fQ\ The Presidential
Green Chemistry Challenge
Awards Program:
Summary of 2008 Award
Entries and Recipients
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An electronic version of this document is available at:
http: //www. epa. gov/ greenchemistry
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Environmental Protection Prevention and June 2008
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The Presidential Green Chemistry
Challenge Awards Program:
Summary of 2008 Award Entries
and Recipients
Contents
Introduction .................................................. 1
Awards ...................................................... 3
Academic Award 3
Small Business Award 4
Greener Synthetic Pathways Award 5
Greener Reaction Conditions Award 6
Designing Greener Chemicals Award 7
Entries from Academia .......................................... 9
Entries from Small Businesses 17
Entries from Industry and Government 33
Index ...................................................... 55
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Introduction
The Presidential Green Chemistry Challenge Awards Program is a competitive incentive
to create environmentally preferable chemicals and chemical processes. Each year the United
States Environmental Protection Agency (EPA) celebrates innovative, award-winning tech-
nologies developed by high-quality nominees. The year 2008 marks the 13th year of the
program. This compilation summarizes the entries submitted for the 2008 awards. Five of
the more than 90 entries were nationally recognized on June 24, 2008, at an awards cere-
mony in Washington, D.C.
The national policy established by the 1990 Pollution Prevention Act is aimed at reduc-
ing pollution at its source whenever feasible. By applying scientific solutions to real-world
environmental problems, the Green Chemistry Challenge has significandy reduced the haz-
ards associated with designing, manufacturing, and using chemicals.
Through a voluntary EPA Design for the Environment partnership with the chemical
industry and professional scientific community, this annual awards program seeks to discov-
er, highlight, and honor green chemistry. An independent panel of technical experts
convened by the American Chemical Society judged the entries for the 2008 awards. The
judges used criteria that included health and environmental benefits, scientific innovation,
and industrial applicability. These technologies are also meant to succeed in the marketplace:
each illustrates the technical feasibility, marketability, and profitability of green chemistry.
For further information about the Presidential Green Chemistry Challenge and EPA's
Green Chemistry Program, go to www.epa.gov/greenchemistry.
Note: The summaries provided in this document were obtained from the entries received for the 2008 Presidential Green
Chemistry Challenge Awards. EPA edited the descriptions for space, stylistic consistency, and clarity, but they were not written
or officially endorsed by the Agency The summaries are intended only to highlight a fraction of the information contained in
the nominated projects. These summaries were not used in the judging process; judging was conducted on all information con-
tained in the entries received. Claims made in these summaries have not been verified by EPA
1
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Academic Award
Green Chemistry for Preparing Boronic Esters
Innovation and Benefits
One way to build complex molecules, such as pharmaceuticals and pesticides, is with a
Suzuki "coupling" reaction. This versatile coupling reaction requires precursors with a
carbon—boron bond. Making these precursors, however, typically requires harsh condi-
tions and generates significant amounts of hazardous waste. Professors Maleczka and
Smith developed a new catalytic method to make these compounds under mild condi-
tions and with minimal waste and hazard. Their discovery allows the rapid, green
manufacture of chemical building blocks, including some that had been commercially
unavailable or environmentally unattractive.
Professors Robert
E. Maleczka, Jr. and
Milton R. Smith, III,
Michigan State
University
"Coupling" reactions are one way to build valuable molecules, such as pharmaceuticals,
pesticides and similar complex substances. Coupling reactions connect two smaller mol-
ecules, usually through a new carbon—carbon (C—C) bond. A particularly powerful cou-
pling reaction is the Suzuki coupling, which uses a molecule containing a carbon—boron
bond to make a larger molecule through a new C-C bond. In fact, the Suzuki coupling is
a well-established, mild, versatile method for constructing C-C bonds and has been report-
ed to be the third most common C—C bond-forming reaction used to prepare drug
candidates.
Chemical compounds with a carbon—boron bond are often prepared from the corre-
sponding halides by Grignard or lithiate formation followed by reaction with trialkyl
borate esters and hydrolytic workup. Miyaura improved this reaction with a palladium cat-
alyst, but even this new reaction requires a halide precursor.
Several years ago, Professors Milton R. Smith, III and Robert E. Maleczka, Jr. began
collaborating to find a "halogen-free" way to prepare the aryl and heteroaryl boronic esters
that are the key building blocks for Suzuki couplings. Their collaboration builds upon
Smith's invention of the first thermal, catalytic arene carbon—hydrogen bond (C—H) acti-
vation/borylation reaction. This led to transformations using iridium catalysts that are
efficient, have high yields, and are tolerant of a variety of functional groups (alkyl, halo-,
carboxy, alkoxy-, amino, etc.). Sterics, not electronics dictate the regiochemistry of the
reactions. As a consequence, 1,3-substituted arenes give only 5-boryl (i.e., meta-substitut-
ed) products, even when both the 1- and 3-substituents are ortho/para directing. Just as
significantly, the reactions are inherently clean as they can often be run without solvent,
and they occur with hydrogen being the only coproduct. The success of these reactions has
led Miyaura, Ishiyama, Hartwig, and others to use them as well.
In brief, catalytic C—H activation/borylation allows the direct construction of aryl
boronic esters from hydrocarbon feedstocks in a single step, without aryl halide interme-
diates, without the limitations of the normal rules of aromatic substitution chemistry, and
without many common functional group restrictions. Moreover, due to its mildness, the
borylation chemistry combines readily in situ with subsequent chemical reactions.
