U.S. EPA Office of Research
and Development's Science
H'll
To Achieve Re
(STAR)
Research in Progress
Vol.3 Issues November 1999 A product of the National Center for Environmental Research and Quality Assurance
EARLY RESULTS FROM TSE STAR RESEARCH GRANTS
While most Technology for a Sustainable Environment
(TSE) STAR grants are still active, and final results are not
yet complete, practical methodologies have already been
successfully demonstrated and "scaled up" for commer-
cial application in three important areas:
1. Supercritical Fluids for cleaner, safer
industrial processes
2. Green Cleaning and Related Processes
3. Biotechnology
Supercritical Fluids for Cleaner,
Safer Industrial Processes
A type of industrial process called "alkylation reactions",
used in gasoline formulation and other commercial ap-
plications, typically uses strong acids as catalysts. Alky-
lates are blending agents in
gasoline formulation. Because
they contain virtually no toxic
components, alkylates
are playing an increas-
ingly important role in
meeting the reduced
Pollution prevention is the preferred strategy for reducing risks posed by the design, manufacture, and use of
manufactured products and commercial chemicals. The long-range goal of this program is to develop safer com-
mercial substances and environmentally friendly chemical syntheses to reduce risks posed by existing practices.
vvEPA
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*****
the CO2 solvents can be used, for ex-
ample a potentially widespread appli-
cation in polymer manufacturing that
requires forming epoxidesfrom allylic
alcohols. A key scientific product of
this work is a reliable computational
thecnique generally applicable in high
pressure phase behavior calculations
across a range of reaction systems. In
another study relevant to the petro-
chemical and plastics industries, EPA
and NSF supported research by Drs.
Alan Russell and Eric Beckman along
with a team at the University of Pitts-
burgh, investigating the use of
supercritical CO2 to make polyester in-
termediates for urethane production.
Their published findings provide a
framework around which commer-
cially viable processes can be devel-
oped.
emissions gasoline requirements established by the 1990
Clean Air Act. However, alkylation presents environmen-
tal and safety concerns because of two factors: 1) health,
safety and environmental problems from liquid acid spill-
age, and 2) the need to dispose of toxic by-products. De-
veloping "environmentally-friendlier" alkylation is thus es-
pecially needed and could have particularly widespread
pollution prevention impacts. An alternative approach is
to use solid rather than liquid catalysts, but these have the
drawback of rapidly becoming inactive as coke deposits
clog catalyst pores. Dr. Bala Subramaniam of the Univer-
sity of Kansas , working under a STAR grant, has demon-
strated the effectiveness in this catalyzation of using a
supercritical fluid (SCF). SCFs are neither liquids nor gases,
having an optimum combination of liquid-like densities
and gas-like transport properties. This application of the
supercritical decoking concept to extend the life of solid
alkylation catalysts may eliminate a major technological
barrier to the use of solid acid catalysts in petroleum re-
lated and other alkylation processes.
A team of University of Notre Dame researchers led
by Dr. Joan Brennecke is studying the behavior of
supercritical CO2 reaction systems. Their findings are di-
rectly applicable to the replacement of organic solvents in
chemical reaction and purification processes. Their pio-
neering basic research on phase equilibria of CO2-based
reaction systems lays a foundation for carrying out indus-
trial chemical reactions without toxic solvents. Their pub-
lished findings document specific conditions under which
Green Cleaning and Related
More than 30 billion pounds
of toxic solvents are used world-wide each year as clean-
ing agents, dispersants and process agents. A team led by
Dr. Joe DiSimone of the University of North Carolina at
Chapel Hill has completed previous research with an en-
vironmentally benign, surfactant modified form of CO2, in
processes that eliminate the use of toxic volatile organic
compounds (VOCs). They received a STAR grant to build
on this research, collecting the data needed to scale-up
the use of compounds that act as soaps in CO2, potentially
replacing VOCs in a wide range of cleaning and other ap-
plications. This research has led to successful commercial-
ization of a new environmentally friendly dry cleaning pro-
cess, using CO2 rather than perchloroethylene. Other in-
dustrial cleaning and solvent applications are also being
commercially explored.
This work involves en-
gineering renewable organic materials to replace petro-
chemicals. Dr. Nancy Ho of Purdue University has made
a significant breakthrough in producing ethanol from cel-
lulose biomass rather than from petrochemical feedstocks,
using yeasts to produce the necessary enzymes. Bioengi-
neering of yeast rather than bacteria allows her to take
advantage of existing, well-defined yeast-based process-
ing methods.
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Their pioneering basic research on phase equilibria of CO2-based reaction systems
lays a foundation for carrying out industrial chemical reactions without toxic solvents.
