9

STAR

REPORT

Vol. 3 Issue 3 November 1999 A product of the National Center for Environmental Research and Quality Assurance

EARLY RESULTS FROM TSE STAR RESEARCH GRANTS

U.S. EPA Office of Research

and Development’s Science

To Achieve Results (STAR)

Research in Progress

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 commercial 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 applications, typically uses strong acids as catalysts. Alkylates are blending agents in

gasoline formulation. Because

they contain virtually no toxic

components, alkylates

are playing an increasingly 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 commercial substances and environmentally friendly chemical syntheses to reduce risks posed by existing practices.
emissions gasoline requirements established by the 1990

Clean Air Act. However, alkylation presents environmental and safety concerns because of two factors: 1) health,

safety and environmental problems from liquid acid spillage, and 2) the need to dispose of toxic by-products. Developing “environmentally-friendlier” alkylation is thus especially 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 University of Kansas , working under a STAR grant, has demonstrated 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 related 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 directly applicable to the replacement of organic solvents in

chemical reaction and purification processes. Their pioneering basic research on phase equilibria of CO2

-based

reaction systems lays a foundation for carrying out industrial chemical reactions without toxic solvents. Their published findings document specific conditions under which

the CO2 solvents can be used, for example a potentially widespread application in polymer manufacturing that

requires forming epoxides from 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 petrochemical and plastics industries, EPA

and NSF supported research by Drs.

Alan Russell and Eric Beckman along

with a team at the University of Pittsburgh , investigating the use of

supercritical CO2 to make polyester intermediates for urethane production.

Their published findings provide a

framework around which commercially viable processes can be developed.

Green Cleaning and Related

Processes Results More than 30 billion pounds

of toxic solvents are used world-wide each year as cleaning 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 environmentally 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 applications. This research has led to successful commercialization of a new environmentally friendly dry cleaning process, using CO2

 rather than perchloroethylene. Other industrial cleaning and solvent applications are also being

commercially explored.

Biotechnology Results This work involves engineering renewable organic materials to replace petrochemicals. Dr. Nancy Ho of Purdue University has made

a significant breakthrough in producing ethanol from cellulose biomass rather than from petrochemical feedstocks,

using yeasts to produce the necessary enzymes. Bioengineering of yeast rather than bacteria allows her to take

advantage of existing, well-defined yeast-based processing methods.

2
TSE RESEARCH SUPPORTED BY

EPA’S STAR RESEARCH GRANTS

PROGRAM

These projects, begun in 1995 to 1998, will be completed from 1999

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 working to optimize the solid-acid alkylation process to increase

yields. They are also moving it into new applications, including extending the life of catalysts for a chemical synthesis process called skeletal isomerization, and optimizing 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 chemistry to study in detail the performance of three types

of catalysts.

The University of Iowa is developing an approach 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 organic 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 spraying aerosol powders onto the hot glass. Standard

methods for preparing these powders involve spraydrying chemicals dissolved in methylene chloride, a

highly volatile and toxic organic solvent whose emission presents significant environmental and worker

safety concerns. The University of Colorado , working in technical collaboration with Ford’s Glass Division, has received a STAR grant to develop a process for depositing the films with water and supercritical

CO2, using no organic solvents. The researchers will evaluate 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

dry plasma deposition. Dry plasma deposition could eliminate the need for wet chemical processing and resulting

treatment of toxic liquid wastes, and also reduce solid

waste.

Nearcritical water (NCW) is an environmentally benign solvent with potential application in the chemical,

pharmaceutical and plastics industries. EPA and NSF are

supporting work by the Georgia Institute of Technology

to expand available data on NCW interactions with numerous chemicals. NCW may replace solvents such as aromatic hydrocarbons and chlorinated compounds, avoid

the use of strong acids and hazardous catalysts, and minimize byproducts. Under a second EPA grant, the Georgia

Institute of Technology is studying miniemulsion polymerization, 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 production, and high purity aldehydes used to make flavors and

fragrances. These

membranes offer

technical advantages over ceramic

or metallic membranes in addition to

decreasing overall

waste production

and toxic

byproducts.