This technology allows rapid, low-impact preparations of chemical building blocks that
currently are commercially unavailable or only accessible by protracted, costly, and envi-
ronmentally unattractive routes. Indeed, most recently, Michigan State University licensed
the nominated technology to BoroPharm, Inc., which is using these catalytic borylations
to produce much of the company's product line. Thus, the nominated technology is prov-
ing to be practical green chemistry beyond the laboratory bench.
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SiGNa Chemistry,
Inc.
Small Business Award
New Stabilized Alkali Metals for Safer, Sustainable Syntheses
Innovation and Benefits
Alkali metals, such as sodium and lithium, are powerful tools in synthetic chemistry
because they are highly reactive. However, unless they are handled very carefully, their
reactivity also makes them both flammable and explosive. SiGNa Chemistry devel-
oped a way to stabilize these metals by encapsulating them within porous, sand-like
powders, while maintaining their usefulness in synthetic reactions. The stabilized met-
als are much safer to store, transport, and handle. They may also be useful for
removing sulfur from fuels, storing hydrogen, and remediating a variety of hazardous
wastes.
Alkali metals have a strong propensity for donating electrons, which makes these metals
especially reactive. That reactivity has enormous potential for speeding chemical reactions
throughout science and industry, possibly including new pathways to clean energy and envi-
ronmental remediation. Unfortunately, that same reactivity also makes them highly unstable
and dangerous to store and handle. In addition, increased risk of supply-chain interruption
and the expense of handling these metals have made them unattractive to the chemical indus-
try. Industries from pharmaceutical to petroleum have developed alternative synthetic routes
to avoid using alkali metals, but these alternates require additional reactants and reaction
steps that lead to inefficient, wasteful manufacturing processes.
SiGNa Chemistry addresses these problems with its technology for nanoscale absorption
of reactive alkali metals in porous metal oxides. These new materials are sand-like powders.
SiGNa's materials eliminate the danger and associated costs of using reactive metals directly
but retain the utility of the alkali metals. Far from their hazardous precursors, SiGNa's mate-
rials react controllably with predictable activation that can be adapted to a variety of industry
needs. By enabling practical chemical shortcuts and continuous flow processes, the encapsu-
lated alkali metals create efficiencies in storage, supply chain, manpower, and waste
disposal.
For the pharmaceutical, petrochemical, and general synthesis industries, SiGNa's break-
through eliminates the additional steps that these industries usually take to avoid using the
alkali metals and produces the desired reaction in 80—90 percent less time. For the pharma-
ceutical industry in particular, the materials can accelerate drug discovery and manufacturing
while bolstering worker safety.
Beyond greening conventional chemical syntheses, SiGNa's materials enable the devel-
opment of entirely new areas of chemistry. In clean-energy applications, the company's
stabilized alkali metals safely produce record levels of pure hydrogen gas for the nascent fuel
cell sector. With yield levels that already exceed the U.S. Department of Energy's targets
for 2015, SiGNa's materials constitute the most effective means for processing water into
hydrogen. SiGNa's materials also allow alkali metals to be safely applied to environmental
remediation of oil contamination and the destruction of PCBs and CFCs.
SiGNa's success in increasing process efficiencies, health, and environmental safety and
in enabling new chemical technologies has helped it attract more than 50 major global
pharmaceutical, chemical, and energy companies as customers.
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Greener Synthetic Pathways Award
Development and Commercialization ofBiobased Toners Battelle
Innovation and Benefits
Laser printers and copiers use over 400 million pounds of toner each year in the United
States. Traditional toners fuse so tightly to paper that they are difficult to remove from
waste paper for recycling. They are also made from petroleum-based starting materials.
Battelle and its partners, Advanced Image Resources and the Ohio Soybean Council,
have developed a soy-based toner that performs as well as traditional ones, but is much
easier to remove. The new toner technology can save significant amounts of energy and
allow more paper fiber to be recycled.
More than 400 million pounds of electrostatic dry toners based on petroleum-derived
resins are used in the United States annually to make more than 3 trillion copies in photo-
copiers and printers. Conventional toners are based on synthetic resins such as styrene
acrylates and styrene butadiene. These conventional resins make it difficult to remove the
toner during recycling, a process called de-inking. This makes paper recycling more difficult.
Although others have developed de-inkable toners, none of the competing technologies has
become commercial due to high costs and inadequate de-inking performance.
With early-stage funding from the Ohio Soybean Council, Battelle and Advanced
Image Resources (AIR) formed a team to develop and market biobased resins and toners
for office copiers and printers. This novel technology uses soy oil and protein along with
carbohydrates from corn as chemical feedstocks. Battelle developed bioderived polyester,
polyamide, and polyurethane resins and toners from these feedstocks through innovative,
cost-effective chemical modifications and processing, with the de-inking process in mind.
By incorporating chemical groups that are susceptible to degradation during the standard
de-inking process, Battelle created new inks that are significantly easier to remove from the
paper fiber. AIR then scaled up the process with proprietary catalysts and conditions to
make the new resins.
The new technology offers significant advantages in recycling waste office paper with-
out sacrificing print quality. Improved de-inking of the fused ink from waste copy paper
results in higher-quality recovered materials and streamlines the recycling process.