TSE RESEARCH SUPPORTER RY dryplasma deposition. Dry plasma deposition could elimi-
nate the need for wet chemical processing and resulting
EPA S STAR RESEARCH GRANTS treatment of toxic liquid wastes, and also reduce solid
PROGRAM waste
• UUIlHIf Nearcritical water (NCW) is an environmentally be-
These projects, begun in 1995 to 1998, will be completed from 7999"lign solvent with potential application in the chemical,
through 2002
Green Chemistry and Engineering Methods
for industrial Pollution Prevention
Under a 1998 grant following on their earlier STAR
work described above, the University of Kansas is work-
ing to optimize the solid-acid alkylation process to increase
yields. They are also moving it into new applications, in-
cluding extending the life of catalysts for a chemical syn-
thesis process called skeletal isomerization, and optimiz-
ing solid-catalyzed hydrogenation, a process widely used
in the fine chemicals, pharmaceutical and food industries.
Texas A&M University is also conducting research on solid
acid catalysts for alkylate production. They are using
nuclear magnetic resonance and computational chemis-
try to study in detail the performance of three types
of catalysts.
The University of Iowa is developing an ap-
proach to reduce hazardous waste products from
catalytic chemical syntheses that use zeolites. These
aluminosilicate crystals are used in many processes,
including oil cracking and detergent manufacture.
Researchers are designing reactions to break down
hydrocarbons in a gas phase so that hazardous or-
ganic solvents are not needed. Also, their process
uses solar energy, and so is independent of fossil
fuel energy sources.
Films that coat glass to provide solar shading
are typically metal oxide coatings applied by spray-
ing aerosol powders onto the hot glass. Standard
methods for preparing these powders involve spray-
drying chemicals dissolved in methylene chloride, a
highly volatile and toxic organic solvent whose emis-
sion presents significant environmental and worker
safety concerns. The University of Colorado , work-
ing in technical collaboration with Ford's Class Divi-
sion, has received a STAR grant to develop a pro-
cess for depositing the films with water and supercritical
CO2, using no organic solvents. The researchers will evalu-
ate this method for full scale industrial use. Printed circuit
board manufacturing is also a pollution intensive industry.
Colorado State University is conducting basic research
on properties of films of copper, nickel and gold made by
pharmaceutical and plastics industries. EPA and NSF are
supporting work by the Georgia Institute of Technology
to expand available data on NCW interactions with nu-
merous chemicals. NCW may replace solvents such as aro-
matic hydrocarbons and chlorinated compounds, avoid
the use of strong acids and hazardous catalysts, and mini-
mize byproducts. Under a second EPA grant, the Georgia
Institute of Technology is studying miniemulsion poly-
merization, to help develop water-based polymer coatings
to replace coatings made using organic solvents. Alkyd
resins produced by this process have potential use in hard,
long-lasting coatings with adjustable gloss.
Another Georgia Institute of Technology researcher
is studying high yield membranes, which can be useful in
producing olefins for gasoline, styrene for plastics produc-
tion, and high purity aldehydes used to make flavors and
fragrances. These
membranes offer
technical advan-
tages over ceramic
or metallic mem-
branes in addition to
decreasing overall
waste production
and toxic
byproducts.
In microelectron-
ics manufacturing,
wafers are cleaned
between process
steps using hydrof-
luoric acid (HF),
other acids, bases
and solvents. This
is problematic in
terms of environ-
mental impact, ma-
terial costs, produc-
tivity and disposal costs. The avoidance of aqueous baths
that inherently risk worker exposure would increase safety,
as well as reducing facility floor area needed for the clean-
ing process. The Massachusetts Institute of Technology
is studying a novel HF-water vapor process for in situ dry
cleaning of wafers, to develop it as a replacement for cur-
&EPA
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rent wet cleaning processes in microelectronics manufac-
turing. This "HF-H2O process" for removal of silicon ox-
ides, other oxides and alkali metals greatly reduces the use
of baths of liquid acids, bases and solvents with their asso-
ciated risks. Additional potential process benefits include
the following:
1) very rapid etching rates;
2) allowing the cleaning of layered oxides;
3) the surface after etching is not roughened; and
4) etching rate promotion by patterned wafer sur-
faces can be avoided.