 In microelectronics manufacturing,

wafers are cleaned

between process

steps using hydrofluoric acid (HF),

other acids, bases

and solvents. This

is problematic in

terms of environmental impact, material costs, productivity 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 cleaning 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 curTheir pioneering basic research on phase equilibria of CO2

-based reaction systems

lays a foundation for carrying out industrial chemical reactions without toxic solvents.

3
rent wet cleaning processes in microelectronics manufacturing. This “HF-H2O process” for removal of silicon oxides, other oxides and alkali metals greatly reduces the use

of baths of liquid acids, bases and solvents with their associated 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 synthesis routes, or new

mixtures of traditionally used solvents. The

aim of the MIT research is to modify the

solvents’ needed

chemical attributes

and minimize their potential to enter the environment, while retaining their physical

properties. As an example, the new techniques will be tested

for producing chemicals used to make the

HIV protease inhibitor

Crixivan. One approach is to immobilize solvent molecules

by attaching them to other large molecules so that they

do not enter the aqueous wastestream, yet the same critical chemical reactions can still take place. Research products will include guidelines for product recovery and solvent regeneration, including a complete life cycle analysis

of the new solvents from synthesis through processing and

regeneration. Under another grant, Massachusetts Institute of Technology scientists are analyzing solvation effects in SCF reaction media. They will attempt to develop

Raman spectroscopy as an in situ diagnostic technique to

assess solvation of reactants and the influence of solvent

density on reaction pathways in SCFs. This will provide

predictive modeling tools to enhance commercial applications of SCFs.

EPA and NSF are supporting a partnership project between Oklahoma State University and Technology Assessment & 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 methods, which greatly reduce environmental releases. Tool

life and wear studies will be conducted experimentally, and

some prototype tools will be provided to users for evaluation.

In research jointly funded by EPA and Eastman Kodak,

the Research Triangle Institute of North Carolina is developing an acid-based catalyst for industrial condensation products. Over one billion pounds of two condensation 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 environmentally benign, resulting in processes

that are cleaner as

well as cheaper.

In a refrigeration study, EPA and

NSF are jointly supporting research at

George Washington University aimed at developing an experimental “pressure-exchange ejector” system that would use steam as

the refrigerant instead of ozone-depleting chlorofluorocarbons (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-consuming, solvent-based chemical reactions and using simpler, 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 the candi4
date compound insoluble without using toxic intermediate compounds and producing toxic byproducts.

A number of fundamental “green chemistry ” research

studies are being supported that have potentially broad application across various industries. Iowa State University and Virginia

Polytechnical Institute are collaborating to

develop photochemical (light-induced) reactions which, if scaled up for commercial production, would reduce the need for toxic reagents and byproduct disposal. Industrial processes 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 water 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 electroplating. There are over 3000 U.S. plants that electroplate

parts with one or a combination of over 100 metallic coatings. This has given rise to waste streams containing a

great variety of potentially toxic pollutants. While a number of waste minimization (WM) techniques have been

developed, they are not fully in use throughout the industry. 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 accomplish significant WM while maintaining productivity

at affordable cost is not a trivial task. Wayne State University 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 computerized 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 industrial plants is conversion to zero discharge processes, with

closed circuits of water replacing standard wastewater discharge cycles. University of Oklahoma researchers are

developing methods to design or retrofit closed circuit water cycles for chemical and petrochemical plants, based

on a “state space

approach” originally developed to

optimize heat and

mass exchanges

in other systems.

The closed circuit

design could allow better pollutant interception

and eliminate pollutant discharge

to surface waters.

Another study applying 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 various system change options. The program will be developed 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. Software 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 industries. North Carolina State University is developing an

approach relevant to the power generation, waste management 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 parts

with one or a combination of

over 100 metallic coatings.

This has given rise to waste

streams containing a great

variety of potentially toxic

pollutants.

5

A number of fundamental “green chemistry” research studies are being supported

that have potentially broad application across various industries.
Factors considered include cost simulation, process performance, 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 designing and reviewing new

process proposals. Researchers at

C a r n e g i e

Mellon University are

working to

s t r e a m l i n e

standard LCA

m e t h o d s ,

which are typically very data intensive and thus expensive

and time consuming. A simplified method, Environmental Input-Output Assessment, has been developed for the

500 economic sectors into which the Department of Commerce divides the USA economy. This research will develop 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 specific organic compounds. The literature concerning all precedents for relevant reactions will be searched by the computer program. The fully operational version of the program, SYNGEN, will support choosing the synthesis approach with the least involvement of toxic or carcinogenic

materials throughout the production cycle.