Preliminary life-cycle analysis shows significant energy savings and reduced carbon dioxide
(CO2) emissions in the full value chain from resin manufacture using biobased feedstocks
to toner production and, finally, to the recovery of secondary fibers from the office waste
stream. At 25 percent market penetration in 2010, this technology could save 9.25 trillion
British thermal units per year (Btu/yr) and eliminate over 360,000 tons of CO2 emissions
per year.
Overall, soy toner provides a cost-effective, systems-oriented, environmentally benign
solution to the growing problem of waste paper generated from copiers and printers. In
2006, AIR, the licensee of the technology, successfully scaled up production of the resin
and toners for use in HP LaserJet 4250 Laser Printer cartridges. Battelle and AIR coordi-
nated to move from early-stage laboratory development to full-scale manufacturing and
commercialization. Their efforts have resulted in a cost-competitive, highly marketable
product that is compatible with current hardware. The new toner will be sold under trade
names BioRez® and Rezilution®. Once commercial, it will provide users with seamless,
environmentally friendly printing and copying.
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Greener Reaction Conditions Award
Nafco Company TRASAR® Technology
Innovation and Benefits
Cooling water touches many facets of human life, including cooling for comfort in com-
mercial buildings and cooling industrial processes. Cooling systems require added
chemicals to control microbial growth, mineral deposits, and corrosion. Nalco developed
3D TRASAR* technology to monitor the condition of cooling water continuously and
add appropriate chemicals only when needed, rather than on a fixed schedule. The tech-
nique saves water and energy, minimizes the use of water-treatment chemicals, and
decreases environmental damage from discharged water.
Most commercial buildings, including offices, universities, hospitals, and stores, as well as
many industrial processes, use cooling systems based on water. These cooling systems can
consume vast quantities of water. Also, unless mineral scale and microbes are well-controlled,
several problems can arise leading to increased water and energy consumption and negative
environmental impacts.
Mineral scale, which consists mostly of carbonates of calcium and magnesium, forms
on heat-exchange surfaces; this makes heat transfer inefficient and increases energy use.
Similarly, microbial growth can lead to the formation of biofilms on heat-exchange sur-
faces, decreasing exchange efficiency. Conversely, high levels of biocide intended to prevent
biofilm cause several adverse effects including increased corrosion of system components.
Gradually, the integrity of the system becomes compromised, increasing the risk of system
leaks. The material from these leaks, along with metal-containing byproducts of corrosion
and the additional biocide, are ultimately discharged with the cooling water. Every time
water is discharged, called "blowdown", pollutants are released in the wastewater, and fresh
water is used to replace the blowdown. Traditionally, antiscalants and antimicrobials are
added at regular intervals or, at best, after manual or indirect measurements show scale or
microbial buildup.
In 2004, Nalco commercialized its 3D TRASAR* Cooling System Chemistry and
Control technology. By detecting scaling tendency early, cooling systems with Nalco's tech-
nology can operate efficiently; in addition, they can use less water or use poor-quality
water.
3D Scale Control, part of the 3D TRASAR* system, prevents the formation of miner-
al scale on surfaces, maintaining efficient heat transfer. The system monitors antiscalant
levels using a fluorescent-tagged, scale-dispersant polymer and responds quickly when con-
ditions favor scale formation. In addition, 3D Bio-control, also part of the 3D TRASAR*
system, is the only online, real-time test for measuring planktonic and sessile bacteria. It
uses resazurin, another fluorescent molecule, which changes its fluorescent signature when
it interacts with respiring microbes. By adding an oxidizing biocide in response to micro-
bial activity, 3D Bio-control generally reduces the use of biocide and also prevents biofilm
from building up on surfaces, maintaining efficient heat transfer.
A proprietary corrosion monitor and a novel corrosion inhibitor, phosphino succinic
oligomer, provide improved corrosion protection. In 2006, the 2,500 installations using
the 3D TRASAR* system saved approximately 21 billion gallons of water. These installa-
tions have also significantly reduced the discharge of water-treatment chemicals to
water-treatment plants or natural waterways.
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Designing Greener Chemicals Award
Spinetoram: Enhancing a Natural Product for Insect Control Dow AgroSciences
Innovation and Benefits
Spinosad biopesticide from Dow AgroSciences controls many insect pests on vegetables,
but is not particularly effective against certain key pests of tree fruits. To solve this prob-
lem, Dow AgroSciences used an "artificial neural network" to identify analogous
molecules that might be more effective against fruit-tree pests. They then developed a
green chemical synthesis for the new insecticide, called spinetoram. Spinetoram retains
the favorable environmental benefits of spinosad while replacing organophosphate pesti-
cides for tree fruits, tree nuts, small fruits, and vegetables.
Spinosad biopesticide won the Presidential Green Chemistry Challenge Award for
Designing Greener Chemicals in 1999. Spinosad, a combination of spinosyns A and D, is
effective against insect pests on vegetables, but there have been few green chemistry alterna-
tives for insect-pest control in tree fruits and tree nuts. Dow AgroSciences has now developed
spinetoram, a significant advancement over spinosad that extends the success of spinosad to
new crops.
The discovery of spinetoram involved the novel application of an artificial neural net-
work (ANN) to the molecular design of insecticides. Dow AgroSciences researchers used
an ANN to understand the quantitative structure-activity relationships of spinosyns and to
predict analogues that would be more active. The result is spinetoram, a mixture of
3'-0-ethyl-5,6-dihydro spinosyn J and 3'-0-ethyl spinosyn L. Dow AgroSciences makes
spinetoram from naturally occurring fermentation products spinosyns J and L by modify-
ing them with a low-impact synthesis in which catalysts and most reagents and solvents are
recycled. The biology and chemistry of spinetoram have been extensively researched; the
results have been published in peer-reviewed scientific journals and presented at scientific
meetings globally.