The Massachusetts Institute of Technology (MIT)
has also received joint EPA/NSF funding to develop a new
class of solvents tailored for pollution reduction in the fine
chemical and pharmaceutical industry. Typically, waste
minimization involves
either entirely new syn-
thesis routes, or new
mixtures of tradition-
ally used solvents. The
aim of the MIT re-
search is to modify the
solvents' needed
chemical attributes
and minimize their po-
tential to enter the en-
vironment, while re-
taining their physical
I properties. As an ex-
lam pie, the new tech-
Iniques will be tested
Ifor producing chemi-
Icals used to make the
I HIV protease inhibitor
ICrixivan. One approach is to immobilize solvent molecules
I by attaching them to other large molecules so that they
I do not enter the aqueous wastestream, yet the same criti-
Ical chemical reactions can still take place. Research prod-
lucts will include guidelines for product recovery and sol-
Ivent regeneration, including a complete life cycle analysis
I of the new solvents from synthesis through processing and
I regeneration. Under another grant, Massachusetts Insti-
Itute of Technology scientists are analyzing solvation ef-
Ifects in SCF reaction media. They will attempt to develop
I Raman spectroscopy as an in situ diagnostic technique to
I assess solvation of reactants and the influence of solvent
[density on reaction pathways in SCFs. This will provide
[predictive modeling tools to enhance commercial applica-
tions of SCFs.
EPA and NSF are supporting a partnership project be-
Itween Oklahoma State University and Technology As-
sessment & Transfer Inc. to develop nanocoatings for
cutting tools using "clean manufacturing" methods. One
aspect of the approach involves creating nanocoats on
cemented carbide tools through a process involving no
chemicals and no harmful byproducts. The second aspect
is to use the nanolayer coated tools in dry machining meth-
ods, which greatly reduce environmental releases. Tool
life and wear studies will be conducted experimentally, and
some prototype tools will be provided to users for evalua-
tion.
In research jointlyfunded by EPA and Eastman Kodak,
the Research Triangle Institute of North Carolina is de-
veloping an acid-based catalyst for industrial condensa-
tion products. Over one billion pounds of two condensa-
tion products, methyl isobutyl ketone and 2-ethyl hexanol,
are produced in the
U.S. every year, with
a ratio of about 1:10
of spent catalyst
generation per
pound of product.
Alternative catalysts
produced in lower
volumes will likely
prove to be environ-
mentally benign, re-
sulting in processes
that are cleaner as
well as cheaper.
In a refrigera-
tion study, EPA and
NSF are jointly sup-
porting research at
George Washing-
ton University aimed at developing an experimental "pres-
sure-exchange ejector" system that would use steam as
the refrigerant instead of ozone-depleting chlorofluorocar-
bons (CFCs) or other harmful chemicals.
An important way of evaluating potential hazards of
chemicals that are not yet commercially produced involves
producing compounds in small amounts and subjecting
them to toxicity and carcinogenicity tests. The University
of Massachusetts at Boston is evaluating a way to make
candidate compounds for such studies, replacing time-con-
suming, solvent-based chemical reactions and using sim-
pler, inexpensive and readily available complexing reagents.
The approach, called non-covalent derivation, involves
forming molecular assemblies to manipulate bulk physical
properties of compounds under study. As one example,
one can form an association of the molecules with a simple,
non-toxic water insoluble compound - making thecandi-
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A number of fundamental ^reen chemistry research studies are being supported
that have potentially broad application across various industries.
date compound insoluble without using toxic intermedi-
ate compounds and producing toxic byproducts.
A number of fundamental "green chemistry " research
studies are being supported that have poten-
tially broad application across various indus-
tries. Iowa State University and Virginia
Polytechnical Institute are collaborating to
develop photochemical (light-induced) reac-
tions which, if scaled up for commercial pro-
duction, would reduce the need for toxic re-
agents and byproduct disposal. Industrial pro-
cesses to be studied are acylation, alkylation
and the addition of aldehydes to quinones,
all using environmentally benign supercritical
solvents. An Ohio State University researcher
is investigating ways to better control the
shapes of molecular structures formed in wa-
ter solutions with an indium metal catalyst. A
second grant to Ohio State supports work
with transition metal catalysts and cheap,
abundantly available carbohydrate-derived
ligands to promote water-based syntheses of commercially
important products ranging from amino acids to the widely
used anti-inflammatory drugs called aryl propionic acids.
Decision Support Tools and Process Design
Most precious metal manufacturing involves electro-
plating. There are over 3000 U.S. plants that electroplate
parts with one or a combination of over 100 metallic coat-
ings. This has given rise to waste streams containing a
great variety of potentially toxic pollutants. While a num-
ber of waste minimization (WM) techniques have been
developed, they are not fully in use throughout the indus-
try. This is in part because methods have not been well
classified and compared in terms of cost and efficiency.
Selecting techniques by which particular plants can ac-
complish significant WM while maintaining productivity
at affordable cost is not a trivial task. Wayne State Uni-
versity is developing a decision support system to help
plating plants of any size make sense of the many WM
options and select those optimum for them. Researchers
hope that "deep" WM can be made attractive to more
plant operators based on the ability of a sophisticated com-
puterized knowledge base to help tailor processes to their
needs. The system has been tested by selected plating
plants over the project period, with an ultimate goal of
introducing it throughout the plating industry.
