronics called it "radical." Futuretech called it
"indispensable." In December 1995, the Radiance Process was selected by IndustryWeek mag-
azine as a Technology of the Year, one of only five, calling it "revolutionary." In 1997, the
National Pollution Prevention Roundtable awarded Radiance its Most Valuable Pollution
Prevention Award, the only private sector organization to receive this distinction. Radiance
provides the ultimate Green Chemistry by eliminating toxic chemicals in cleaning while
achieving equal or superior results at a competitive or lower cost. The Radiance Process exem-
plifies a new innovative pollution prevention technology with broad based applications.
Rynex Biodegradable Dry Cleaning Solvent
In response to the recent problems associated with perchloroethylene, the primary solvent
used in the dry cleaning industry in the United States, Rynex Holdings, Ltd. has developed
an exciting new and environmentally safe and effective dry cleaning solvent that is econom-
ical to use and recycle. Rynex is the trade name for a novel dry-cleaning solvent and a method
for effective dry-cleaning. The Rynex dry-cleaning solvent is non-flammable, non-com-
bustible, biodegradable, non-carcinogenic, non-toxic, non-polluting to the water supply and
the ozone layer, recyclable, effective detergency compatible with existing dry-cleaning equip-
ment, and economical to use. The Rynex dry-cleaning solvent is superior to
perchloroethylene in it attributes and benefits. The Rynex dry-cleaning solvent has superior
cleaning abilities and does not cause shrinkage to the 160 types of fabrics and is dye-fast or
non-bleeding with respect to the 900 types of dyes. Most important is that it does not have
the problems associated with perchloroethylene and can therefore be used without serious
environmental, health, and occupational risks and problems associated with the use of
perchloroethylene. The Rynex solvent has been identified as having the advantage of
behaving like a single substance. This unique technological breakthrough brings forth
new properties that allow for the effective removal of water and oil soluble stains without
shrinkage of wool fibers that occurs with wet cleaning methods. Rynex does not suffer from
serious environmental, health, and occupational hazards and problems associated with the
use of perchloroethylene.
34
-------
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 is based on innocuous and renewable feedstocks. Arkenol's proprietary
acid hydrolysis technology produces mixed sugars from locally available lignocellulosic mate-
rials such as agricultural residues, forest residues, and municipal solid wastes. The mixed sugar
solution derived from these indigenous and low-value feedstocks is a cost effective raw mate-
rial for the production of a myriad of chemicals from fermentation or other synthesis.
Patented improvements make the acid hydrolysis commercially viable by making it possible
to economically and competitively convert feedstocks such as rice straw, sugar can bagasse,
and municipal solid wastes into ethanol and other chemicals (ethanol, for example, is pro-
duced from the Arkenol process at a cost of $0.60 per gallon compared to $1.29 per gallon
from the industry standard process).
An advanced project in Sacramento County, California will use Arkenol's technology to
divert approximately 132,000 tons per year of rice straw from open-field burning to produce
12 million gallons per year of ethanol and co-products including precipitated silica, gypsum,
and lignin. Eliminating the burning of some 60,000 acres of rice fields, will also result in sig-
nificant improvements to the region's air quality due to annual net emissions reductions of
280 tons of NOX, 173 tons of PMIO, 130 tons ofVOCs, 138 tons of SO2, and 4988 tons
of CO. In addition, significant greenhouse gas benefits from the use of renewable feedstocks
will be realized. Since the products are derived from biomass, the carbon dioxide produced
in making the products is equal to the amount taken up from the atmosphere by the growth
of the crop. As an example, the reduction of greenhouse gas emissions from the use of ethanol
produced by the biorefinery to displace fossil fuels provides a significant contribution to
reduction of "greenhouse" atmospheric pollution. Arkenol's Sacramento project reduces
greenhouse gas emissions by approximately 141,000 tons per year when the ethanol is used
in place of gasoline. Arkenol's ability to use a wide variety of feedstocks will enable placement
of near zero discharge production facilities (or bio refineries) 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. Widespread implementa-
tion of Arkenol's technology will lead to environmentally responsible and sustainable
economies relying on local resources.
Ultraviolet (UV) Curing of Small Wood Products: An
Industrial Demonstration Project
The "Ultraviolet (UV) Curing of Small Wood Products: An Industrial Demonstration
Project" relied on judicious cofunding from the New York State Energy Research and
Development Authority to finance the procurement of a compact, fully integrated spray coat-
ing/UV curing unit. Two major challenges have been met thus far: (a) the ability to down
scale a spray coating/UV curing process so that it could process the small wood products
made by E&J Industries, such as brush blocks as small as 6.3cm by 17.8cm, and (b) to do so
within the context of a small business environment, wherein personnel have limited, if any,
technical background. The sprayable UV curable coating supplied by Strathmore Products
has exhibited industry accepted performance while completely eliminating the use of solvent
coating systems in E&J Industries' production operation. Production rates as high as 80
meters/minute have been attained in the spray coating/UV curing process with complete
Arkenol, Holdings, L.L.C.
E&J Industries,
Incorporated
35
-------
AMSOIL Incorporated
lonEdge Corporation
recycling of overspray. Dialogue has begun with another small wood products manufacturer,
a producer of the walnut backing used for plaques and trophies, in order to initiate technol-
ogy transfer to similar small businesses. Additional interest has been shown by a major
manufacturer to use this process to apply an insulating coating to the torroidal ferrite-ceram-
ic cores used in motors and bushings that have dimensions as small as 1.3cm in height and
1.9cm in circumference.
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. However, used oil generated by
households is currently disposed of improperly at an alarming rate nationally; 220 million
gallons per year as estimated by the U.S. Department of Energy.
In 1972, AMSOIL Inc., introduced the first 100 percent synthetic motor oil to meet
American Petroleum Institute service requirements, passing performance testing for gasoline
fueled consumer passenger vehicles. AMSOIL Inc. has since developed synthetic oil formu-
las 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 analysis program. AMSOIL Inc. also manufactures extended life, premium grade lubri-
cation and related products for commercial and industrial applications, including hydraulics,
compressors, gears, and Diesel engine power plants. The scope of AMSOIL lubricating prod-
ucts' ability to provide uncompromising engine and machine wear protection, while reducing
the volume of waste oil generation. Synthetic oil basestocks are comprised of well defined par-
ticular molecule types that can be designed for specific performance characteristics. One
distinct advantage over crude petroleum is that they can be "tailor made" to fit the require-
ments of the application. The uniform molecular structure of synthetic oil basestocks reduces
the lubricant volatility (aromatic boil off) in extreme heat, which in turn reduces oil con-
sumption. With long drain synthetics, the average American can use 75 percent 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. However, cadmium is a known toxic material and 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
36
-------
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 percent 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.
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 content, 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 environmental 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 not only eliminate significant solvent use for environmental, health, and safety con-
cerns. It is particularly satisfying that it eliminated hazardous materials in this area of
aerospace manufacturing that EPA had exempted from its regulation because of the absence
of available 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
-------
IMC-Agrico Company
American Air Liquid
Entries from Industry
and Government
AGROTAIN® N-(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 percent in 1962 to 37 percent in 1986 for urea. There
are many reasons for this increase. Urea is a source of nitrogen for crop fertilization that is
easily handled and transported, higher in nitrogen content than other common solid nitro-
gen fertilizers, and can be readily bulk blended with other fertilizer components such as
potassium chloride, diammonium phosphate, and other materials to prepare multi-nutrient
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 percent of the available nitrogen in urea under certain climatic and soil
conditions.
AGROTAIN® is a formulation containing N-(n-butyl) thiophosphoric triamide (NBPT)
the precursor to the active ingredient, N-(n-butyl) phosphoric triamide (the oxygen analog
of NBPT). BNPO is far too unstable to be an article of commerce. NBPT serves as an effec-
tive 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
NBPT treatment rate is only 0.4 Ibs/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, Cp4, Np3, CHF3, SFg, and C3pg 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 life time 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 dollars. This amount could be double by the year 2000. The U.S. gov-
ernment 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 choices for addressing the immediate emission reduction: (1) abating these
gases at considerable financial and environmental cost and (2) recycling of PFCs developed
by Air Liquid. Air Liquid has developed a system to capture these gases from process exhaust,
to further concentrate, purify, and recycle. This process went through a rigorous qualification
test under the umbrella of SEMATECH, demonstrating both capturing and concentrating
the PFCs above 95 percent. In summary, this technology improves the environment by
38
-------
reducing PFC emissions that are part of 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 non-aqueous liquid hazardous waste has tra-
ditionally 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 5 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 comparison
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 calibra-
tion. Also, the frequency of preparing and running standards is much less than traditional
techniques because of the inherent stability of EDXRF systems. It is an environmentally-
friendly technique because it virtually eliminates the generation of hazardous lab waste.
Application of Freeze Drying Technology to
the Separation of Complex Nuclear Waste
The nuclear industry must comply with increasingly stringent Standards for radioactive
material levels present in liquid effluents. Current conventional methods of decontamination
include distillation, ion exchange, precipitation reactions, or chelating agents. Freeze drying
technology (FDT) has been applied to the decontamination of radioactive liquids and shown
to be thousands of times more effective than conventional methods. Distillation, ion
exchange, and chelating agents often require multiple passes, and because additional compo-
nents (resins or chelating agents, which in turn must be disposed as radioactive) are typically
needed by these methods, reductions in the volume of radioactive waste are rarely realized.
FDT will efficiently separate solvents and volatile acids from complex waste solutions and
process liquids. The separated liquids will be virtually free of radioactive contamination and
can be re-used or discarded as nonradioactive. FDT will drastically reduce the volume of
radioactive wastes. Volume reductions greater than one thousand times have been achieved
in aqueous solutions, but the exact volume reduction of nuclear waste will depend on its
moisture content. FDT will eliminate the need for storage or destruction of the liquid com-
ponent and will lower transportation costs because of volume and weight reductions. In
addition, this technology can be considered safe; no high temperatures or pressures are used.
The process occurs in a vacuum, so the failure of a component would lead to an inward leak
and the potential for contamination outside the system is significantly reduced. Finally, the
refrigerant used in this technology is environmentally friendly liquid nitrogen.
American Society for
Testing & Materials
(ASTM)
Los Alamos
National Laboratory
39
-------
Asarco Incorporated
Union Camp Corporation
Asarco - West Fork Biotreatment Project
Asarco has developed a biotreatment system for removing metals from mine water prior
to its discharge to surface waters. Asarco's West Fork Unit is an underground lead-zinc mine
that discharges water from mine dewatering to the West Fork of the Black River under
NPDES permit. Recent changes in the Water Quality Standards required Asarco to explore
water treatment alternatives. Asarco initiated passive biotreatment investigations in 1993
which lead to the design and construction of an anaerobic pilot biotreatment cell (biocell) in
February, 1994. The biocell (designed to treat 20 gallons of water per minute) was filled with
a substrate mixture of 50 percent old sawdust, 33 percent mine tailings, 10 percent cow
manure, 5 percent alfalfa hay, and 2 percent lime rock (all material used was obtained local-
ly; other organic materials such as yard waste and sewage sludge can be substituted). Sulfate
Reducing Bacteria (SRB) were cultivated within the anaerobic environment of the substrate.