Monitoring Methodology

The ability to conduct accurate, real time measurement 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 particular 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 Boulder is developing real time and ultrasensitive detection

techniques to monitor a wide range of molecules in the

gas phase, using resonance enhanced multiphoton ionization (REMPI) and time of flight (TOF) mass spectrometry. The new techniques are expected to be particularly

useful for monitoring the products of fossil fuel combustion, 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 nonrenewable petrochemical supplies. Biotechnology methods involving bacteria offer many cost-effective and environmentally benign substitutions for petrochemical-based

chemical production. The University of Wisconsin at

Madison has received a STAR grant to investigate producing propylene glycol using natural sugar fermentation by

the bacterium Clostridium thermosaccharolyticum. Propylene glycol is, among other uses, a less toxic replacement

for ethylene glycol in antifreeze, with an annual production 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 lozenges. It is currently

made from benzene,

which is carcinogenic.

This basic research is assessing chemical pathways by which resorcinol can be most effectively and practically

synthesized. The focus

is on the pathways of

polyketide biosynthesis

and fatty acid biosynthesis, rather than on

previously tried approaches involving aromatic amino acid biosynthesis.

 University of

Florida researchers are combining two environmentally

safer approaches to making pharmaceuticals and other fine

6
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 quality 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

Biodegradable Materials

The films, coatings and foams used in huge quantities

in packaging constitute a high percentage of the plastics

in municipal waste. These typically are not biodegradable, and the packaging cannot be recycled without excessive cost and environmental burden. The University of

Massachusetts at Lowell is doing research to develop substitutes from naturally abundant, renewable and biodegradable resource materials such as cellulose, starch, chitin

and other materials. Although there has been some success with a first generation of such materials, they sometimes 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 production process. Wayne

State University is also

investigating ways to replace petrochemical-derived products with biodegradable materials

from agricultural

byproducts. They are

focusing on two lanthanide catalyst-based

processes: 1) synthesizing cellulose ethers for

a variety of industrial applications, and 2) grafting polyesters onto

polysaccharides to produce novel copolymers

that should combine

water-soluble and insoluble properties and may be useful as new biodegradable materials. The Colorado School of Mines is de7

Biotechnology methods involving bacteria offer many cost-effective and

environmentally benign substitutions for petrochemical-based chemical production.

veloping a method for producing industrial scale quantities 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 packaging needs. The

University of

Washington is also

developing bacteria that can use renewable feedstocks rather than

petrochemicals to

make needed

products. They are

trying to develop

an optimized strain

of the bacterium

Methylobacterium

extorquens AM1 to

convert methanol

into products such

as the biodegradable plastic

polybetahydroxy-butyrate, focusing on directing carbon

flux into the most efficient metabolic pathways by manipulating the bacterial strain’s pathways for formaldehyde 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 transformations based on knowledge of microbial ecology and physiology. This reduces

the potentially large number of transformations that might be relevant, making

the information searching computationally

feasible. BESS is intended to serve at least

three functions: (a) to allow biodegradability to be considered early in product

development; (b) for use by regulatory

agencies in decisions regarding testing; and (c) as a tutorial to teach users what features of chemicals and the
environment restrict or promote biodegradation.

Although a number of processes have been developed or proposed for separation of waste plastics from

manufacturing, none are completely satisfactory in terms

of cost and performance. Brown University is conducting basic research to provide a technical basis for

the development of a novel, liquid-fluidized bed classification (LFBC) technology for continuously separating

complex waste plastic mixtures for in-process recycling

and waste minimization. LFBC has a number of potential advantages: 1) It can be used to separate a number of particle types simultaneously, while other processes 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 similar densities can be can be performed in conjunction

with LFBC. LFBC is compatible with most other separation/identification methods, so it could be used in conjunction with other technology to improve overall cost

efficiency. Data will be collected on dispersion and separation 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 economic analysis of commercialization potential. A potential industrial partner has been identified, and USEPA’s

New England regional office has indicated an interest

in the project.