Spinetoram provides significant and immediate benefits to human health and the envi-
ronment over existing insecticides. Azinphos-methyl and phosmet, two organophosphate
insecticides, are widely used in pome fruits (such as apples and pears), stone fruits (such as
cherries and peaches), and tree nuts (such as walnuts and pecans). The mammalian acute
oral toxicity of spinetoram is more than 1,000 times lower than that of azinphos-methyl
and 44 times lower than that of phosmet. The low toxicity of spinetoram reduces the risk
of exposures throughout the supply chain: in manufacturing, transportation, and applica-
tion and to the public.
Spinetoram has a lower environmental impact than do many current insecticides
because both its use rate and its toxicity to non-target species are low. Spinetoram is effec-
tive at much lower rates than many competing insecticides. It is effective at use rates that
are 10—34 times lower than azinphos-methyl and phosmet. Spinetoram is also less persis-
tent in the environment compared with other traditional insecticides. In the United States
alone, Dow AgroSciences expects spinetoram to eliminate about 1.8 million pounds of
organophosphate insecticides applied to pome fruit, stone fruit, and tree nuts during its
first five years of use. In 2007, EPA granted pesticide registrations to the spinetoram prod-
ucts Radiant™ and Delegate™, and Dow AgroSciences began commercial sales.
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Entries from Academia
Bromine-Free, TEMPO-Based Catalyst System for the
Oxidation of Alcohols
The selective oxidation of alcohols to the corresponding carbonyls is one of the more
important transformations in synthetic organic chemistry. A large number of oxidants have
been reported in the literature, but most of them are based on transition metal oxides such
as those of chromium and manganese. Because most of these oxidants and their reduced
compounds are toxic, their use creates serious problems in handling and disposal, especially
in large-scale commercial applications. An alternative for the oxidation of alcohols is the
Anelli process, which replaces the metal oxides with NaOCl and 2,2,6,6-tetra-
methylpiperidinyloxy (TEMPO). The Anelli process uses a two-phase (CH2CI2—H2O)
system with TEMPO as a catalyst, KBr as a co-catalyst, and NaOCl as the oxidant.
Dr. Augustine's oxidation procedure is a modification of the Anelli process. His pro-
cedure decreases TEMPO by a factor of eight and decreases the volume of buffer by
96 percent. It also replaces KBr with a very small amount of the more benign Na2B40z
(borax) and does not require organic solvents. The reactant alcohol comprises about
38 percent of the total reaction volume compared with only about 2.5 percent in the clas-
sic reaction with dichloromethane as the solvent. This has positive advantages in
environmental and process safety as well as cost. The procedure isolates the product alde-
hyde in excellent yield by phase separation from the aqueous solution, which saves energy.
Dr. Augustine's procedure can oxidize a number of primary alcohols, producing the corre-
sponding aldehydes in very good to excellent yields. His procedure also oxidizes secondary
alcohols to ketones in very good to excellent yields.
The Center for Applied Catalysis collaborated with the NutraSweet Corporation to
scale up this reaction. NutraSweet currently uses Dr. Augustine's procedure to manufacture
3,3-dimethylbutanal on a commercial scale. This aldehyde is a feedstock for Neotame, an
FDA-approved 7V-alkyl derivative of aspartame.
The Mcgyan Process: A New, Heterogeneous, Fixed-Bed Catalyst
Technology for Continuous-Flow Biodiesel Production from
Waste Fats and Oils
Fossil fuels have detrimental effects on the environment. Biobased fuels such as
biodiesel are more environmentally friendly because their use recycles carbon through
renewable biomass, and they burn cleaner than fossil fuels. Current manufacturing process-
es for biodiesel require high-quality, high-purity, virgin oils, mostly soy oil. The price of
high-quality oil accounts for over 80 percent of the price of biodiesel. As a result, the
biodiesel industry is not commercially viable at present without government support.
Working with Professor Arlin E. Gyberg at Augsburg College, SarTec has developed a
technology to produce biodiesel in a fixed-bed, flow-through reactor that could change
how the industry produces this renewable fuel. The key to this new reactor is a highly effi-
cient, heterogeneous catalyst that economically converts inexpensive plant oils and animal
fats to biodiesel. The catalyst contains modified porous microspheres of zirconia, titania,
or alumina.
Dr. Robert L.
Augustine, Center
for Applied
Catalysis, Seton
Hall University;
The NutraSweet
Corporation
Professor Arlin E.
Gyberg, Augsburg
College; SarTec
Corporation
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Professor Shaoyi
Jiang, Department
of Chemical
Engineering,
University of
Washington
In addition to the environmental advantages of biofuels over fossil fuels, SarTec's
process offers several advantages over the current biodiesel production method:
(1) SarTec's process uses less energy overall; (2) the process uses cheap feedstocks such
as waste grease and a variety of plant oils; (3) the zirconia-based catalyst is contained
in a fixed-bed reactor, eliminating the current need to add catalyst to the reaction mixture
continuously and reducing the amount of waste generated; and (4) the new technology
eliminates unwanted side reactions that produce soaps from free fatty acids, thereby reduc-
ing the amount of hazardous waste.