SRB are abundant in nature and are found predominately in bogs and swamps. SRB produce
hydrogen sulfide gas as a byproduct that acts as a sulfiding agent to precipitate dissolved lead
and other metals from mine water. The pilot biocell has demonstrated continued success in
reducing metals from mine water to below Missouri's Water Quality Standards. The biotreat-
ment cell operated efficiently through extremes of ambient temperature, water flow rates, and
metal loading. Unlike conventional chemical water treatment plants, a biotreatment cell does
not require the introduction of chemicals into the water, does not produce sludges on a daily
basis that must be disposed, does not require a full time operator, is not subject to mechani-
cal malfunction, can operate at twice the design rate for short periods of time without a
reduction in treatment efficiency, and can be constructed at a fraction of the cost.
C-FREE™ Pulp Ozone Bleaching Project
For decades, ozone has been acknowledged as the most promising alternative to chlorine
in the bleaching of wood pulp in the forest products industry for the protection of our envi-
ronment. Despite this recognition, no satisfactory technology was commercially available
that met both cost and quality criteria of pulp producers until the early 1980s. Union Camp
Corporation, a world leader in pulp and paper production, embarked on a research and
development program to solve the problems identified with ozone delignification, including
the erection and operation of a $6 million, 25 TPD pilot plant. Based on the results of its
R&D and pilot plant studies, Union Camp became convinced that an environmentally
friendly bleaching process could be developed on a commercial scale. The result was the full
scale implementation of the world's first high consistency ozone OZ(EO)D bleach line
for kraft pine pulp in Union Camp's Franklin, Virginia, fine paper mill during the fall of
1992. The ozone pulp bleaching process is patented under the trade mark C-Free™. While
the C-Free™ pulp bleaching technology has significantly lower bleaching costs at equivalent
product quality compared to conventional chlorine based bleaching, the most important
benefit is the significant reduction in effluent properties, volume and fresh water require-
ments. The effluent Biological oxygen demand (BOD), chemical oxygen demand (COD),
color, absorbable organic halides (AOX) and chloroform have been reduced by 73 percent,
83 percent, 98 percent, 99 percent, and 99 percent respectively compared to conventional
chlorine CEDED bleaching. In addition, dioxin and the 28 chlorophenols identified by the
EPA are nondetectable.
40
-------
The Chemical Kinetics Simulator Program
Computer simulators offer a powerful means of minimizing waste generated through
physical experimentation during process development and optimization, a waste stream not
usually addressed in green chemistry programs. The potential impact of simulations will not
be realized, however, unless 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 in IBM for 3 years for process research and development. Since May 1996, the package
has been available globally for a no-cost license through the World Wide Web and is used in
many other industries for process research and development because of its exceptional ease-
of-use and functionality. It also has been frequently licensed by environmental researchers in
universities, corporate and government laboratories, and environmental regulatory agencies
to develop models and evaluate hazards.
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 percent magnesium (Mg). Because the specifications for
most diecast aluminum alloys call for a Mg level of less than 0.1 pet Mg, the charge must be
demagged. The excess Mg is removed through the addition of chlorine (CbJ gas, or occa-
sionally through the addition of A1F3. Most of the demagging reaction schemes use C^ and
in practice require 6 Ibs. of C^ gas to remove 1 Ib. of Mg as MgCl2 (approximately 4500 Ibs.
Cl2 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 which 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 C^ 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 (Li2Ti3O7) 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.
IBM Research Division,
Almaden Research
Center
Albany Research
Center, U.S. Department
of Energy
41
-------
U.S. Bureau of
Engraving & Printing
BetzDearborn, Inc.
Designing a Safer, Less Toxic, Less Pollutant and
Environmentally Friendly Solvent-ISOMET
The U.S. Bureau of Engraving and Printing (the Bureau), the world's largest security
manufacturing establishment, produces currency, postage stamps, revenue stamps, natural-
ization 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 presses. Typewash is a solvent mixture composed of methylene chloride (55
percent), toluene (25 percent), and acetone (20 percent). 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 hydrocarbon (55 percent), propylene glycol monomethyl ether
(10 percent), and isopropyl alcohol (35 percent). Isomet is less toxic, less polluting, and envi-
ronmentally 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 environ-
mentally friendly. The performance of Isomet is excellent and it has been used for cleaning
all postage stamp and overprinting presses in the Bureau.
Designing an Environmentally Friendly Copper
Corrosion Inhibitor for Cooling Water Systems
Copper alloys are widely used in industrial cooling systems because of their good heat
transfer qualities. However, unless they are protected by an inhibitor, copper alloys will cor-
rode in cooling systems. This corrosion produces extremely toxic copper compounds which
are then released into the environment. Azole materials are the best available copper corro-
sion 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 which is not protective to copper. When corrosion protec-
tion is lost, TTA feed rates are usually increased in an attempt to overcome the reaction with
chlorine 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) which 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 which was utilizing chlorine for MB control. HRA was
compared 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 fivefold decrease in the amount of copper released to the envi-
ronment, compared to TTA. In addition, substantially lower concentrations of HRA are
required for copper alloy protection compared to TTA. Furthermore a mass balance showed
that only 9 percent of the TTA was recovered compared to 90 percent of the HRA. The TTA
loss was due to the reaction with chlorine and the formation of a chlorinated azole. Since
HRA does not react with oxidizing biocides, considerably less chlorine or bromine is required
for prevention of MB activity, resulting in lower amounts of chlorine- or bromine-contain-
42
-------
ing compounds being released in discharge waters. A reduction in chlorine usage of 10 to 20
percent was observed at the above nuclear power plant, and a reduction of 36 percent was
observed at another industrial site. 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.
Designing Safer Chemicals: Spitfire Ink
As the information age enters 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 ten 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, solvent, etc.) are rapidly progressing to the extent that traditional printing
technologies 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 printing 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 print-
ing processes associated with the well defined, centuries old printing methods, (e.g. offset,
fiexography, gravure, letterpress).
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 non-reusable consumables. The traditional
printing 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
regulations 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.
Development and Implementation of Low Vapor
Pressure Cleaning Solvent Blends
Lockheed Martin Tactical Aircraft Systems (LMTAS) (formerly General Dynamics Fort
Worth Division) has developed low vapor pressure organic solvents. LMTAS patented these
solvent blends and the technology is being used by the aerospace industry, the military, and
various industries. Additionally LMTAS substituted one of the new solvent blends (DS-104)
for a CFC-113 based general purpose cleaning solvent used in the surface wiping of aircraft
parts, components, and assemblies in all aspects of aircraft manufacturing. The substitution
resulted in major reductions in solvent use and air emissions, the elimination of ozone deplet-
Tektronix, Inc.
Lockheed Martin
Tactical Aircraft
Systems
43
-------
ing compounds from cleaning during aircraft assembly, cost reductions, and improved chem-
ical handling and usage practices.
From 1986 to 1992, LMTAS produced mainly F-16 fighter aircraft at a rate of 220 to
350 aircraft per year. Throughout the 6 years, LMTAS used a general purpose wipe solvent
containing 85 percent CFC-113 by weight throughout the manufacturing process. The use
of the CFC-113 solvent blend resulted in the emission of approximately 255 tons per year of
CFC-113 and 45 tons per year of volatile organic compounds (VOC) The implementation
of DS-104 at LMTAS has reduced wipe solvent VOC emissions to 7 tons per year in 1993,
3 tons per year in 1994, and 2 tons per year in 1995, with no CFC emissions. Cost savings
plus cost avoidance have been documented at $0.95 million for 1993 and $1.3 million for
1994. LMTAS management recently estimated the cost savings from the wipe solvent imple-
mentation to be $8.2 million for the five year period of 1993 to 1997.
After the LMTAS implementation, other companies and military operations throughout
the United States have implemented this technology. Additionally, this technology has been
implemented in several countries, such as Australia, Canada, Greece, Israel, Mexico, the
Netherlands, South Korea, Taiwan, and Turkey. Several other European countries will imple-
ment this technology in 1997. These cleaners were developed primarily for aerospace;
however, they have found cleaning applications in many industries such as: automotive, bub-
ble gum removal in movie theaters and universities, various ink removal industries, postal
operations, electronics, building maintenance, steel industry, and nondestructive testing
methods. EPA has recognized this technology in the Aerospace National Emission Standard
Hazardous Air Pollutants and the proposed Aerospace Control Technology Guideline
Rochester Midland
Corporation
Development of a New 'Core' Line of Cleaners
Cleaning is an important practice and necessity of modern civilization. An effective clean-
er must be able to penetrate through soil to disrupt and destroy the complicated types of
bonding that cause it to adhere to the surface being cleaned. Most modern cleaners are com-
prised of surface active agents derived from petrochemical resources. While these components
are effective, they tend to be environmentally harsh and depend upon a natural resource
whose supply is finite and limited. The market for these products is estimated to be in the
range of $5 billion, which equates to approximately 5 billion pounds of product annually.
The impact of developing chemistries that are less polluting during the extraction, manufac-
turing, use, and disposal of these products is, therefore, quite significant, as are the human
health and safety impacts.
During the past few years a new family of cleaners was developed that are less toxic and
have reduced impacts to both people and the environment when compared to traditional
products used for the same purpose. The chemistries incorporated into these products result-
ed in products that are readily biodegradable, comprised of zero to very low volatile organic
components and ozone depleting substances, effective in their intended purpose (i.e., clean-
ing), and economically competitive. In addition, these products have low human and aquatic
toxicity and low corrosivity. Main molecular components of these products are derived from
renewable, bio-based resources that are lower polluting and typically less toxic than their
petrochemical alternatives. This new 'core' line of cleaners is an innovative approach to the
formulation of an important series of products and is the safest yet developed in its field.
44
-------
DuPont Petretec Polyester Regeneration
Technology—Making Polyester Evergreen
Thirty-five billion pounds of polyethylene terephthalate polyester (PET) are produced
globally each year. PET goes into thousands of end uses and it is also the "greenest" of the
polymers. Due to this polymer's inherent thermal stability, PET-type thermoplastics lend
themselves to direct recycling and serve as a raw material for the production of numerous
products. The success of PET bottle recycling, for example, annually diverts more than 600
million pounds of PET bottles per year from landfills. This recycling technology, however,
requires high-purity waste and the recycled material generally may only be used for carpeting
or pillow fibers. There are a large number of uses for virgin PET where the material has been
dyed, coated, or mixed with a co-polymer and therefore is not suitable for direct recycling.
This material is landfilled.
The patented DuPont Petretec™ polyester regeneration technology provides an environ-
mental and economical alternative to landfills and offers many advantages over recycling.
Petretec™, DuPont's proprietary form of methanolysis, makes polyester evergreen. The
process provides a safer and more economical way to reuse materials, especially those with
much higher contaminant levels than other recycling methods. It takes PET fibers, films, and
resins currently going to landfills, unzips the PET molecule, and breaks it down into its raw
materials, dimethyl terephthalate (DMT) and ethylene glycol (EG). The Petretec™ process
allows these raw materials to retain their original properties so they can be reused over and
over again in any first-quality application. The process accepts polyester with a broader vari-
ety of contaminants and at higher levels than any other process. Petretec™ reduces
dependence on oil-derived feedstocks and diverts polyester from the solid-waste stream into
useful new products.
DuPont invested $12 million to convert part of its Cape Fear facility, near Wilmington,
North Carolina, to a methanolysis plant. The new plant can handle more than 100 million
pounds of scrap PET and capacity is easily expandable. By actually unzipping the molecules,
we can begin the cycle of using these materials in an endless series of new applications.