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. "HighPressure NMR of Polymers

Dissolved in Supercritical

Carbon Dioxide", Macromolecules, 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 Technologies 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, 1998, 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).

TSE Project Publications for Work

Described in “Early Results” Section

Grants described in this report are part of EPA’s Science to Achieve Results (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 approximately 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 supporting graduate students conducting environmental research.

8
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 (WI)

Fermentation of Sugars to 1,2

Propanediol by Clostridium

thermosaccharolyticum

Georgia Institute of Technology (GA) High-Yield Membrane Reactors

University of ColoradoBoulder (CO) Replacement of

Organic Solvents by Carbon

Dioxide for Forming Aerosols in

Coating Processes

University of Kansas (KS)

Coking and Activity of SolidAcid Alkylation in Supercritical

Reaction Media

University of Notre Dame (IN)

Phase Equilibria of CO2-Based

Reaction Systems

Wayne State University (MI)

Intelligent Decision Making and

System Development for

Comprehensive Waste

Minimization in the Electroplating Industry

University of Pittsburgh (PA)

Biocatalyst of Polymers in

Carbon Dioxide

1996 EPA Awards

University of Iowa (IA)

Environmentally Benign Photoassisted Catalysis:

SelectiveOxidation Reactions in

Zeolites

Georgia Institute of Technology (GA) Water-Based

Coatings via Miniemulsion

Polymerization

Research Triangle Institute

(NC) Pollution Prevention in

Industrial Condensation

Reactions

University of MassachusettsBoston (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 Syntheses

1996 Joint EPA/NSF Awards

George Washington University (DC) A Novel PressureExchange Ejector Refrigeration

System with Steam as the

Refrigerant

Georgia Institute of Technology (GA) Near-Critical Water

for Environmentally Benign

Chemical Processing

Michigan Technological

University (MI) Environmentally Conscious Design and

Manufacturing with InputAnalysis and Markovian

Decision Making

Oklahoma State University

(OK) Novel Nanocoatings on

Cutting Tools for Dry Machining

University of Pittsburgh (PA)

Biocatalytic Polymer Synthesis

in and from Carbon Dioxide for

Pollution Prevention

1996 NSF Awards

University of MassachusettsLowell (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 Biodegradable Deicer Production

Washington State University

(WA) Coexisting ChemicalBiological Modifications of

Chlorinated Solvents as a Basis

for Waste Reduction in Pollution

Prevention

University of MassachusettsAmherst (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 MarylandBaltimore (MD) Advanced

Fluorescence-Based Environmental 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 (MI)

Environmentally Benign

Synthesis of Resorcinol from

Glucose

Engineering Purdue University (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 Manufacturing of Fine Chemicals

University of Massachusetts at

Lowell (MA) Aqueous

Processing of Biodegradable

Materials from Renewable

Resources

Michigan State University (MI)

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 & M University (TX)

Combined NMR and Theoretical Investigation of Alkylation

Reactions on Solid Acids

Wayne State University (MI)

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

Biotechnology methods involving bacteria offer many cost-effective and

environmentally benign substitutions for petrochemical-based chemical production.

9
United States

Environmental Protection Agency

Mail Code 8701R

Washington, D.C. 20460

Offical Business

Penalty for Private Use

$300

EPA/600/F-99/015

University of Florida (FL)

Synthesis and Characterization

of Solid Acids

Cornell University (NY) InVivo 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 MetalMediated Carbon-Carbon Bond

Formations

University of Washington at

Seattle (WA) Ion Exchange

without Chemical Regeneration: Raman Spectroscopy

Studies of Hexacyanoferrate

Derivatized Electrodes

1998 EPA Awards

University of Notre Dame (IN)

Multiphase Reactive Equilibria

of CO2-based Systems

Brown University (RI)

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 Environmental 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 VOC's 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 BeamCured 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 Environmental Compability

University of Akron (OH)

Environmentally Benign CO

Insertion

Wayne State University (MI)

Polymer Processing With

Supercritical Fluid Solvents

Brown University (RI)

Continuous Micro-Sorting of

Complex Waste Plastics

Mixtures via Liquid-Fluidized

Bed Classification (LFBC) for

Waste Minimization and

Recycling

"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.