During 2007, SarTec produced biodiesel from an ever-expanding list of feedstocks,
including corn oil reclaimed from distiller's syrup, the byproduct of ethanol production.
SarTec also constructed a pilot plant to prove scalability (ASTM-grade biodiesel is cur-
rently being produced at this facility) and began construction
three-million-gallon-per-year facility that will use this technology.
on
Development of Environmentally Benign, Nonfouling Materials
and Coatings for Marine Applications
Biofouling on ship hulls and other marine surfaces is a global environmental and eco-
nomic problem. The majority of current marine coating products are antifouling coatings
(i.e., coatings that release biocides to kill marine microorganisms). Because biocides are
harmful to the marine environment, their applications are extremely limited. Nontoxic,
fouling-release coatings based on silicone compounds are also available, but have not
gained popularity and are only effective on vessels moving at high speeds (over 14 knots).
Furthermore, these coatings require expensive material, application, and maintenance.
Professor Jiang has developed unique nonfouling coatings (i.e., coatings to which
marine microorganisms cannot attach). Unlike antifouling coatings, his nonfouling coat-
ings are nontoxic; they neither contain nor release biocides. Unlike fouling-release
coatings, his coatings are highly resistant to attachment by marine microorganisms, even
on stationary surfaces.
Professor Jiang's discovery of super-low-fouling zwitterionic materials based on sulfo-
betaine (SB) and carboxybetaine (CB) enabled his development of nonfouling marine
coatings. SB and CB are highly effective, very stable, nontoxic, and low-cost. His
"hydrophobic" zwitterionic precursors enabled Professor Jiang to develop self-polishing,
durable coatings for long-term applications. The "hydrophobic" zwitterionic precursors
have strong mechanical strength as coatings; in seawater, they hydrolyze to "hydrophilic"
nonfouling zwitterionic groups at the outer-most layer of the coatings. Over the last three
years, Professor Jiang and his group have developed three generations of SB- and CB-based
nonfouling marine coatings. Both laboratory tests and field tests in Florida have been suc-
cessful.
Among many technologies under development for marine coatings, Professor Jiang's
nonfouling technology clearly stands out as the most promising. Its environmental and
economic impacts are enormous. These SB- and CB-based materials are very promising for
biomedical applications as well; Stericoat, an MIT spin-off business, is using the technol-
ogy to prohibit microbial growth from attaching to medical devices. Professor Jiang has
filed several patents for his technology.
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Microwave Heating as an Enabling Tool for Greener Synthesis
Dr. Leadbeater and his research group are using microwave heating to develop clean-
er, greener synthetic routes to commodity chemicals, pharmaceuticals, and biofuels.
Microwave heating can enhance the rate of reactions and, in many cases, improve product
yields. He and his group have developed fast, easy, metal-catalyzed reactions that form
C-C bonds; many of these reactions use water as a solvent. They can perform Suzuki and
Heck couplings using sub-ppm quantities of simple palladium salts as catalysts and can also
perform hydroxy- and alkoxycarbonylation reactions using near-stoichiometric quantities
of carbon monoxide.
They have been working to scale up microwave-promoted chemistries and have inves-
tigated both batch and continuous-flow methods. They have developed a fast, easy route
for preparing biodiesel with a commercially available microwave unit that works with both
new and used oil and is energy-efficient. Their continuous-flow apparatus makes approxi-
mately two gallons of biodiesel per minute.
It is difficult to optimize reactions using microwave heating because monitoring the
reaction progress generally requires stopping the microwave, allowing the reaction mixture
to cool, and then analyzing it. Dr. Leadbeater's group has been using Raman spectroscopy
to monitor microwave-promoted reactions in real time. They developed a prototype
Raman unit in conjunction with CEM Microwave Technology and EnWave Optronics.
With real-time monitoring, they can optimize reaction conditions and stop a reaction
when it is complete, avoiding decomposition or byproduct formation. By using only the
minimum energy required for a reaction, they save considerable energy over other
microwave technologies. With the Raman apparatus, they are probing the kinetics of reac-
tions and comparing microwave and conventional heating in much more detail than was
possible previously.
Dr. Leadbeater and Professor Cynthia McGowan from Merrimack College have writ-
ten a manual, "Clean, Fast Organic Chemistry: Microwave-Assisted Laboratory
Experiments", for use in undergraduate chemistry laboratories.
Atom Transfer Radical Polymerization with a Low
Concentration of Copper Catalyst in the Presence of
En i'i ron men tally Friendly Reducing Agents
Atom transfer radical polymerization (ATRP) is a transition-metal-mediated, con-
trolled polymerization process for radically polymerizable monomers that was discovered
at Carnegie Mellon University (CMU) in 1995. Since then, Professor Matyjaszewski has
been working continually to make the process more environmentally benign.