Elimination of Ozone-Depleting Chemicals
(ODCs) Through the Use of a Water Soluable
Adhesive "Green Wax"
The process operations involved in manufacturing polished silicon wafers include silicon
crystal growth and wafering. Crystal growth refers to process steps to convert polycrystalline
silicon into single crystal ingots (also called silicon rods). The crystal growth process is care-
fully controlled to produce silicon rods meeting different electrochemical properties specified
by customers. Wafering refers to process steps to slice silicon rods into wafers
and to prepare the wafer surface for microchip manufacturing by customers. The final
polished silicon wafer must meet exacting standards for flatness, chemical purity, and surface
cleanliness. An epitaxial layer of silicon is added to the surface of some polished wafers
to produce premium product required for microprocessors and logic devices.
In 1992, MEMC Electronic Materials, Inc., a silicon wafer manufacturer, began investi-
gating ways to eliminate all Class I Ozone Depleting Chemicals (ODCs) from
manufacturing operations. Over 80 percent of the target ODCs used by MEMC were in
direct silicon processing steps like slice mounting, polishing, slice demounting, and slice
dewaxing. The mounting of silicon slices prior to polishing was performed with a material
known as "wax" which was capable of controlled viscosity and thickness application. The old
DuPont Polyester
MEMC Electronic
Materials, Inc.
45
-------
Pharmacia & Upjohn
wax formulation contained trichloroethylene (TCE), while the old block cleaning method
utilized 1,1,1-trichloroethane (TCA), and the old slice dewaxing process utilized Freon 113.
The wax formulation was changed to a water soluble one ("green wax"), that utilized a com-
mercially available water soluble resin (a modified maleic resin in solution with ammonium
hydroxide and water). Slice mounting (block cleaning) and dewaxing were modified to use a
dilute basic solution (such as ammonium hydroxide) instead of TCA and Freon 113. The
flatness, particle count, and metal concentration of slices produced with green wax are equal
to or better than the old wax. It is estimated that, since 1993, MEMC has avoided the pro-
duction of almost 5 million pounds of ODC emissions worldwide through the use of green
Environmental Improvements from Redesigning the
Commercial Manufacture of Progesterone
For more than 40 years, the steroid bisnoraldehyde (BNA) has been produced at
Pharmacia & Upjohn because it is a key intermediate for the commercial synthesis of prog-
esterone and corticosteroid classes of pharmaceuticals. Recently, a redesigned route to BNA
was implemented. This new synthetic route to progesterone is founded on both the devel-
opment of a new fermentation process which improves the utilization of a renewable,
naturally derived feedstock from 15 to 100 percent, and the development of a chemical
oxidation process that offers high selectivity and reduced waste streams. The fermentation
employs a genetically modified bacterium to convert soya sterols directly to a new synthetic
intermediate, bisnoralcohol. The new chemical process oxidizes bisnoralcohol (BA) to bisno-
raldehyde, a key intermediate for the registered, commercial manufacture of progesterone.
Contrary to standard chemical methods for oxidizing alcohols to aldehydes, the new oxi-
dation process does not use hazardous or noxious materials and does not generate toxic waste
streams. The reaction conditions developed to oxidize BA to BNA are environmentally supe-
rior to the standard methods used to convert primary alcohols to aldehydes. During the
development of the process, considerable focus was placed on waste minimization, not just
for that step but also for the production of the substrate and the catalyst. The process min-
imizes solvent use and maximizes solvent recovery as well. The new bisnoralcohol route
eliminated a process with a running, recycled inventory of 60,000 gallons of ethylene dichlo-
ride (EDC), a known carcinogen, which needed up to 5,000 gallons of EDC input annually.
The new route produces the same amount of product as the previous route with 89 percent
less nonrecoverable organic solvent waste and 79 percent less aqueous waste. The new route
also has the chemical selectivity required for high quality bulk pharmaceutical manufacture
and can be applied to the oxidation of other primary alcohols.
The development and implementation of the new chemical oxidation process allowed for
the utilization of the new bioconversion, thereby creating a new synthetic route from soya
sterols to therapeutic steroids. The new bisnoralcohol route exemplifies the synergism possi-
ble between biochemical and chemical process development. By implementing this
redesigned, commercial synthesis of BNA, Pharmacia & Upjohn has substantially reduced
the chemical waste associated with manufacturing progesterone, while simultaneously
improving process economics through a dramatic increase in feedstock utilization.
46
-------
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 which employ organic solvents or catalysts requiring post reaction
disposal. 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 CC>2 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 synthesis for producing monoglyceride-containing mixtures via
glycerolysis, that employ CC>2, 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 percent that have high value as
emulsifiers, lubrication aids, and food additives. Using carbon dioxide under pressure, we
have shown that 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 a mono-
glyceride content between 35 to 45 weight percent, depending on botanical oil source.
Alternatively, the National Center for Agricultural Utilization Research has demonstrated
and patented a synthesis which uses CC>2 in the supercritical state to dissolve vegetable-based
oils prior to transport over a supported enzyme catalyst which also affects glycerolysis, but
depending on variables such as CC>2 flow rate and the water content content of the starting
reactants, can yield designer glyceride mixtures having a variable monoglyceride content
between 50 to 90 weight percent. Finally, by coupling one of the two CCvbased synthesis
processes with a thermal gradient fractionation column, it is possible to utilize a totally envi-
ronmentally benign process for the production and enrichment 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 percent 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
National Center for
Agricultural Utilization
Research
Nalco Chemical
Company
47
-------
Lawrence Livermore
National Laboratory
U.S. Department of
Defense, Office of
Munitions
U.S. Department of
Energy, Weapons
Supported Research
U.S. Army Edgewood
Research, Development,
and Engineering Center
using an aqueous salt solution as a reaction medium instead of oil and surfactants. These
dispersions are completely water soluble and are very easily dissolved in water. They contain
almost zero volatile organic contents and eliminate the environmental and health hazards
associated with the respective emulsion and dry polymer forms.
Environmentally-Driven Preparation of
Insensitive Energetic Materials
The Vicarious Nucleophilic Substitution (VNS) of hydrogen is a well-established proce-
dure for the introduction of carbon nucleophiles onto electrophilic aromatic rings. An
innovative approach was developed at Lawrence Livermore National Laboratory to synthe-
size l,3)5-triamino-2,4,6-trinitrobenzene (TATB) and other insensitive energetic materials
through the use of VNS. TATB is a reasonably powerful insensitive high explosive (IHE),
whose thermal and shock stability is considerably greater than that of any other known mate-
rial of comparable energy. The high cost of TATB ($100 per pound) has precluded its use for
civilian applications such as deep-hole explorations. TATB is manufactured in the United
States by nitration of the relatively expensive and domestically unavailable 1,3,5-
trichlorobenzene (TCB) to give 2,4,6-trichloro-l,3,5-trinitrobenzene (TCTNB), which is
then animated to yield TATB.
The new VNS method developed at Lawrence Livermore National Laboratory for the
synthesis of TATB has many 'environmentally friendly' advantages over the current method
of synthesis of insensitive energetic materials. The new synthesis of TATB uses unsymmetri-
cal dimethylhydrazine (UDMH), a surplus propellant from the former Soviet Union, and
ammonium picrate (Explosive D) as starting materials in lieu of the chlorinated species, TCB.
Several million pounds of Explosive D are targeted for disposal in the United States; 30,000
metric tons of UDMH also await disposal in a safe and environmentally responsible manner.
The use of these surplus energetic materials as feedstocks in the new VNS method of syn-
thesizing TATB allows an improved method of demilitarization of conventional munitions
that also should offer significant savings in production, thereby making this IHE more acces-
sible for civilian applications.
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 Egdewood 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-
48
-------
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.
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 which 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 percent 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 that 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, eliminates the emission of massive amounts of greenhouse gases,
while greatly reducing the production of organic wastes.
Solutia Inc.
49
-------
Ciba Specialty
Chemicals Corporation
Mallinckrodt Baker Inc.
Imation Corporation
Heavy Metal Free Alternative to Standard
Anti-Corrosive Pigments
The coatings industry in the United States has had to focus their efforts to develop prod-
ucts which are compliant with an ever expanding set of federal, state, and local regulations,
all designed to reduce or eliminate materials which pose a threat to either human health and
safety or more broadly, environmental safety. The Irgacor family of organic corrosion
inhibitors was designed and developed specifically to replace the standard anti-corrosive
pigments which are based on heavy metals such as lead, chrome, zinc, strontium, and bari-
um. These heavy metals are classified as being harmful to humans and/or the environment.
In addition to toxicity generally associated with heavy metal-based anti-corrosive 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) .The volume of Irgacor necessary to replace the 11.0 million pounds will only
be 2.0 million pounds. In addition, if Irgacor can further stimulate the replacement of sol-
vent based systems with waterborne coatings in the maintenance, auto refinish, and marine
markets by 20 percent, 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 organ-
ic corrosion inhibitors provide both long term anti-corrosive 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,
higherVOC products.
Hydrogen Sulfide Elimination From the Substances
Not Precipitated by H2S Test
Mallinckrodt Baker has developed a method that eliminates hydrogen sulfide from the
substances not precipitated by HjS 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
plated precoated with photoactive polymers did not enter volume production until the
1950s. Availability of these presensitized plates fueled rapid growth in the lithographic print-
ing industry due to superior print performance and economy. When a conventional
presensitized plate is exposed to ultraviolet radiation through a contact masking film, forma-
tion 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 dis-
solved 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
50
-------
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 many regions of the United States. In addition, more than 1.2 bil-
lion 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, their 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 rollup 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 re 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.
Implementation and Verification of Aqueous,
Alkaline Cleaners
Lockheed Martin Tactical Aircraft Systems (LMTAS) was the first aerospace company to
implement innovative aqueous cleaning technology for cleaning tubing and honeycomb core.
Tubing is used in the aerospace industry for transferring pressurized oxygen within an aero-
space vehicle. Honeycomb core is used in the aerospace industry for producing bonded
structural parts. Both applications require that the parts meet stringent cleanliness require-
ments. These requirements were previously met by using cold cleaning or vapor degreasing
with chlorinated solvents. These solvents included 1,1,1-trichloethane (TCA) and
trichloroethylene (TCE). These chlorinated solvents are toxic, and TCA is an ozone deplet-
ing compound. The use of chlorinated solvents posed a threat to the environment because
the solvents were commonly released into the air during cleaning operations and because the
likelihood of a spill during their use was significant.
These solvents were successfully replaced with aqueous cleaning technology at LMTAS.
As of November 1993, 100 percent of tubing manufactured at LMTAS (including oxygen
tubing) is being cleaned in an aqueous cleaning system. As of May 1994, 100 percent of all
honeycomb core used at LMTAS is also being cleaned in an aqueous cleaning system.
Implementation of aqueous cleaning technology at LMTAS has eliminated approximately
360 tons of air emissions per year and has resulted in a cost savings of $490,000 per year. In
addition to replacing chlorinated solvents with the innovative aqueous cleaning technology,
LMTAS has also explored the use of environmentally safe methods for quantifying surface
contaminants on parts cleaned by various cleaning technologies. Traditionally, extraction
with CFC-113 followed by gravimetric or FTIR analysis has been used for quantifying sur-
face contaminants. The use of CFC-113 is undesirable due to its ozone depleting potential.
LMTAS has demonstrated the usefulness of carbon dioxide coulometry for determining the
amount of residue remaining on a surface after cleaning and has used this technique for com-
paring the cleaning effectiveness of various cleaning technologies.