One model pollution prevention approach for indus-
trial plants is conversion to zero discharge processes, with
closed circuits of water replacing standard wastewater dis-
charge cycles. University of Oklahoma researchers are
developing methods to design or retrofit closed circuit wa-
ter cycles for chemical and petrochemical plants, based
on a "state space
approach" origi-
nally developed to
optimize heat and
mass exchanges
in other systems.
The closed circuit
design could al-
low better pollut-
ant interception
and eliminate pol-
lutant discharge
to surface waters.
An other study ap-
plying the state
space approach,
jointly supported
by EPA and NSF, is
being done at Michigan Technological University . The
objective is to create a method by which manufacturers
can construct an "environmentally conscious" state space
model of a product or process system, to predict long term
use and flow of materials and the transient effects of vari-
ous system change options. The program will be devel-
oped based on data for representative large, medium and
small facilities. The initial effort will be to collect data and
build the input/output model for each company. Soft-
ware will be created, and ultimately available on the World
Wide Web.
Two groups are developing life cycle analysis (LCA)
approaches for pollution prevention in a number of indus-
tries. North Carolina State University is developing an
approach relevant to the power generation, waste man-
agement and related industries. As a test case, researchers
will apply their analysis to the waste gasification process.
There are over 3000 U.S\
plants that electroplate part\
with one or a combination
over WO metallic coating i
This has given rise to wash
streams containing a greal
variety of potentially toxil
pollutants]
&EPA
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Factors considered include cost simulation, process per-
formance, energy efficiency and emissions. An important
component is a quantified approach for assessing and
managing the risk involved in using new technologies. It
is hoped that the resulting methodology will be used by
industry and
environmental
agencies in de-
signing and re-
viewing new
process pro-
posals. Re-
searchers at
Carnegie
Mellon Uni-
versity are
working to
streamline
standard LCA
methods,
which are typically very data intensive and thus expensive
and time consuming. A simplified method, Environmen-
tal Input-Output Assessment, has been developed for the
500 economic sectors into which the Department of Com-
merce divides the USA economy. This research will de-
velop the tool in more detail, so that specific products and
processes within the major sectors can be assessed
indipendently. The resulting method and an extended
datbase using EPA discharge data will be provided on the
Internet, together with an interactive user manual.
A potentially widely applicable decision support tool
for industries interested in green chemistry approaches is
being developed by Brandeis University. Scientists there
are developing a computer program to predict the least
environmentally hazardous synthetic routes for making spe-
cific organic compounds. The literature concerning all pre-
cedents for relevant reactions will be searched by the com-
puter program. The fully operational version of the pro-
gram, SYNCEN, will support choosing the synthesis ap-
proach with the least involvement of toxic or carcinogenic
materials throughout the production cycle.
Monitoring Methodology
The ability to conduct accurate, real time measure-
ment of process emissions is important for the success of
industrial pollution prevention. Measurement of gases at
trace levels in a complex background mixture is of particu-
lar concern because many toxic pollutants are present at
parts per trillion (ppt) to parts per million (ppm) levels in
process emissions. The University of Colorado at Boul-
der is developing real time and ultrasensitive detection
techniques to monitor a wide range of molecules in the
gas phase, using resonance enhanced multiphoton ion-
ization (REMPI) and time of flight (TOP) mass spectrom-
etry. The new techniques are expected to be particularly
useful for monitoring the products of fossil fuel combus-
tion, including trace levels of aromatics, polycyclic aromatic
hydrocarbons and dioxins and their derivatives, some of
which are highly toxic.
Biotechnology
Producing organic chemicals from resources other than
petrochemical feedstocks can eliminate toxic precursor
chemicals and byproducts and reduce dependence on non-
renewable petrochemical supplies. Biotechnology meth-
ods involving bacteria offer many cost-effective and envi-
ronmentally benign substitutions for petrochemical-based
chemical production. The University of Wisconsin at
Madison has received a STAR grant to investigate produc-
ing propylene glycol using natural sugar fermentation by
the bacterium Clostridium thermosaccharolyticumPropy-
lene glycol is, among other uses, a less toxic replacement
for ethylene glycol in antifreeze, with an annual produc-
tion in the US of over one billion pounds, with a rapidly
expanding market.
Researchers at Michigan State University are using
genetically modified bacteria to make resorcinol from the
natural sugar glocose. Resorcinol is a chemical building
block with uses ranging from wood adhesives and tire
manufacture to the synthesis of sunblocks and throat loz-
enges. It is currently
made from benzene,
which is carcinogenic.