During the last four years, he and his team at CMU developed new catalytic systems
that allow a dramatic decrease in the concentration of transition metal, while preserving
good control over polymerization and polymer architecture. The latest improvements are
called activators generated by electron transfer (AGET, 2004), activators regenerated by
electron transfer (ARGET, 2005), and initiators for continuous activator regeneration
(ICAR, 2006). These methods allow the preparation, storage, and use of the most active
ATRP catalysts in their oxidatively stable state as well as their direct use under standard
industrial polymerization conditions. The recently discovered ARC ET ATRP allows a
reduction in the amount of copper catalyst from over 1,000 ppm to less than 10 ppm in
the presence of environmentally friendly reducing agents such as FDA-approved tin (II)
Dr. Nicholas
Leadbeater,
Department of
Chemistry,
University of
Connecticut
Professor Krzysztof
Matyjaszewski,
Department of
Chemistry,
Carnegie Mellon
University
11
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Professor Ramani
Narayan,
Department of
Chemical
Engineering &
Materials Science,
Michigan State
University; KIM
Industries, Inc.
octanoate, sugars, and ascorbic acid (Vitamin C). AC ET and ARC ET ATRP provide
routes to pure block copolymers. The new processes allow oxidatively stable catalyst pre-
cursors to be used in aqueous homogeneous, dispersed (miniemulsion, inverse
miniemulsion, microemulsion, emulsion, and suspension), and solventless bulk polymer-
izations. Professor Matyjaszewski's work is opening new routes for producing many
advanced polymeric materials in a more environmentally benign, green way.
Since 2002, ATRP has been licensed to 8 of the 15 corporations presently funding the
research at CMU (PPG, Dionex, Ciba, Kaneka, Mitsubishi, WE P. Lion, and Encapson).
Licensees have begun commercial production of high-performance, less toxic, safer mate-
rials including sealants, dispersants, coatings, adhesives, lubricants, additives, pigment
dispersants, and materials for electronic, biomedical, health, and beauty applications in the
United States, Europe, and Japan.
Biodegradable Starch Foams for Protective Packaging
The annual U.S. market for cushioning foam is approximately $800 million
(Freedonia Group, 2003). This market segment is facing growing pressure from regulations
and initiatives in market-based sustainability and carbon management. Plastic foam pack-
aging, often made from polyethylene, is not biodegradable; because it is lightweight, bulky,
and not profitable to recycle, it presents a major disposal problem. There is also growing
pressure to reduce the carbon footprint of packaging by switching to biorenewable feed-
stocks. Previous biobased foams have been brittle, however, and unsuitable for protective
packaging products.
Professor Narayan and KTM Industries have successfully designed and engineered
biodegradable, starch-based biofoams using a one-step, reactive extrusion process. The
resulting foams have the flexibility and reduced moisture sensitivity to be suitable for pro-
tective packaging. This technology uses water as the plasticizer and blowing agent along
with starch polymer modifiers. Water and the shear during the extrusion process break the
hydrogen bonds holding the starch molecules and release the polymer chains without sig-
nificantly reducing their molecular weight. Nucleating agents and process aids allow
control of cell structure and foam flexibility. Screw configurations and designer screw ele-
ments control the foaming process.
Some of their patented biodegradable, chemically modified plasticized starches
(CMPS) include starch (amylase and amylopectin), maleic anhydride, or other dibasic acids
as modifiers, plasticizers like glycerol, and a free-radical initiator; they have also developed
a version of CMPS with nanoclays. In other work, Professor Narayan and KTM Industries
have developed foams for foam sheet manufacture by grafting poly(butylene adipate-co-
terephthalate) (PBAT) or maleated PBAT onto starch. In lifecycle assessments, these
foams compare favorably with polyethylene foams in all eight environmental impact cat-
egories except eutrophication.
KTM Industries has successfully commercialized the biodegradable, starch-based bio-
foam technology under the trade name of GreenCell™ for packaging automotive parts,
printers, and electronic parts.
12
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Highly Efficient, Practical Monohydmlysis of Symmetric Diesters
The development of environmentally friendly, cost-effective organic reactions is of
central importance in academia and industry. Water is among the most environmentally
friendly solvents because it generates no hazards during chemical conversion processes.
Desymmetrization of symmetric compounds is one of the most cost-effective synthetic
reactions because symmetric compounds are typically available commercially at low cost or
are produced easily from inexpensive precursors on a large scale. Desymmetrization of sym-
metric organic compounds mediated by water has the potential to be a greener reaction
process of tremendous synthetic value.
Monohydrolysis of symmetric diesters produces half-esters, which are highly versatile
building blocks in organic synthesis and have considerable commercial value. Because the
two ester groups in the symmetric diesters are equivalent, however, it can be challenging to
distinguish the ester groups chemically. The most common method for effective monohy-
drolysis uses enzymes, which provide no basis for predicting the yield or enantioselectivity.
Classical saponification usually produces complex mixtures of dicarboxylic acids, the start-
ing diesters, and a small amount of the half-esters, which are difficult to separate. As a
result, saponification yields a large amount of undesirable, dirty waste.
Professor Niwayama pioneered and has been developing a highly efficient, practical
monohydrolysis of symmetric diesters. Her reaction is the first selective, nonenzymatic
monohydrolysis of a series of symmetric diesters. In this reaction, aqueous sodium hydrox-
ide (NaOH) is added to a water—tetrahydrofuran (THF) suspension of a symmetric diester
at 0 °C. The reaction rapidly produces pure half-esters in high to near-quantitative yields
without dirty waste. The reaction can also occur without THF. It uses only relatively sim-
ple apparatus, allowing large-scale production of half-esters and potential industrial
applications. Professor Niwayama has filed a provisional patent for this work. She antici-
pates that this reaction will contribute to environmentally friendly green chemistry in
industry and academia.