Lockheed Martin
Tactical Aircraft
Systems
51
-------
DuPont Company
Praxair, Inc
The INFINITY Process
The INFINITY dyeing process was developed as an alternative method to manage the
dyeing cycle for nylon textiles. Over 8 billion pounds of nylon textiles are consumed each
year and most are dyed to meet aesthetic and functional demands. In the United States alone,
consumption of dyes for nylon exceeds 30 million pounds, much of which is left in the spent
dye bath after the fabric is dyed. This waste must be treated to avoid pollution of downstream
waterways. Mills are meeting regulatory requirements through conventional process control
techniques and end-of-pipe treatment, The INFINITY dyeing process lets mills reduce their
consumption of dyes and other chemicals by 25 percent, and, in some applications, water
and steam use per dye cycle is cut in half. Conventional methods use up to 4,000 gallons of
water, 20 pounds of dye, and 10 pounds of dye assist chemicals per 1,000 pounds of fabric.
The INFINITY dyeing process uses only 75 percent of the dye previously required, half the
water, and less dye assist chemicals to get the same fabric color. In addition, dye discharge
into mill effluent streams can be reduced as much as tenfold. A mill with a 90 percent exhaust
rate may discharge 500 pounds of unused dye into the mill's wastewater treatment stream
each week. With INFINITY, the same mill can move to 99 percent exhaust, reducing the
amount of dye discharged to 50 pounds per week; a significant step toward attacking waste
at the source. The process is currently being used at nylon textile mills in the United States,
and work has begun on the feasibility of using the process on wool, cotton, and polyester
blend fabrics. Cost savings by most mills using this process could easily exceed $100,000
per year.
Liquid Oxidation Reactor (LOR)
Praxair, Inc. has developed a unique process that allows the safe oxidation of organic
chemicals with pure or nearly pure oxygen. This technology, known as the Liquid Oxidation
Reactor, (LOR), provides significant environmental advantages compared to conventional,
air-based oxidation processes. The use of oxygen in place of air reduces the total gas through-
put to the reactor, thereby reducing the compression energy and the amount of vent gas that
must be treated prior to atmospheric release. In addition, the oxygen use can positively affect
the chemistry of the reaction, allowing the operation of the process at lower temperatures or
pressures, thereby improving selectivity without sacrificing production rate. The use of the
Praxair LOR increases the overall rate of reaction and volumetric productivity of hydrocar-
bon oxidations while increasing selectivity and reducing the loss of solvent and reactant to
carbon oxides. The increased chemical efficiency with oxygen results in substantial raw mate-
rials cost saving, and a 96 percent reduction in the quantity of waste gases. The cost of
product purification and waste disposal is reduced substantially. In addition, the lower
temperature operations afforded by the LOR process reduces the loss of reactant or solvent
to byproducts and to waste streams that also can contribute to environmental problems and
must be treated prior to release. The LOR will enable a large and important segment of the
U.S. chemical industry to realize more efficient use of raw materials, reduced environmental
emissions, and energy saving. Because the LOR also allows for higher productivity, lover
capital costs, and, consequently, improves competitiveness, there are significant incentives for
the implementation of the technology. Average operating-cost savings and productivity gains
worth $5 to $20 million per plant per year have been projected.
52
-------
Magnetic Separation for Treatment of Radioactive
Liquid Waste
High gradient Magnetic Separation (HGMS) is the application of intense magnetic
fields to selectively separate solids from other solids, liquids, or gases. The HGMS process
has demonstrated promise for the treatment of waste streams containing actinide at Los
Alamos National Laboratory (LANL). The caustic liquid waste generated by operations in
the LANL Plutonium Processing Facility (TA-55) can produce up to 30,000 L of liquid
effluent annually, with an average alpha activity of 1010 dpm/L. Treatment and disposal of
the liquid effluents at the LANL Waste Water Treatment Facility (TA-50) can ultimately
produce up to 15 tons of TRU solid waste per year. In order to avoid the TA-50 treatment,
the goal at TA-55 is to reduce the radioactivity in the waste streams to less than 5.8 x 105
dpm/L.
Physical separation processes, such as HGMS , are particularly attractive because no
additional waste is generated during processing. HGMS is capable of concentrating the
actinides in process waste streams to form a low volume, actinide-rich stream for recycling,
and a high volume, actinide-lean stream for direct discard. The proposed technology has
been demonstrated successfully on a laboratory scale at TA-55 where results from screening
experiments on radioactive caustic liquid waste water indicate that over 99.9 percent extrac-
tion of Pu activity can be achieved using HGMS (represents decontamination levels of three
orders of magnitude to about 4.4 x 105 dpm/L). The application of this technology to
radioactive liquid waste effluents would eliminate radioactivity from the source, in addition
to reducing the volume of transuranic solid waste that is produced with the current treat-
ment technologies. The hazard of pumping radioactive liquid waste to offsite facilities
would also be eliminated because treatment of TA-55 effluent would occur prior to trans-
portation.
Molyphos: A Chromate-Free Alternative for Corrosion
Protection of Metal Parts
For over forty years, metal fabricators have used a yellow chromate coating for the cor-
rosion protection of metal parts and for electromagnetic shielding protection. While this
coating has been a very successful corrosion preventative, it has a serious drawback—it uses
hexavalent chromium, a known human carcinogen. Metal finishing for corrosion resistance
is a significant source of chromium waste generation and emissions to the environment and
a danger to worker and public health. The Toxic Release Inventory reported over 2 million
pounds (1000 tons) of chromium and chromium compounds generated or released from
metal finishing facilities with an average of approximately 15,000 pounds (7.5 tons) report-
ed per facility in 1993. Additionally, the electromagnetic interference (EMI) protection
provided by yellow chromate is proving inadequate for today's higher speed electronic appli-
cations.
Nortel (Northern Telecom) developed an alternative to the use of hexavalent chromium
for the corrosion protection of metal parts. The new technology—a molybdenum-phos-
phate (Molyphos) based conversion coating—replaces the chromate conversion technology
(yellow chromate). In 1997, Nortel successfully applied the Molyphos technology in tests
and commercial production of several of its telecommunications products. Molyphos tech-
nology achieves multiple environmental benefits. First, and most importantly, hexavalent
chromium is eliminated as a raw material in the metal coating process, resulting in a safer
work environment and the reduction in hazardous emissions and wastes. Second, Molyphos
Los Alamos
National Laboratory
Nortel Technology
-------
Dupont Company
Nalco Chemical
Company
alleviates the internal stresses of zinc plating, which allow Nortel to replace cyanide-based
zinc electroplating with an alkaline process. Third, the superior electrical conductivity of
Molyphos coatings, compared to chromate conversion coatings, allows Nortel to eliminate
the beryllium copper gaskets and the tin-lead precoat required to achieve continuous con-
ductivity in some applications further reducing toxicity. For one product, the Spectrum/I
Link, Nortel will reduce the lead content of the system by 770 pounds annually. In addi-
tion, removal of this processing step and associated costs is expected to result in a 70 percent
cost savings. Fourth, for end-use applications that require painting, Molyphos allows the use
of powder paints, rather than liquid volatile organic content-based paints required by chro-
mate-coated products.
NAFIONMembrane Technology
Membrane technology is now recognized as state-of-the-art for chloralkali chemical pro-
duction, which constitutes the second largest commodity chemical volume produced
globally. NAFION membranes are acknowledged as the world leader in bringing about a
technology 'revolution,' which has made the membrane electrolyzer system the technology
of choice over the incumbent mercury amalgam cells and asbestos diaphragm electrolyzers.
While significantly reducing the environmental impact of the old technologies, membrane
systems confer the advantages of a new electrolysis process with lower investment and lower
operating costs. Before NAFION and membrane technology, the production of chloralkali
chemicals was dependent on either mercury amalgam cells or asbestos diaphragm systems.
Wile these systems might be operated safely, they pose health and environmental concerns in
use and disposal. Membranes, such as NAFION, now offer a more environmentally friend-
ly and economically attractive alternative, which accounts for the rapid global adoption of
membrane technology. Another rapidly emerging application of NAFION is in the area of
alternative energy, where electricity is produced from the 'combustionless burning' of hydro-
gen with oxygen in air via a membrane fuel cell. Fuel cell technology, with hydrogen as a fuel,
is pollution-free. NAFION membranes often are cited in the many commercial develop-
ments of membrane fuel cell systems. As membrane fuel cells mature in the commercial mass
market, more global energy needs will be served by renewable, sustainable, and environmen-
tally friendly sources of power.
Nalco Fuel Tech NOXOUTProcess
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 major "primary"
pollutant, and reducing it directly reduces acid rain, particulate matter less than 2.5 microns
in diameter, "greenhouse" gases and mitigates nitrogen eutrophication sensitive watersheds.
NOX also is a precursor in the formation of ground level ozone which, along with NOD 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., ambi-
ent air ozone levels exceed 120 parts-per-billion (ppb). High ozone levels are linked to many
forms of respiratory 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
welfare. 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 NOx-
OUT® process provides an economical solution for complying with the stringent regulatory
54
-------
requirements for NOX reduction from fuel combustion sources. NOxOUT® can reduce NOX
emissions by 75 percent compared to the 20-50 percent reduction from existing treatment.
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 SARA (Superfund Amendment and Reauthorization Act)
Title III chemicals, and increased energy efficiency.
Nalco LAZON Technology
The U.S. paper industry suffers more than $1,000,000,000 per year in lost production
alone due to biological contamination problems. Nalco LAZON Technology gives paper-
makers a new integrated approach that allows them to improve control of microorganisms
with significantly lower environmental impact. This technology is a unique bundling of
innovations that includes a synergistic biocide combination, two new monitoring technolo-
gies and specialized feed equipment. The primary component of LAZON Technology is the
chemistry, a combination of the non-halogen oxidant peracetic acid and a standard organic
biocontrol agent, which together provide antimicrobial activity that is far greater than expect-
ed 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 on-site. Finally, a specially designed chemical feed system and
Nalco's PORTA-FEED® returnable container complete the program. This interlocking net-
work 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 conservation, reduces operating costs, and minimizes point source release.
Nalco NALMET® Heavy Metal Removal Technology
Stricter NPDES discharge limits for effluent metals impact both metal and non-metal
industries. The parts-per-billion (ppb) limits for heavy metals removal cannot be met by
traditional metal precipitation processes. Membrane processes such as ion exchange, ultrafil-
tration and reverse osmosis are historically recommended for metal removal. They require
significant capital investment and still require pre-treatment of these waste streams. A chem-
ical 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 percent,
product overfeed is reduced, environmental releases of treatment chemical are reduced, a
less toxic treatment chemical is used, customers consistently meet ppb metals discharge
limits. Through Nalco's integrated, innovative approach, our customers achieve pollution
prevention. Cradle-to-grave environmental management is achieved with environmental
toxicity reduction.
Nalco Chemical
Company
Nalco Chemical
Company
55
-------
Nalco Chemical
Company
Nalco PORTA-FEELf
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
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 percent of our
annual sales $659 million were shipped in 500,000 nonreturnable drums. Fifteen percent of
1996 annual sales of $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 renew-
able 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 percent have resulted from this process. The second approach
involves direct, automatic detection of a fluorescence tagged treatment chemical. The chem-
ical's presence can be detected in systems where low level detection was not possible,
correlating variations in treatment consumption with variations in the water system's opera-
tion. The final approach tracks the resulting product performance, such as corrosion
protection or foam elimination in the process system, allowing further refinement of chemi-
cal 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
management and minimization of environmental release. These applications provide a com-
plete 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 percent 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
systems are either hazardous to the environment or have other drawbacks, such as instability
in the presence of oxidizing biocides, limiting their applicability. A new, all-organic corrosion
inhibitor, Bricorr® 288, a phosphonocarboxylate mixture, has been discovered and patented.