This basic research is as-
sessing chemical path-
ways by which resorci-
nol can be most effec-
tively and practically
synthesized. The focus
is on the pathways of
polyketide biosynthesis
and fatty acid biosyn-
thesis, rather than on
previously tried ap-
proaches involving aro-
matic amino acid bio-
synthesis.
University of
Florida researchers are combining two environmentally
safer approaches to making pharmaceuticalsand other fine
1
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Biotechnology methods involving bacteria offer many cost-effective and
environmentally benign substitutions for petrochemical-based chemical production.
chemicals: 1) electrochemistry, by which oxidation and
reduction reactions are mediated without organic solvents
or harsh reaction conditions, and 2) biocatalysis, in which
recombinant organisms and soil bacteria with certain genes
blocked convert aromatic compounds to specific high qual-
ity biochemical reagents. Using these methods in tandem
is expected to produce needed biochemical compounds
with little creation of new toxic byproducts. In some cases,
toxic chemicals can be used as feedstocks, resulting in a
net decrease in toxics for which safe disposal methods must
be found.
Recycling and Reuse, and the Use of
Riodegradable Materials
Thefilms, coatings and foams used in huge quantities
in packaging constitute a high percentage of the plastics
in municipal waste. These typically are not biodegrad-
able, and the packaging cannot be recycled without ex-
cessive cost and environmental burden. The University of
Massachusetts at Lowell is doing research to develop sub-
stitutes from naturally abundant, renewable and biode-
gradable resource materials such as cellulose, starch, chitin
and other materials. Although there has been some suc-
cess with a first generation of such materials, they some-
times fail to meet needed performance standards. The
current study will focus on product quality concerns, and
emphasizes water-based technologies to reduce chemical
pollution in the produc-
tion process. Wayne
State University is also
investigating ways to re-
place petrochemical-de-
rived products with bio-
degradable materials
from agricultural
byproducts. They are
focusing on two lan-
thanide catalyst-based
processes: 1) synthesiz-
ing cellulose ethers for
a variety of industrial ap-
plications, and 2) graft-
ing polyesters onto
polysaccharides to pro-
duce novel copolymers
that should combine
water-soluble and in-
soluble properties and may be useful as new biodegrad-
able materials. The Colorado School of Mines is de-
veloping a method for producing industrial scale quan-
tities of polylactic acid (PLA) from agricultural feedstocks,
also for use in packaging materials. PLA degrades to
non-toxic lactic acid, can also be made into compostable
packaging, and can be tailored through combination
with other materials to meet a wide variety of packag-
ing needs. The
University of
Washington is also
developing bacte-
ria that can use re-
newable feed-
stocks rather than
petrochemicals to
make needed
products. They are
trying to develop
an optimized strain
of the bacterium
Me thylo bacterium
extorguensAMI to
convert methanol
into products such
as the biodegrad-
able plastic
polybetahydroxy-butyrate, focusing on directing carbon
flux into the most efficient metabolic pathways by ma-
nipulating the bacterial strain's pathways for formalde-
hyde production and consumption.
To examine cleaner processes based
on biodegradable materials, Michigan
State University has developed software
called the Biodegradation Evaluation and
Simulation System (BESS). This predicts
the biodegradability of a compound based
its structure and prevailing environmental
conditions. The University has been
awarded a STAR grant to refine BESS by
organizing data on plausible enzyme trans-
formations based on knowledge of micro-
bial ecology and physiology. This reduces
the potentially large number of transfor-
mations that might be relevant, making
the information searching computationally
feasible. BESS is intended to serve at least
three functions: (a) to allow biodegrad-
ability to be considered early in product
development; (b) for use by regulatory
agencies in decisions regarding testing; and (c) as a tu-
torial to teach users what features of chemicals and the
wEPA
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environment restrict or promote biodegradation.
Although a number of processes have been devel-
oped or proposed for separation of waste plastics from
manufacturing, none are completely satisfactory in terms
of cost and performance. Brown University is con-
ducting basic research to provide a technical basis for
the development of a novel, liquid-fluidized bed classi-
fication (LFBC) technology for continuously separating
complex waste plastic mixtures for in-process recycling
and waste minimization. LFBC has a number of poten-
tial advantages: 1) It can be used to separate a num-
ber of particle types simultaneously, while other pro-
cesses can only separate "lights" from "heavies"; 2)
only unmodified water is required, eliminating the need
for separation and recovery of water density modifying
agents; and 3) unlike other denisty-based methods,
processes to separate particles of different sizes but simi-
lar densities can be can be performed in conjunction
with LFBC. LFBC is compatible with most other separa-
tion/identification methods, so it could be used in con-
junction with other technology to improve overall cost
efficiency. Data will be collected on dispersion and sepa-
ration performance as related to factors such as particle
size and engineering factors, particularly for irregularly
shaped particles. These data and a model derived from
them will be the basis for process design and an eco-
nomic analysis of commercialization potential. A po-
tential industrial partner has been identified, and USEPA's
New England regional office has indicated an interest
in the project.