Doped Semiconductor Nanocrystals as Heavy-Metal-Free
Quantum Dots
Nearly all the colloidal fluorescent quantum dots being produced today with quality
high enough for real-world applications contain toxic heavy metals such as cadmium, mer-
cury, and lead. Although these quantum dots have better size-dependent electrical and
optical properties than do bulk semiconductors, they are not used widely, due in part to
the toxicity of their heavy metals.
Other researchers have studied doped nanocrystals as alternatives to heavy-metal-based
quantum dots since the 1980s, but they have not discovered reaction schemes that achieve
pure dopant emission at high fluorescence quantum yield. Often, a large portion of the
nanocrystals were undoped, resulting in emission peaks from both the undoped and doped
nanocrystals.
Professor Peng and NN-Labs have developed a breakthrough synthesis for doped
quantum dots (D-dot™) that are free of heavy metals. Professor Peng developed quantum
dots that replace the toxic dimethyl metal precursors with metal oxides. This technology
produces doped semiconductor nanocrystals with pure dopant emission (over 99 percent)
at fluorescence quantum yields greater than 80 percent. These doped quantum dots do not
suffer the reabsorption self-quenching inherent in intrinsically emitting quantum dots, due
to the large Stokes shift between the host absorption and dopant emission. In addition,
Professor Satomi
Niwayama,
Department of
Chemistry and
Biochemistry,
Texas Tech
University
Professor
Xiaogang Peng,
Department of
Chemistry and
Biochemistry,
University of
Arkansas;
Nanomaterials
and
Nanofabrication
Laboratories, LLC
(NN-Labs)
13
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Professor Arthur
Ragauskas, School
of Chemistry and
Biochemistry,
Georgia institute
of Technology
Professors Shelby F.
Thames and James
W. Rawlins, School
of Polymers and
High Performance
Materials, The
University of
Southern
Mississippi
these new high-quality, doped quantum dots have far greater thermal and photo stabilities
than do conventional quantum dots. The superior quality of these new, heavy-metal-free,
doped quantum dots will enable quantum dot applications to reach the commercial level
without introducing toxins into the environment. These quantum dots are a suitable alter-
native in many applications from solid-state lighting to biomedical labeling.
Professor Peng has filed a patent for this technology. During 2007, NN-Labs launched
its first two doped nanocrystal product lines, Yellow and Orange D-dots™. It is develop-
ing a full spectrum of D-dot™ emitters.
Developing Lignocellulosic Bioreflneries
Lignin typically represents 20—30 percent of plant biomass. Catalytic oxidative crack-
ing of lignin is a crucial component of the efficient conversion of biomass resources to
biofuels, biochemicals, and biomaterials. At present, however, the only use of lignin is as a
low-value heating fuel.
Historically, oxidation reactions have required stoichiometric amounts of oxidizing
reagents that have considerable drawbacks such as high cost, waste byproducts, and serious
environmental disposal issues. The traditional oxidants include KMnO.,, MnCh, CrO>,
and Br2- In comparison, molecular oxygen is a superior oxidant that is abundant, costs less,
and has a better safety and environmental profile. Researchers have directed concerted
effort at developing systems that use various transition metals to catalyze aerobic alcohol
oxidation, but many of these catalytic systems also require aromatic or halogenated hydro-
carbon solvents that are volatile organic compounds (VOCs).
Professor Ragauskas is focusing on developing catalytic systems to replace previous
VOC solvents with ionic liquids. The unique properties of ionic liquids include low
volatility, high polarity, selective dissolving capacity, and reaction stability over a wide tem-
perature range. These properties lead many to recognize ionic liquids as attractive,
alternative, green reaction media. Professor Ragauskas has developed ionic liquid systems
that are capable of solubilizing lignin. He and his group have discovered novel aerobic cat-
alytic oxidative systems that can functionalize or fragment lignin. They have developed an
oxidative chemistry based on ionic liquids that exhibits excellent selective catalytic proper-
ties, allows simple recovery of product, recycles its catalyst, uses O.- as an ultimate oxidant,
and does not generate hazardous heavy metal wastes. Professor Ragauskas's oxidative sys-
tem makes a unique contribution to green chemistry, especially in applications relevant to
converting lignin to biodiesel and biogasoline.
In 2007, Professor Ragauskas published his recent work in the Journal of Organic
Chemistry and in Tetrahedron Letters.
Development of Commercial-Grade Particleboards Based Solely
on Soybean Protein Adhesive
Commercial particleboards use urea—formaldehyde resins as the adhesive to bind wood
furnish. The occupational exposure to formaldehyde during particleboard production and
the slow liberation of formaldehyde during the service life of particleboards pose serious
health concerns due to formaldehyde's toxicity and carcinogenicity. Professors Thames and
Rawlins have developed adhesives based on soybean protein that yield particleboards with
performance properties comparable or superior to commercial particleboards. These parti-
cleboards are free of synthetic formaldehyde precursors and petroleum derivatives.
14
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The adhesive synthesis involves mechanically blending commercial-grade soybean pro-
tein at 70 °C for 3Vi hours with water and various raw materials. The process is
energy-efficient and does not involve toxic chemicals. The adhesive blends easily with
wood furnish at ratios similar to those used for commercial particleboards. The manufac-
ture of particleboard with their new adhesive releases water as the primary volatile material,
unlike the manufacture of commercial particleboards, which liberates water, methanol, and
formaldehyde.