Bricorr® 288 is a highly effective corrosion inhibitor with wide applicability to industrial
cooling systems. Bricorr® 288 has an environmental profile permitting, in many instances,
56
-------
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
solvents. The process is inherently 'clean', in that it does not produce any discharges to water
or air, nor any by-products. 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.
No-Clean Soldering
CTS Corporation Resistor Networks produces solid ceramic resistor networks in various
single in-line, dual in-line, surface mount, and through-hole packages with standard or
custom circuit designs. Through CTS Corporation's commitment to a responsible environ-
mental policy, many of its manufacturing methods have been modified with the goal of
reducing or eliminating hazardous waste byproducts. One such method to reduce waste was
the implementation of a No-Clean soldering process. This No-Clean soldering process,
which began in March 1993, has eliminated the use of wave oil, soldering fluxes, and solvent
cleaning. Changing to the No-Clean soldering process involved installing hoods over the
solder pots. Using the hoods, an inert atmosphere is maintained over the molten solder.
By using the inert atmosphere, oil and flux are no longer required. The parts are clean after
solder and thus no solvent cleaning is needed.
Previously, TCA (1-1-1 Trichloroethane) and TCE (1,1,2 Trichloroethylene) were used as
part of a post-solder cleaning operation to remove flux and wave oil residues. Due to the elim-
ination of flux and wave oil, these cleaning operations became unnecessary. Therefore, the
amounts of waste TCA and TCE from soldering operations were reduced from 9,900 pounds
and 226,000 pounds in 1992, respectively, to zero in 1995. As an added benefit of eliminat-
ing solvent-based cleaning operations, air emissions due to the use of these chemicals have
dramatically decreased. From 1992 through 1996, TCA and TCE related air emissions from
soldering operations have been reduced from 99,000 pounds and 250,000 pounds, respec-
tively, to zero. A cleaning operation, not related to soldering, generated a small amount of
TCE air emissions in 1995. This operation was eliminated in June of 1995. The No-Clean
soldering process has eliminated the generation of waste oil, flux, and cleaning solvents at the
solder operation. Workers are no longer exposed to fumes from fluxes, oils, and cleaning sol-
vents, which are typical of soldering operations. The product quality has also been improved.
Polyacrylamide Technology Reduces Soil Erosion
Irrigated agriculture produces one-third of earth's total harvested crop and comprises one-
half of the total value of all harvested crop yet it comprises only one-sixth of the world's
cropland. Erodible irrigated soils typically lose over 20 tons of soil per acre per year under fur-
row irrigation. Scientists at the Northwest Irrigation and Soils Research Laboratory developed
and verified the use of a polyacrylamide (PAM) to reduce sediment loss by an average of 94
percent. In 1997 farmers used PAM to control erosion on an estimated 600,000 acres of fur-
row irrigated land, saving an estimated 12 million tons of soil in the third year of use. The
key to developing an economical PAM technology for use in agriculture is in the conditions
under which the primary reactive components polymer and soil were allowed to react. The
conventional method applied polymers directly to the soil surface and mixed them with the
soil to a maximum depth of six inches. This method was effective, but required the use of up
CTS Corporation
Resistor Networks
Northwest Irrigation
and Soils Research
Laboratory, U.S.
Department of
Agriculture
57
-------
Eastman Kodak
Company
to 500 pounds per acre of polymer and sometimes required the application of a second agent
used to activate the PAM. Associated costs made this method impractical for agricultural
applications.
The scientists at Northwest Irrigation and Soils Research Laboratory altered the tradi-
tional approach by first dissolving very small quantities of water soluble PAM (10 mg per
liter) in the irrigation source water and supplying furrows with the amended water only dur-
ing the irrigation advance phase, i.e., during that time when irrigation water initially advances
along the furrow and first wets the soil. This procedure greatly simplified the use of the poly-
mer, minimized the amount of reactants required, and selectively limited PAM-soil
stabilization reactions to those soil surfaces that were exposed to furrow-stream shear flow.
This efficient methodology required only 1 to 2 pounds per acre of PAM and was equal or
more effective than previous soil conservation approaches. PAM technology sustains agricul-
ture/soil productivity because millions of tons of soil and associated fertilizers/pesticides
remain in the field. Its use substantially reduces maintenance expenses (more than $100,000
per year for some irrigated tracts) required to remove and dispose of sediment from regional
irrigation systems and reservoirs, and can save farmers $25 to $50 per acre by eliminating on-
farm pond/ditch cleaning and soil redistribution costs. This nontoxic, environmentally safe,
and affordable chemical will provide irrigated agriculture a tool to greatly reduce sediment
and associated pollutant contributions to streams and other water sources. Its use will help
preserve irrigated agriculture production which is twice as productive as rainfed agriculture.
Polycarbonate/Polydimethylsiloxane Copolymers
for Thermal Print Media
The process to make polycarbonates using bischloroformates and bisphenols or diols was
developed and commercialized in the early 1990s by the Polymer Products Unit of the
Eastman Kodak Company in Rochester, New York. The original process to produce the poly-
carbonate of bisphenol A, diethylene glycol, and bisaminopropyl polydimethylsiloxane was
developed in 1992 and commercialized in 1993 for use in a new thermal print media prod-
uct. Concerns over waste and air emissions, as well as cost and capacity issues, prompted a
research and development effort to replace this polymer before production volumes increased
to forecasted high levels. The new process to produce a similar polycarbonate/polydimethyl-
siloxane copolymer was certified early in 1994. Improvements include the following: (1) the
new process is made in the solvent in which the polymer is coasted, and is delivered to the
manufacturing department dissolved in that solvent, eliminating the methanol precipitation,
methanol washing, and vacuum drying steps; (2) in the new process, triethylamine is used as
the acid acceptor instead of pyridine, making the water wash waste streams less hazardous;
(3) the new process uses the commercially available diethylene glycol bischloroformate, elim-
inating the need to manufacture the bisphenol A bischloroformate at Kodak in Rochester
(the bisphenol A bischloroformate synthesis uses phosgene as a key reactant, and its purifica-
tion produces large quantities of hazardous waste containing heptane and silica gel). The new
process will yield over 1.2 million pounds of hazardous waste reductions and more than
3,000 pounds of air emissions reductions from 1994 to 1996.
58
-------
Production ofCumene with Zeolite Catalyst—
The Mobil/Badger Cumene Process
About 7 billion pounds of cumene are produced each year in the United States (15 bil-
lion pounds worldwide). Most of it is converted to acetone and phenol, an intermediate in
the production of epoxy resins, nylon 6, and polycarbonate plastics. Conventional cumene
processes, based on Friedel-Crafts alkylation of benzene with propylene, use either solid phos-
phoric acid (SPA) or aluminum chloride (AlC^) catalysts. Both catalysts are corrosive,
hazardous when spent, and difficult to dispose of safely. And SPA, the most widely used
cumene catalyst, generates heavy aromatic by-products, once used to enhance gasoline
octane, but now increasingly restricted by the U.S. Clean Air Act. A new environmentally
friendly catalytic process for producing cumene is rapidly sweeping the industry, due to its
substantial environmental and economic performance advantages. In 1998, about 70 percent
of U.S. produced cumene will be made by this new technology, a Mobil/Badger joint
development introduced in 1996. The Mobil/Badger technology employs a new zeolite
catalyst that is environmentally benign and significantly more stable, more active, and more
selective to cumene. Manufactured by Mobil, this zeolite requires no special handling and
is returned environmentally inert to Mobil after use. The Mobil/Badger technology, proven
in Badger pilot units, will remove 4.4 million pounds of SPA from use, while reducing
heavy aromatic by-products by 250 million pounds/year. Its use will boost cumene yield by
5 percent and energy efficiency by more than 15 percent, enabling U.S. industry to meet
growing cumene demand with substantially reduced costs.
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
animals 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 poly-
mers 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 poly-
merization.
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 polyolefin utilizing selected
non-volatile 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 polyolefin product contains no
dissolved liquid and results in a multi-phase polymer system. This same system can be uti-
lized 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 to their chemical structure. Their unique polymerization process
results in each polymer chain having a terminal double bond. This double bond can partici-
pate in the free radical polymerization of the liquid monomers (methacrylate and acrylate).
Mobil Technology
Company
McDonough Braungart
Design Chemistry, LLC
59
-------
U.S. Army Tank
and Automotive
Armaments Command
The copolymers that result will contain both olefinic and acrylic segments. Such combined
polymers will act as compatibilizers for the two polymeric phases. This compatibilization will
play a major role in several characteristic functions of various applications.
Recycling of Hydraulic Fluid
The U.S. Army, in cooperation with industry, recently developed a methodology for
returning used hydraulic fluid to vehicle service. The effort was conducted in three phases.
First, a laboratory investigation was conducted to determine the viability of restoring used
fluid to specification performance (the test fluid was obtained through the military supply
system and consisted of new and used fluid qualified to specification MIL-H-46170 (FRH),
hydraulic fluid, rust inhibited, fire resistant, synthetic hydrocarbon). Second, a field investi-
gation designed to identify commercially available equipment that could successfully process
the used fluid as well as demonstrate the performance of the restored fluid in military vehi-
cles was conducted. Third, the Army pursued an automated diagnostic effort aimed at
optimizing the process. The developed technologies were successfully demonstrated with
innovative technologies and processes in place to implement throughout both military and
commercial industry
Phillips Petroleum
Company
M.A. Hanna Color—
Technical Center
Reduced Volatility Alkylation Process
Alkylate is considered to be a critical component of reformulated gasolines. It is a clean
burning, high octane mixture of paraffins and isoparaffins and contains no sulphur, olefins,
or benzene. Reduced volatility Alkylation Process (ReVAP) provides refiners with a low-cost
option for risk management and olefin conversion to such a high octane, clean-burning
gasoline component. The process employs an additive in the acid phase of a hydrogen fluo-
ride (HF) alkylation which suppresses the vapor pressure of HF and reduces its tendency to
form aerosols when released to the atmosphere. It is a drop-in replacement acid system for
existing HF alkylation units, which minimizes capital investments. The technology differs
from existing sulphuric acid processes in that recovery and re-use of the additive is required.
Separation from byproducts and recovery of the additive was deceptively complex initially.
To remove all traces of acid required large capital investments and would lead to more waste
generation. With ReVAP, a simple but elegant separation vessel was designed, allowing the
recovery and reuse of the additive with minimal capital costs. The additive is a commercial-
ly available product, with extremely low toxicity high chemical and thermal stability, and
is soluble with HF in all proportions. HF aerosol reductions of 60 to 90 percent can be
achieved. These results have been combined with extensive process development chemistry
and engineering to design a commercial process which is as safe as, if not safer than, existing
sulfuric acid processes.
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
surface treatments before paint will adhere. In certain environments, printed marks lack
durability and may require a protective topcoat. Self-adhesive labels, another option, pose sim-
ilar durability problems coupled with high scrap rates. A new technology to mark plastic parts
in color with a laser has been developed by MA. Hanna Color. This technology offers dra-
matic improvements in the ability of processors and end users to permanently mark a wide
60
-------
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 elimination of solvents in ink production, usage, and clean up), enhanced recyclability of
scrap plastic parts (unlike labels, there is no effect on melt reprocessability), and reduced lia-
bility 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 thermo-
plastics 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 wallstock 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 22,400,000 pounds (11,200 tons) annually, conservatively assuming an average sol-
vent content of 30 percent. M.A. Hanna Color estimates that within the first 2 years of use, the
new color laser marking technology could effectively replace approximately 10 percent of the
plastics decorating processes that involve inks. Within 10 years, this figure could rise to 50 per-
cent. Meeting the 10 percent projection would eliminate approximately 1,120 tons (2,240,000
pounds) of VOC emissions from the production of plastic parts in the U.S. annually.