Grants described in this report are part of EPA's Science to Achieve Re-
sults (STAR) program, a major research initiative designed to improve
the quality of scientific information available to support environmental
decision making. The STAR program is managed by EPA's National
Center for Environmental Research and Quality Assurance in the Office
of Research and Development (ORD). The program funds approxi-
mately 190 new grants every year, with the typical grant lasting three
years. Funding levels vary from $50,000 to over $500,000 per year,
with FY 1999 funding level at about $95 million for grants to individual
principal investigators or groups of investigators. Additional STAR funds
are provided for a number of Research Centers specializing in scientific
areas of particular concern to EPA, and for fellowship programs sup-
porting graduate students conducting environmental research.
TSE Project Publications for Work
Described in "Early Results" Section
University of Kansas (KS)
B. Subramanian, "Applications
of Supercritical Reaction Media
in Fuels Production", seminar
presented at Center for Applied
Energy Research, University of
Kentucky. January 27, 1998.
University of North Carolina
(NC) Dardin, A.; Cain, J. B.;
DeSimone, J. M.; Johnson, Jr.,
C. S.; Samulski, E. T. "High-
Pressure NMR of Polymers
Dissolved in Supercritical
Carbon Dioxide", Macromol-
ecules, 1997, 30, 3593-3599.
Clark, M. R.; Kendall, J. L;
DeSimone, J. M., "Cationic
Dispersion Polymerization in
Liquid Carbon Dioxide",
Macromolecules, 1997, 30,
6011-6014.
Canelas, D. A.; DeSimone, J.
M., "Polymerizations in Liquid
and Supercritical Carbon
Dioxide", Adv. Polym. Sci.,
1997, 133, 103-140.
Cooper, A. I.; Londono, J. D.;
Wignall, G.; McClain, J. B.;
Samulski, E. T.; Lin, J. S.;
Dobrynin, A.; Rubenstein, M.;
Burke, A. L. C.; Frechet, J. M. J.;
DeSimone, J. M., "Extraction of
a Hydrophilic Compound From
Water Into Liquid CO2 Using
Dendritic Surfactants", Nature,
1997,389,368-371.
Commercial website, Dr
DiSimone's MiCELL Technolo-
gies company:
http://www.micell.com
University of Notre Dame (IN)
Benito A. Stradi, James P. Kohn,
Mark A. Stadtherr and Joan F.
Brennecke, "Phase Behavior of
the Reactants, Products and
Catalysts Involved in the Allylic
Epoxidation of trans-2-Hexen-1-
ol to(2R,3R)-(+)-3-
Propyloxiramethanol in High
Pressure Carbon Dioxide," J.
Supercritical Fluids, 12, 1998,
p. 109-122.
James Z. Hua, Robert W. Maier,
Steven R. Tessier, Joan F.
Brennecke and Mark A.
Stadtherr, "Interval Analysis for
Thermodynamic Calculations in
Process Design: A Novel and
Completely Reliable Approach,"
Fluid Phase Equilibria, accepted
for publication, 1998.
University of Pittsburgh (PA)
A. Chaudhary, J. Lopez, E.J.
Beckman, A.J. Russell,
"Biocatalytic Solvent-Free
Polymerization to Produce High
Molecular Weight Polyesters",
Biotech. Progr. (1997), 13, 318
Purdue University (IN)
N.W. Y. Ho, Z. D.Chen, M.
Sedlak, S. Mohammad, and A.
Brainard. "Factors Crucial for
Recombinant Saccharomyces
Effective in Fermenting Xylose".
Paper presented at Twentieth
Symposium on Biotechnology
for Fuels and Chemicals", May
3-7, 1 998, Gatlinburg,
Tennessee, USA. Abstract, 28-
Aug-1998, at Oak Ridge
National Laboratory website:
http://www.ornl.gov/divisions/
ctd/Chem_Dev/Biochemical/
Abstracts/PaperList.htm
(Paper09).
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Biotechnology methods involving bacteria offer many cost-effective and
environmentally benign substitutions for petrochemical-based chemical production.