Reduction of Carbon Tetmchloride Emissions 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 pro-
duction 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 million,
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 scaleup of greater than 250,000
times. The catalyst was purchased, shipped from Siberia, and implemented in less than 1 year
after the start of the program. After 1.5 years of commercial production, the new catalyst has
consistently demonstrated high phosgene production rates and achieved a 90 percent reduc-
tion in the level of carbon tetrachloride generation (to less than 50 ppm, apparently a new
global record). By conceptualizing, identifying, testing, securing from Russia, and imple-
menting 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 mainte-
nance 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 CC\4 by up to 5 million pounds per year.
DuPont Company
61
-------
Mallinckrodt Inc.
Eastman Kodak
Company
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 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, and it was proposed to oxidize the NOX
back to nitric acid by adding hydrogen peroxide directly to the process, thus completely elim-
inating NOX emissions. This proposal was demonstrated in the laboratory. Next, two trial
runs using this technology was 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.
The hydrogen peroxide addition process was successfully started. The new process has elim-
inated 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, 13,000,000 gallons per year of scrubber
waste water were eliminated since the scrubber is no longer needed.
Replacement ofMethanol Solutions with Aqueous
Dispersions in Photographic Coatings
Photographic films and papers are based on coatings of small silver halide crystals. A few
photons of light absorbed by a crystal are converted to a small cluster of silver atoms and this
cluster serves as the catalyst for the reduction of the entire grain when the coating is immersed
in a solution of a reducing agent. The contrast between exposed and subsequently reduced
areas of the coating and the unexposed areas forms the basis of black and white photography.
In color photography, reducing agent byproducts react with very small oil droplets of color-
forming precursors in the same layer as the silver halide to produce a dye. Differently
sensitized silver halide crystals made sensitive to specific wavelengths of light are paired with
oil droplets of appropriate color-forming precursors in a multiple layer sandwich to make
photographic film and paper capable of giving full color images.
Along with the silver halide crystals and color-forming precursors, small amounts of other
organic chemicals are essential for photographic performance. Antifoggants are need to con-
trol the stability and catalytic activity of the silver atom clusters generated by exposure.
Sensitizing dyes are used to make the silver halide sensitive to different wavelengths of light.
These chemicals are substantially water insoluble and their introduction into the aqueous
coating melt can be accomplished by making methanol solutions of these chemicals. Mixed
with the coating melt, these chemicals in these solutions rapidly adsorb onto the silver halide
grains. In some cases, the low solubility of the chemical requires very dilute methanol solu-
tions. This, and the need to add several different dyes and antifoggants to a given
photographic product results in coating melts with significant percentages of methanol.
There are workplace concerns associated with such melts as well as the undesirable emission
of methanol to the atmosphere during the coating and drying of the photographic product.
To reduce or eliminate methanol use, Eastman Kodak Company has prepared aqueous
dispersions of sensitizing dyes and antifoggants using milling techniques. Such dispersions
consist of small particles (less than 1 micrometer in diameter) of the chemical of interest
stabilized by surfactant and/or polymer. Methods such as ball, sand, or media milling can
62
-------
be used with the processing details such as milling time and composition optimized for the
chemical of interest. These dispersions are miscible with the aqueous coating melt and give
chemical activity comparable, and in some cases superior, to that of methanol solutions.
Using this technology, methanol emission to the atmosphere during coating and drying has
been greatly reduced even in time of increasing production.In addition, environmental con-
cerns regarding the storage, and handling of methanol in manufacturing operations have
been avoided.
Selective Hydrodechlorination of Carbon Tetrachloride
In 1987, 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
elimination 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 is
about 60,000 tons excess CC\4 produced per year. The disposal of this byproduct, CC\4,
typically by incineration, has become an environmental challenge and major economic
burden to manufacturers of methylene chloride/chloroform.
Hydrodechlorination of carbon tetrachloride to chloroform is an attractive alternative to
the disposal of by-product carbon tetrachloride by incineration. Until now, the catalytic con-
version of CC\4 to CHCi3 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 CC\4
to CHCi3 that resists deactivation for over 2,000 hours. In contrast, untreated catalysts were
rapidly deactivated with conversions dropping from 90 percent to 2 percent 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 imple-
menting this technology internally and might offer it for commercial licensing in the future.
Splittable Surfactants
Union Carbide has developed a new class of surfactants, splittable surfactants, which
provide 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 non-toxic to
aquatic 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.
Akzo Nobel Business
Unit Base Chemicals
Union Carbide
Corporation
63
-------
Nalco Chemical
Company
Sequa Chemicals, Inc.
STABREXMicroorganism Control Chemical
Water treatment is mostly about managing surface-fouling processes. There are three
surface-fouling processes to manage (microbial, scaling, corrosion) and they occur simulta-
neously. Of these three, the microbial fouling process requires application of the most
potentially hazardous products in water treatment, by far. Effective control of microbial
fouling is the key to water treatment because modern scale and corrosion inhibition chemi-
cals simply do not work unless microbial fouling is properly controlled. Predominately,
chlorine, bromine, and/or other oxidants are used as the principal microbial control agent
with more toxic nonoxidizing biocides used to supplement the program when necessary.
Natural processes to control microbial fouling have been optimized by the test of environ-
mental competition and natural selection. STABREX microorganism control chemical is a
new stabilized liquid hypobromite product that is modeled after antimicrobials used in
natural microbial fouling control processes. Response in the industry to this new technology
has been positive because the product is safer, simpler, and less expensive to use compared
to current alternatives. Marketplace acceptance of this new technology has been dramatical-
ly rapid. There are already over 400 commercial applications of the product in the United
States and several million pounds of product were produced and sold in its first year of
commercial introduction.
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 non-formaldehyde 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 non-woven
mat. This provided a binder system which eliminated formaldehyde emissions and main-
tained good performance and reasonable economics.
These starch graft emulsion polymers are water-based, non-toxic and non-irritating.
Recent work has examined the use of these starch graft polymers as extenders for phenol-
formaldehyde (PF) resins. An aqueous PF resin typically contains approximately 2 percent
free formaldehyde. Approximately a billion pounds of aqueous PF resins are sold in the
United States each year. That adds up to approximately 20 million pounds of free formalde-
hyde emitted to the environment and work place each year. It has been found that starch graft
polymer products not only decrease formaldehyde emissions greatly, but also work synergis-
tically with PF resins. Optimum performance is near the mid-point of composition. Such
synergistic 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.
64
-------
Stepan Company PA Lites Polyester Polyol
Stepan Company's Polyester Polyol product, manufactured using the Phthalic Anhydride
Process Light Ends (PA Lites), uses a previously categorized waste as a raw material in its
manufacture, thereby eliminating the material's disposal via incineration. This Polyester
Polyol is the basic raw material for the manufacture of various types of insulating wallboard
used in the home construction and commercial building industry. By substituting tradition-
al raw materials with PA Lites, Stepan Company is providing the construction industry and
consumer 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 phtalic
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 phtalic anhydride facility was also improved. An estimated 350 tons per year
of organic waste material has been eliminated with the development and implementation
of this technology. This not only represents a significant reduction in waste requiring dispos-
al 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 Poyurethane 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
Trichlorofiuoroethane (CFC-11), or more recently 1,1-Dichloro-l-fiuoroethane (HCFC-
l4lb), as the blowing agent. CFCs and HCFCs have been demonstrated to play a role in the
depletion of 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 which replaces environmental-
ly unfriendly and potentially hazardous blowing agents with water. Stepan's Research and
Development Department and Business Teams have partnered with our customers through-
out the development and continued application of this product to promote its use as a viable
alternative to CFCs and HCFCs.
Stepan Company
Stepan Company
65
-------
AlliedSignal Federal
Manufacturing and
Technologies
U.S. Navy, Office of
Naval Research
U.S. Navy, Naval
Surface Warfare Center
Aerojet Propulsion
Professor Joseph M.
DeSimone, Department
of Chemistry,
University of North
Carolina at Chapel Hill
Synergy CCS™ Precision Cleaning Solvent:
A Government/Industry Solution to a Complex
Environmental Problem
Halogenated solvents have traditionally been used to remove a broad range of soils and
contaminants generated during manufacturing operations. Their use, however, has left a
legacy of potential environmental and health problems. Synergy CCS"" (critical cleaning
solvent) was developed to address these problems. Synergy CCS™, formulated from agricul-
turally-derived, naturally renewable products, is a potential replacement for many of these
traditional cleaning solvents.
Synergy CCS"' had its beginnings at the Department of Energy's Kansas City Plant (man-
aged and operated by AlliedSignal Inc.) when the plant began an effort focused on the
elimination of toxic, restricted, or environmentally damaging solvents. Experience derived
from this solvent substitution and elimination effort proved beneficial when, through its
Technology Transfer Program, Kansas City Plant personnel were asked for help by a small
manufacturer needing a safe, one-step cleaning solvent. Synergy CCS™ Precision Cleaning
Agent was formulated to meet this need. Synergy CCS™ is a blend of environmentally derived
products that forms a safe, powerful, yet distillable precision cleaning solvent capable of being
heavily loaded with contaminants. Synergy CCS™ is comprised of natural components that
have been in industrial use for more than 45 years: d-limoene, a solvent derived from citrus
byproducts, and tetrahydrofurfuryl alcohol, a solvent produced from the waste products of
corn, oats, and sugar production. Individually, these materials are already used for cleaners,
paint stripping formulations, and agricultural applications.
The solvent was further developed and adopted by a Hewlett-Packard Co. division,
patented, and licensed to Petroferm, Inc., a worldwide leader in sales and technical support
for alternative solvents and cleaning technologies. This partnership demonstrates how
government and private industry can work together to develop safe chemical alternatives to
solve environmental problems while simultaneously improving America's industrial
competitiveness.
Use of Carbon Dioxide as an Alternative Green Solvent
for the Synthesis of Energetic Thermoplastic Elastomers
Thermoplastic elastomers based on triblock oxetane copolymers containing azido func-
tional groups offer an improved binding material for solid, high-energy formulations.
Current technology uses chemically cross-linked energetic prepolymer mixes that introduce
the problems of thermally labile chemical linkages, high end-of-mix viscosities, and vulnera-
bility to premature detonation. These materials are also nonrecyclable and generate large
amounts of pollution during disposal The use of energetic thermoplastic elastomers
eliminates the need for chemical cross-linking agents, makes processing easier due to their low
melt viscosities, and eliminates the need for solvents during casting. Their superior process-
ing qualities and the ease of demilitarization and recycling make these materials a much more
environmentally sound choice for energetic binders. However, their synthesis still involves
the use of large quantities of toxic chemicals, such as methylene chloride, as solvents.
Carbon dioxide has been proven to be a viable, environmentally responsible replacement
solvent for many synthetic and processing applications. It is cheap, easily recyclable, and
available from current sources. Research at the University of North Carolina has shown that
carbon dioxide is a viable solvent for the polymerization of vinyl ether monomers.
66
-------
Furthermore, polyoxetanes can be polymerized in carbon dioxide with molecular weight,
molecular weight distribution, and functionality maintained. The University of North
Carolina has demonstrated the synthesis of both nonenergetic and energetic homopolymers
and random copolymers.
The Use of Chlorine Dioxide, the Foundation of
Elemental Chlorine-Free (ECF) Bleaching for Pulp
and Paper, as a Pollution Prevention Process
The use of chlorine dioxide as a pollution prevention process to substantially or
completely replace chlorine in the first stage of chemical pulp bleaching is a unique imple-
mentation of chlorine dioxide chemistry. It can be applied to the entire bleached chemical
pulp and paper industry, both in the United States and abroad. By employing raw material
substitution and process modifications, this technology has allowed the pulp and material
substitution and process modifications, this technology has allowed the pulp and paper
industry to meet the source reduction objectives of the Pollution Prevention Act of 1990.
With this new application of sophisticated chlorine dioxide chemistry, the pulp and paper
industry virtually eliminated dioxin from mill waste waters and our nation's water bodies.
This technology has answered the industry's calls for a more benign chemical pulp bleaching
agent. Virtual elimination of dioxin from mill waste waters and continuing nationwide
ecosystem recovery provide a strong measure of chlorine dioxide's success and the industry's
environmental progress. In fact, downstream of U.S. pulp mills bleaching with chlorine
dioxide, fish dioxin body burdens have declined rapidly and aquatic ecosystems continue to
recover. For example, the Mead Paper Company's Escanaba Mill, in Michigan, implemented
pollution prevention strategies beginning with the use of low precursor defoamers in 1989.
In 1990, the mill increased chlorine dioxide substitution. These process modifications
decreased dioxin in final mill effluent to nondetectable levels. Consequently, dioxin body
burdens declined more than 90 percent in less than 4 years. These indicators of progress
toward broader ecosystem integrity demonstrate the success of chlorine dioxide as
'green chemistry'.
Waste Reduction During Development of a New Process
for Manufacture of Pharmaceutical Products
Evista® is the first of a new class of selective estrogen receptor modulators, or SERMs, that
was approved in December 1997 for the prevention of osteoporosis in postmenopausal
women. Waste reduction and minimization of overall environmental impact were key ele-
ments in development and commercialization of a process for manufacture of Evista®. To
identify, address, and track environmental issues and opportunities early in the development
and commercialization of manufacturing processes, Eli Lilly and Company has developed a
new management system called New Product Environmental Requirements Tracking
(NPERT). Development and commercialization of the manufacturing process for Evista®
served as a pilot for this program.
The initial process proposed for manufacture of Evista® would have generated over 3.1
pounds of solid hazardous aluminum chloride waste per pound of product. In addition, the
manufacture required the use of 114 liters of organic solvents for each pound of product pro-
duced. Of the total solvent used, 85 percent was composed of Superfund Amendment and
Reauthorization Act (SARA) Title III listed material. While the process was still in develop-
Alliance for
Environmental
Technology (AET)
Eli Lilly and Company
67
-------
ment, Lilly chemists and engineers found a way to eliminate the use of aluminum chloride
and the need for disposal of the corresponding hazardous solid waste. This eliminated the
generation and disposal of more than 371,000 pounds of hazardous solid waste during the
first year of commercial production. During process development, the NPERT process
focused attention on reducing total solvent usage and particular attention on the reduction
in the use of all SARA Title III solvents. For example, one of the processing steps initially used
methylene chloride. Evaluation of 26 alternative solvents resulted in the ability to complete-
ly eliminate the use of methylene chloride. Another process step used methyl isobutyl ketone
(MIBK) and generated a waste stream that could not be solvent recovered and required incin-
eration. Process development work resulted in a modification of the process that allowed the
use of amyl acetate rather than MIBK. The revised process was more efficient and economi-
cal, generating an amyl acetate waste stream that could be easily recovered.
By the time the Evista® process was in full scale manufacturing, process modifications and
improvements in efficiency during development and scale-up had reduced the total volume
of solvent required to produce a pound of product by 61 percent. These improvements also
reduce the use of SARA Title III solvents by 67 percent. Currently, on-going efforts are
underway to further decrease waste, reduce volatile emissions and increase the recovery and
recycle of solvent. The NPERT process and the example of its use on Evista®, show that
focused efforts early in development and scale-up can dramatically reduce the environmental
impacts of a new chemical manufacturing process. This effort highlights Lilly's commitment
to minimizing the worldwide environmental impact of its manufacturing operations.
U.S. Navy, Office of
Naval Research
U.S. Navy, Naval
Surface Warfare
Center
U.S. Army Armament
Research,
Development and
Engineering Center
Los Alamos National
Laboratory
Aerojet
Waste Reduction in the Production of an Energetic
Material by Development of an Alternative Synthesis
1,3,3-Trinitroazetidine (TNAZ) is a promising new melt-castable explosive that has
significant potential for providing environmental benefits and capability improvements in a
wide variety of defense and industrial applications. Initial lifecycle pollution burden was
associated with the demilitarization of the munitions, and in particular, the use of thermoset
polymeric binders that require removal with water jet cutting. TNAZ is the only energetic
material other than trinitrotoluene (TNT) that can be melt-cast in existing TNT loading
plants. Demilitarization of TNAZ simply requires heating the device above the melting
point and pouring the liquid out, rather than the complicated and destructive methods used
for RDX- and HMX-based plastic bonded explosives. The stability of TNAZ in the melt
allows it to be easily recycled.
TNAZ has performance slightly better than that of HMX, the most powerful military
explosive in current use. Thus, TNAZ might offer 30 to 40 percent improvements in per-
formance as a replacement for TNT-based formulations such as Composition-B. The
alternative synthesis of TNAZ, developed at the Los Alamos National Laboratory, allows
TNAZ to be produced in a waste-free process that also eliminates the use of halogenated sol-
vents. This alternative synthesis produces 5.3 pounds of waste per pound of product
compared to the original synthesis of TNAZ, which produces 1,200 pounds of waster per
pound of product. The alternate technology has been transferred to industry, where it has
been scaled up to production-plant quantities. Further improvements in waste reduction
have been demonstrated in the laboratory that might eventually lead to a process giving lit-
tle more waste than one pound of salt per pound of TNAZ.
68
-------
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 which is pri-
marily 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
400,000,000 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,
15,000,000 gallons of photographic developer containing thousands of tons of obnoxious
chemicals like hydroquinone is similarly dumped on the POTWs. Further, 15,000,000 gal-
lons of photographic fixer containing high levels of ammonia and silver is also sent to the
POTWs for treatment. Although some of the silver is removed by various processes, these are
not very efficient and recovery of this precious metal is only on the order of 50 percent. 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 percent 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 erythor-
bic acid instead of hydroquinone in a process that allows about 75 percent 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 percent. In addition, the
analytical capability and control at a recycling center allow about 90 percent 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 395,000,000 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 commercial, licensed TSDFs. Packaging waste would drop significantly, the
efficient recycling and reuse of the spent chemical stream would eliminate the need for thou-
sands of tons of raw materials as well.
E.I. duPont de Nemours
& Co., Inc.
69
-------
Index
Award winners are indicated with *.
Akzo Nobel Business Unit Base Chemicals
Selective Hydrodechlorination of Carbon Tetrachloride. 63
Albany Research Center, U.S. Department of Energy
Chloride-Free Processing of Aluminum Scrap 41
Albright & Wilson Americas Inc.
A New, Environmentally Friendly Corrosion Inhibitor for
Industrial Cooling Systems 56
Alliance for Environmental Technology (AET)
The Use of Chlorine Dioxide, the Foundation of Elemental Chlorine-Free (ECF)
Bleaching for Pulp and Paper, as a Pollution Prevention Process 67
AlliedSignal Federal Manufacturing and Technologies
Synergy CCS™ Precision Cleaning Solvent: A Government/Industry Solution
to a Complex Environmental Problem 66
American Air Liquid
Air Liquid PFC Recycle Process 38
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 36^
Antia, Jimmy E. and Govind, Rakesh, Department of
Chemical Engineering, University of Cincinnati
Novel In-Situ Zeolite Coatings in Monoliths 18
*Argonne National Laboratory
Novel Membrane-Eased Process for Producing Lactate Esters—Nontoxic
Replacements for Halogenated and Toxic Solvents 6
Arkenol, Holdings, L.L.C.
Sugars From Lignocellulosic Materials for the Production of Bio-Based
Fuels and Chemicals 35
Asarco Incorporated
Asarco—West Fork Eiotreatment Project 40
Beckman, Eric J., Chemical Engineering Department,
University of Pittsburgh
Design ofCO2-Soluble Ligands for Affinity Extraction Using CO2 10
BetzDearborn, Inc.
Designing an Environmentally Friendly Copper Corrosion Inhibitor for
Cooling Water Systems 42
BIOCORP, Inc.
Biodegradable Thermoplastic Material. 27
Biofine, Incorporated
Conversion of Low-Cost Biomass Wastes to Levulinic Acid and Derivatives 28
70
-------
Bose, Ajay K., Stevens Institute of Technology
Microwave-Induced Organic Reaction Enhancement (More) Chemistry
for Eco-Friendly Synthesis 15
Bowling Green State University
Orphan Chemical Recycling Program 19
Burch Company
Burch Apparatus and Method for Selectively Treating Vegetation to Reduce
Pesticide 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 27
Ciba Specialty Chemicals Corporation
Heavy Metal Free Alternative to Standard Anti-Corrosive Pigments 50
Collins, Terrence J., Department of Chemistry,
Carnegie Mellon University
detent, Selective, Totally Chlorine Free (TCP) Wood Pulp Bleaching Technology 12
CTS Corporation Resistor Networks
No-Clean Soldering 57
Doherty, Michael F. and Malone, Michael F., Department of Chemical
Engineering, University of Massachusetts, Amherst
Reactive Distillation Technology to Reduce Waste at the Source 20
*Draths, Karen M. and Frost, John W., Department of Chemistry,
Michigan State University
Use of Microbes as Environmentally-Benign Synthetic Catalysis 3
DuPont Company
INFINITY Process 52
NAFIONMembrane Technology 54
Reduction of Carbon Tetrachloride Emissions at the Source, by Development
of a New Catalyst 61
DuPont Polyester
DuPont Petretec Polyester Regeneration Technology—Making Polyester Evergreen . 45
E&J Industries, Incorporated
Ultraviolet (UV) Curing of Small Wood Products: An
Industrial Demonstration Project 35
E.I. duPont de Nemours & Co., Inc.
Zero Effluent Photographic Processing in the Printing Industry 69
Eastman Kodak Company
Polycarbonate/Polydimethylsiloxane Copolymers for Thermal Print Media 58
Replacement ofMethanol Solutions With Aqueous Dispersions
in Photographic Coatings 62
Eli Lilly and Company
Waste Reduction During Development of a New Process for Manufacture
of Pharmaceutical Products 67
T\
-------
Environmental Technology and Education Center, Inc. (ETEC)
High Energy Efficiency, Environmentally Friendly Refrigerants 30
EOSystems, Inc.
CerOx Process Technology for Non-Thermal Destruction of
Organic Hazardous Wastes 28
*Flexsys America L.P.