Research Projects
Described in This Report
1995 EPA Awards
Ohio State University (OH)
Opportunities Offered by
Indium-Promoted Carbon Bond
Forming Reactions in Water
University of Wisconsin (Wl)
Fermentation of Sugars to 1,2
Propanediol by Clostridium
thermosaccharolyticum
Georgia Institute of Technol-
ogy (GA) High-Yield Mem-
brane Reactors
University of Colorado-
Boulder (CO) Replacement of
Organic Solvents by Carbon
Dioxide for Forming Aerosols in
Coating Processes
University of Kansas (KS)
Coking and Activity of Solid-
Acid Alkylation in Supercritical
Reaction Media
University of Notre Dame (IN)
Phase Equilibria of CO2-Based
Reaction Systems
Wayne State University (Ml)
Intelligent Decision Making and
System Development for
Comprehensive Waste
Minimization in the Electroplat-
ing Industry
University of Pittsburgh (PA)
Biocatalyst of Polymers in
Carbon Dioxide
1996 EPA Awards
University of Iowa (IA)
Environmentally Benign Photo-
assisted Catalysis:
SelectiveOxidation Reactions in
Zeolites
Georgia Institute of Technol-
ogy (GA) Water-Based
Coatings via Miniemulsion
Polymerization
Research Triangle Institute
(NC) Pollution Prevention in
Industrial Condensation
Reactions
University of Massachusetts-
Boston (MA) Pollution
Prevention with the Use of
Molecular Assemblies
Iowa State University (IA)
Photochemical Alternatives for
Pollution Prevention
University of Oklahoma (OK)
Chemical Plant Wastewater
Reuse and Zero Discharge
Cycles
Brandeis University (MA )
Environmental Hazard
Assessment for Computer
Generated Alternative Synthe-
ses
1996 Joint EPA/NSF Awards
George Washington Univer-
sity (DC) A Novel Pressure-
Exchange Ejector Refrigeration
System with Steam as the
Refrigerant
Georgia Institute of Technol-
ogy (GA) Near-Critical Water
for Environmentally Benign
Chemical Processing
Michigan Technological
University (Ml) Environmen-
tally Conscious Design and
Manufacturing with Input-
Analysis and Markovian
Decision Making
Oklahoma State University
(OK) Novel Nanocoatings on
Cutting Tools for Dry Machin-
ing
University of Pittsburgh (PA)
Biocatalytic Polymer Synthesis
in and from Carbon Dioxide for
Pollution Prevention
1996 NSF Awards
University of Massachusetts-
Lowell (MA) Bioengineering of
Biosurfactants for Cleaning and
Degreasing Applications
Augustana College (SD)
Preparation of More-Biofriendly
Quarternary Ammonium
Compounds and their
Decomposition to Useful
Reagents
Kansas State University (KS)
Two-Stage Fermentation of
Whey Permeate for Biodegrad-
able Deicer Production
Washington State University
(WA) Coexisting Chemical-
Biological Modifications of
Chlorinated Solvents as a Basis
for Waste Reduction in Pollution
Prevention
University of Massachusetts-
Amherst (MA) Reactive
Distillation Systems for Waste
Reduction and Productivity
Improvement
University of Dayton (OH)
Back-End Modifications of
Portland Cement Plants to
Reduce Emissions of Hazardous
Air Pollutant
University of Tennessee (TN)
Molecular-Based Study of
Reversed Micelles in
Supercritical in CO2 for
Solvents Substitution in the U.S.
Chemical Industry
Dartmouth College (NH)
Conversion of Paper Sludge to
Ethanol and Potentially
Recyclable Minerals
Arizona State University (AZ)
Environmentally-Benign
Processing of Low Dielectric
Constant Polymers for
Microelectronics Applications
University of California (CA)
Hydrogen Formation and
Transfer in Alkane Reactions
Catalyzed by Cation-Modified
Zeolites
University of Maryland-
Baltimore (MD) Advanced
Fluorescence-Based Environ-
mental Sensors
Carnegie Mellon University
(PA)
Iron Catalysts for Bleach
Avtivation Funded by NSF
1997 EPA Awards
University of North Carolina
at Chapel Hill (NC) Non-ionic
Surfactants for Dispersion
Polymerization in Carbon
Dioxide
Michigan State University (Ml)
Environmentally Benign
Synthesis of Resorcinol from
Glucose
Engineering Purdue Univer-
sity (IN) Development of
Biotechnology to Sustain the
Production of Environmentally
Friendly Transportation Fuel
Ethanol from Cellulosic Biomass
University of Florida (FL)
Synthetic Methodology
"Without Reagents" Tandem
Enzymatic and Electrochemical
Techniques for the Manufac-
turing of Fine Chemicals
University of Massachusetts at
Lowell (MA) Aqueous
Processing of Biodegradable
Materials from Renewable
Resources
Michigan State University (Ml)
BESS, A System for Predicting
the Biodegradability of New
Compounds
Ohio State University (OH)
Catalysts for Environmentally
Benign Organic Reactions in
Water
Colorado State University (CO)
Microstructural, Morphological
and Electrical Studies of a
Unique Dry Plasma Metal
Deposition for Printed Circuit
Boards (PCBs)
1997 Joint EPA/NSF Awards
Massachusetts Institute of
Technology (MA) Tailored
Solvents for Pollution Source
Reduction in Pharmaceutical
and Fine Chemical Processing
Texas A &t M University (TX)
Combined NMR and Theoreti-
cal Investigation of Alkylation
Reactions on Solid Acids
Wayne State University (Ml)
Development of Green
Chemistry for Syntheses of
Polysaccharide-Based Materials
1997 NSF Awards
Purdue University (IN) An
Integrated Approach to
Environmentally Conscious
Paper Mill Operations
-------
"Green" chemistry and engineering - environmentally friendly, energy efficient approaches for use in industrial processes - are a major
area of emphasis in the joint EPA/NSF research program on Technology for a Sustainable Environment (TSE) since its inception in 1995.