Elimination of Chlorine in the Synthesis of4-Aminodiphenylamine: A New Process
Which Utilizes Nucleophilic Aromatic Substitution for Hydrogen 5
Govind, Rakesh and Singh, Rajit, Department of Chemical Engineering,
University of Cincinnati
Bioconversion of Carbon Dioxide into Organic Feedstocks 8
Great Western Chemical Company
MRA-D, A New Wastewater Treatment Process 31
Gross, Richard A., Department of Chemistry, University of
Massachusetts, Lowell
Biotechnological Routes to 'Tailored' Polymeric Products of Environmental
and Industrial Importance 9
Hauser, Inc.
Paclitaxel Process Improvements 32
Hendrickson, James B., Department of Chemistry, Brandeis University
The SYNGEN Program for Generation of Alternative Syntheses 22
Hill, Craig L., Department of Chemistry, Emory University; Weinstock,
Ira A., USDA Forest Service, Forest Products Laboratory
A New Catalytic Biomimetic Technology to Convert Wood to Paper
Without Pollution 16
Ho, Nancy W.Y., Laboratory of Renewable Resources Engineering,
Purdue University
Successful Development of Recombinant Xylose-Fermenting Saccharomyces Yeasts
Capable of Effectively Co-Fermenting Glucose and Xylose from Renewable Cellulosic
Biomass to Ethanol as Clean Transportation Biofuel 21
Hudlicky, Tomas, Department of Chemistry, University of Florida
Synthetic Methodology "Without Reagents. " Commercial Manufacture of
Inositols and Other Pharmaceuticals by Tandem Enzymatic and Electrochemical
Oxidations and Reductions 23
IBM Research Division, Almaden Research Center
The Chemical Kinetics Simulator Program 41
Imation™ Corporation
Imation No Process Plates 50
IMC-Agrico Company
AGROTAIN® N-(n-butyl) Thiophosphoric Triamide 38
International Metalizing Corporation
Non Toxic Antifouling 32
72
-------
lonEdge Corporation
Zero-Waste Dry Plating of Cadmium ............................... 36
Khalili, Nasrin R., Arastoopour, Ham id, and Walhof, Laura,
Department of Chemical and Environmental Engineering,
Illinois Institute of Technology
Novel Waste Minimization Approach: Production of Carbon-Eased Catalyst or
Sorbent from Eiosolids .......................................... 19
KM Limited Inc.
The PIX Module Software: Combining Life Cycle Assessment With Activity Eased
Costing to Preserve the Global Environment ........................... 33
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 ...................................... 14
Ladisch, Michael R., Laboratory of Renewable Resources Engineering and
Department of Agricultural and Biological Engineering, Purdue
University
or Desiccant Coolers ............................. 8
Lawrence Livermore National Laboratory; U.S. Department of
Defense, Office of Munitions; U.S. Department of Energy, Weapons
Supported Research
Environmentally-Driven Preparation of Insensitive Energetic Materials ........ 48
LeBlanc, Carole, The Massachusetts Toxics Use Reduction Institute,
University of Massachusetts, Lowell
The Determination of Alternative Solvents Quantifying and Qualifying Green
Chemistries in Industrial Surface Cleaning. ........................... 11
Li, Chao-Jun, Department of Chemistry, Tulane University
Water as Solvent for Chemical and Material Syntheses .................... 25
Lin, Chhiu-Tsu, Department of Chemistry and Biochemistry, Northern
Illinois University
Chrome-Free Single-Step In-Situ Phosphatizing Coatings .................. 10
Lockheed Martin Tactical Aircraft Systems
Development and Implementation of Low Vapor Pressure Cleaning Solvent Blends 43
Implementation and Verification of Aqueous Alkaline Cleaners .............. 51
Los Alamos National Laboratory
Application of Freeze Drying Technology to the Separation of
Complex Nuclear Waste ......................................... 39
Magnetic Separation for Treatment of Radioactive Liquid Waste ............. 53
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 ...................... 60
Mallinckrodt Baker Inc.
Hydrogen Sulfide Elimination from the Substances Not Precipitated by H2S Test . 50
Mallinckrodt Inc.
The Removal of Oxides of Nitrogen (NOx) by In-Situ Addition of Hydrogen
Peroxide to a Metal Dissolving Process ............................... 62
73
-------
Manousiouthakis, Vasilios, Department of Chemical Engineering,
University of California Los Angeles
Source Reduction Through Mass Integration: Mass Exchange Network Synthesis. . 21
Mathews, Alexander P., Department of Civil Engineering,
Kansas State University
Waste Biomass Utilization in the Production of a Biodegradable Road Deicer ... 23
McDonough Braungart Design Chemistry, LLC
PVC Replacement Technology 59
MEMC Electronic Materials, Inc.
Elimination of Ozone-Depleting Chemicals (ODCs) Through the Use of a Water
Soluble Adhesive "Green Wax" 45
Mobil Technology Company
Production ofCumene with Zeolite Catalyst—The Mobil/Badger Cumene Process 59
Nalco Chemical Company
STABREX® Microorganism Control Chemical 64
Nalco NALMET* Heavy Metal Removal Technology 55
Nalco Fuel Tech NOxOUT* Process 54
Nalco TRASAR® Technology 56
Nalco LAZON" Technology 55
Environmentally-Responsible Liquid Polymers 47
Nalco PORTA-FEED® 56
Nassaralla, Claudia Lage, Department of Metallurgical and
Materials Engineering, Michigan Technological University
Waste Reduction and Recycling of Magnesite-Chrome Refractory into
the Steelmakin? Process 24
National Center for Agricultural Utilization Research
Environmentally Benign Synthesis of Monoglyceride Mixtures Coupled
With Enrichment by Supercritical Fluid Fractionation 47
NICCA U.S.A., Inc.
Heavy Metals Free, Non-Formaldehyde Fixing Agent for Direct and
Fiber Reactive Dyes 30
Nikles, David E., Department of Chemistry, University of Alabama
Waterborne Coating Formulations for Video Tape Manufacture 25
Nortel Technology
Molyphos: A Chromate-Free Alternative for Corrosion Protection of Metal Parts . 53
Northwest Irrigation and Soils Research Laboratory,
U.S. Department of Agriculture
Polyacrylamide Technology Reduces Soil Erosion 57
74
-------
Novon International
Natural Recycling of Plastics Through Chemical and Biological Degradation . ... 31
Paquette, Leo A., Department of Chemistry, The Ohio State University
Environmental Advantages Offered by Indium-Promoted Carbon-Carbon
• Reactions in Water 13
Pharmacia & Upjohn
Environmental Improvements from Redesigning the Commercial Manufacture
of Progesterone 46
Phillips Petroleum Company
Reduced Volatility Alkylation Process 60
Praxair, Inc.
Liquid Oxidation Reactor (LOR) 52
*PYROCOOL Technologies, Inc.
Technology for the Third Millennium: The Development and Commercial
Introduction of an Environmentally Responsible Fire Extinguishment and
Cooling Agent. 4
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 17
Rochester Midland Corporation
Development of a New 'Core' Line of Cleaners 44
*Rohm and Haas Company
Invention and Commercialization of a New Chemical Family of Insecticides
Exemplified by CONFIRM Selective Caterpillar Control Agent and the
Related Selective Insect Control Agents MACH 2™ and INTREPID™ 7
Rybarczyk, James P., Department of Chemistry, Ball State University
Premature Degradation of Coolant Oil in the Machining of Magnesium in the
Automobile Industry 20
Rynex Holdings, Ltd.
Rynex Biodegradable Dry Cleaning Solvent 34
Sequa Chemicals, Inc.
Starch Graft Polymers as Phenolic Resin Extenders 64
Singh, Mono M., National Microscale Chemistry Center,
Merrimack College
National Microscale Chemistry Center: The Leader in Worldwide Implementation
of Microscale Technology 15
Solutia Inc.
Greenhouse Gases: From Waste to Product 49
75
-------
Solvent Kleene, Inc.
Non-Hazardous Degreaser that Degreases as Efficiently as Triehloroethane
and Outperforms Aqueous Products 32
Stepan Company
Stefan Company PA Lites Polyester Polyol 65
Stepanfoam® Water-Blown Polyurethane Foam HCFC-Free, Environmentally
Friendly, Rigid Polyurethane Foam 65
Stewart, Jon D., Department of Chemistry, University of Florida
Engineered Baker's Yeast as a Means to Incorporate Bio'catalysis Early in Process
Design: Application to the Asymmetric Baeyer-Villiger Oxidation 12
Subramaniam, Bala, Department of Chemical and
Petroleum Engineering, University of Kansas
A Novel Solid-Acid Catalyzed 1-Butene/Isobutane Alkylation Process 18
Synthon Corporation
Development and Commercialization of High-Value Chemical Intermediates
from Starch and Lactose 29
Taylor, Larry T., Department of Chemistry, Virginia Tech and
Virginia Tech Intellectual Properties
A Non-Toxic Liquid Metal Composition for Use as a Mercury Substitute 17
TechMatch, Incorporated
N-Methylmorpholine-N-oxide (NMMO): A Novel, Non-Toxic Reusable Solvent
for Cellulose as Source Reduction in the Production of Textile Fibers 31
Tektronix, Inc.
Designing Safer Chemicals: Spitfire Ink 43
Thompson, Stephen, The Center for Science, Mathematics,
and Technology Education, Colorado State University
Small Scale Chemistry: Pollution Prevention in Inorganic Chemistry
Instruction Program 20
*Trost, Barry M., Department of Chemistry, Stanford University
The Development of the Concept of Atom Economy 2
Union Camp Corporation
C-FREE™ Pulp Ozone Bleaching Project 40
Union Carbide Corporation
Splittable Surfactants 63
U.S. Army Edgewood Research, Development, and Engineering Center
Filter Leak Test Using Ozone-Benign Substances 48
o o
U.S. Army Tank & Automotive Armaments Command
Recycling of Hydraulic Fluid. 60
U.S. Bureau of Engraving & Printing
Designing a Safer, Less Toxic, Less Pollutant and Environmentally
Friendly Solvent—ISOMET 42
76
-------
U.S. Navy, Office of Naval Research; U.S. Navy, Naval Surface Warfare
Center; Aerojet Propulsion; and Professor Joseph M. DeSimone,
Department of Chemistry, University of North Carolina at Chapel Hill
Use of Carbon Dioxide as an Alternative Green Solvent for the Synthesis of Energetic
Thermoplastic Elastomers 66
U.S. Navy, Office of Naval Research; U.S. Navy, Naval Surface Warfare
Center; U.S. Army Armament Research, Development and Engineering
Center; Los Alamos National Laboratory; Aerojet
Waste Reduction in the Production of an Energetic Material by Development of
J o ,/ i J
an Alternative Synthesis 68
Varma, Rajender S., Texas Regional Institute for Environmental Studies,
Sam Houston State University
Environmentally Benign Solvent-Free Chemical Processing 13
Warner, John C., Department of Chemistry,
University of Massachusetts, Boston and Polaroid Corporation
Environmentally Benign Supramolecular Assemblies of Hydroquinones in
Polaroid Instant Photography 14
Weimer, Alan W., Department of Chemical Engineering,
University of Colorado
Vibrating Fluidized Bed Combustion Nitridation Processing Using Concentrated
Solar Energy 23
Zyvax Incorporated
The Zyvax "Watershield" Mold Release 37
77
-------
?? "° °
g» *
O Q) °
=: ffl
*<: —
-H DO
o c
•^ C/)
Tl 5'
=!. CD
< CO
ffl CO
CD
c
en
CD
ffl
CO
3-
3
to
O
^
D
O
K3
O
-P'
CD
O
2=1
sll
T
1 "
CD ffl
E. CD
£B CO
Tl
O
CD
O
5'
3
>
to
CD
m
------- |