University of Florida (FL)
Synthesis and Characterization
of Solid Acids
Cornell University (NY) In-
Vivo Synthesis of Lepidopteran
Pheromone Precursors in
Saccharomyces cereviseae
Purdue University (IN)
Cellulose Conversion Using
Aqueous Pretreatment and
Cellulose Enzyme Mimetic
Tulane University (LA)
Water as Solvent for Metal-
Mediated Carbon-Carbon Bond
Formations
University of Washington at
Seattle (WA) Ion Exchange
without Chemical Regenera-
tion: Raman Spectroscopy
Studies of Hexacyanoferrate
Derivatized Electrodes
1998 EPA Awards
University of Notre Dame (IN)
Multiphase Reactive Equilibria
of CO2-based Systems
Brown University (Rl)
Continuous Micro-Sorting of
Complex Waste Plastics Particle
Mixtures Via Liquid-Fluidized
Bed Classification for Waste
Minimization and Recycling
Colorado School of Mines (CO)
Environmentally Benign
Polymeric Packaging from
Renewal
North Carolina State
University (NC)
New Methods for Assessment
of Pollution Prevention
Technologies: Integration of
Probabilistic Process Modeling
and Design; Life-Cycle Analysis;
and Regional Environmental
Benefits Assessment
Carnegie Mellon University
(PA)
Economic Input-Output Life
Cycle Assessment: A Tool to
Improve Analysis of Environ-
mental Quality and
Sustainability
University of Washington at
Seattle (WA) Metabolic
Engineering of Methylotrophic
Bacteria for Conversion of
Methanol to Higher Value
Added Products
Carnegie Mellon University
(PA)
Elimination of VOCs in the
Synthesis and Application of
Polymeric Materials Using Atom
University of Colorado -
Boulder (CO) Optimal
Operation of Electric Arc
Furnaces to Minimize the
Generation of Air Pollutants at
the Source
University of Alabama (AL)
Polymer-Based Aqueous
Biphasic Extraction Technology
for Reaction Engineering of the
Alkaline Paper Pulping Process
University of California at Los
Angeles (CA) Real-Time,
Ultrasensitive Measurement of
Process Emissions for Pollution
Prevention
Massachusetts Institute of
Technology (MA)
In Situ Diagnostic Techniques
for Probing Solvation Effects in
Supercritical Fluid Reaction
Media for Synthetic Organic
Chemistry
University of Kansas (KS)
Solid-Catalyzed Reactions in
Supercritical Reaction Media
University of Alabama (AL)
Solventless, Electron Beam-
Cured Vinyl Ether Coating
Formulations for Flexible
Magnetic Media Manufacture
Massachusetts Institute of
Technology (MA) Alternative
Wafer Cleaning Using HF-H2O
Processing
1998 NSF Awards
University of Kansas (KS)
Catalytic Oxidations in
Supercritical Carbon Dioxide
Massachusetts Institute of
Technology (MA) Collodial
Ferrofluids as Reactive
Extractants for Sulfur Removal
from Gasoline and Fuel Oils
North Carolina State
University (NC) Towards a
Greening of the Petroleum
Industry: Minimizing Emulsion
and Foam Formation
Lehigh University (PA)
Dynamically Responsive
Polymeric Additives for Process
Improvements an Environmen-
tal Compability
University of Akron (OH)
Environmentally Benign CO
Insertion
Wayne State University (Ml)
Polymer Processing With
Supercritical Fluid Solvents
Brown University (Rl)
Continuous Micro-Sorting of
Complex Waste Plastics
Mixtures via Liquid-Fluidized
Bed Classification (LFBC) for
Waste Minimization and
Recycling
SEPA
United States
Environmental Protection Agency
Mail Code 8701R
Washington, D.C. 20460
Offical Business
Penalty for Private Use
$300
EPA/600/F-99/015
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