Professors Thames and Rawlins have developed a range of particleboards that meet
American National Standards Institute (ANSI) performance specifications for M-l, M-2,
M-3, and M-S grades. The particleboards based on their soybean protein adhesive are total-
ly biodegradable, as validated by soil biodegradability and marine respirometry studies.
These particleboards can be safely discarded in landfills or marine environments at the end
of their useful lives. If one percent of the 2006 production of particleboard had been made
with their new adhesive, 10 million pounds of soybean protein would have been used and
16 million pounds of urea—formaldehyde resin would have been eliminated.
Professors Thames and Rawlins have received two patents for their work in this area;
a third patent is pending. Several pilot-scale trials at a particleboard manufacturing plant
in Texas have validated the scalability and feasibility of commercializing this soybean pro-
tein adhesive.
Vegetable Oil Based Macromonomers in Emulsion Polymers for
High-Performance, Zero- VOC Architectural Coatings
Most waterborne coatings contain significant levels of volatile organic compounds
(VOCs) as cosolvents to facilitate efficient film formation of high-glass-transition-temper-
ature polymers. Vegetable oil based macromonomers (VOMMs) are a series of vegetable oil
derivatives functionalized for efficient incorporation into emulsions by copolymerization
with conventional monomers. The synergistic combination of vegetable oil derivatives and
an acrylic backbone provides storage-stable, self-cross-linking systems for architectural and
industrial coatings with reduced- or zero-VOC emissions. Professors Thames and Rawlins
developed a series of VOMMs including soybean oil amide acrylate (SoyAA-1), a
monomer that imparts flexibility to emulsion polymers and can replace butyl acrylate.
Professors Thames and Rawlins have successfully formulated emulsions synthesized
with up to 80 percent by weight of SoyAA-1 into zero-VOC, waterborne architectural
coatings that perform competitively against commercial zero-VOC coatings. They have
also formulated SoyAA-1 into low-VOC, waterborne Navy Haze Gray (NHG) coatings as
a potential replacement for current NHG coatings formulated with solvent-based, silicone-
modified alkyds that contain high levels of VOCs (336 g/L). Their SoyAA-l-based NHG
coatings contain very low levels of VOCs (less than 15 g/L), have fast drying rates, and
meet military specifications MIL-PRF-24635C and MIL-PRF-24596A. Additional advan-
tages include easy clean-up, reduced fire hazards, and low toxicity to Navy personnel. Their
coatings have passed initial trials at the Naval Research Laboratory in Washington, DC and
are scheduled for evaluation onboard naval ships to simulate and characterize the coatings
in actual use.
If one percent of the 2006 production of flat, water-thinned coatings had incorporat-
ed 20 weight-percent of SoyAA-1, almost 300,000 pounds of soybean oil would have been
used and 2.1 million pounds of VOC emissions would have been eliminated. Upon com-
Professors Shelby
F. Thames and
James W. Rawlins,
School of
Polymers and
High Performance
Materials, The
University of
Southern
Mississippi
15
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mercialization, VOMM technology will have the ability to transform the marketplace: the
resulting high-value-added monomers, polymers, and finished products would reduce the
VOC emissions of coatings significantly without affecting their performance.
Passive Treatment of Metal-Contaminated Water
A serious environmental consequence of the mining legacy in the United States is large
flows of water laden with metals, usually known as acid mine drainage. These waters have
concentrations of hazardous contaminants such as arsenic, cadmium, and lead that are
harmful to human health and aquatic ecosystems. The typical treatment for these waters is
to add industrial chemicals to precipitate the metals and then send the water through clar-
ifying, settling, and filtering tanks. Such a labor- and material-intensive process is
expensive; it is also impossible to use at the remote sites of many of the abandoned mines
within the western United States.
Passive treatment is a process for removing contaminant metals from water using nat-
ural materials such as wood chips, sawdust, hay, manure, and limestone instead of
industrial chemicals. The breakdown of these materials is catalyzed by natural bacterial
consortia to produce sulfide, carbonate, and hydroxide ions that precipitate the contami-
nating metals. Natural, constructed, wetland structures filter these precipitates from water.
The process does not require continuous monitoring. It requires only periodic inspections
and sampling, cutting annual operating costs in half. This method of treatment is more
sustainable ecologically than are conventional, active-treatment systems. Passive treatment
both looks green and is chemically green.
Passive treatment was first successful at the Westfork Lead Mine in Missouri; since
then, full-scale systems have been built for several private clients. The systems at all of these
sites eliminate active precipitating chemicals, eliminate energy and material-intensive sep-
aration steps, and remove metal contaminants such as lead, cadmium, and arsenic, as well
as zinc, copper, and mineral acidity from the water. Following these successes, the EPA
recently adopted this technology at two places in the Ten Mile Creek Superfund Site near
Helena, MT for a savings of over $100,000 per year.
Professor Thomas
Wildeman,
Department of
Chemistry and
Geochemistry,
Colorado School of
Mines
16
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Entries from Small Businesses
Changing the Nature of Surfactants: Protein Synergists with
Microbial Uncoupling
Advanced BioCatalytics (ABC) has combined low-molecular-weight proteins from
yeast fermentation (i.e., yeast stress proteins) with synthetic surfactants and adjuvants to
develop a family of products. These products are cost-effective, nontoxic, and fully
biodegradable. They exhibit low surface tension (especially low interfacial tension),
reduced critical micelle concentration, high wettability, and efficient penetration. Besides
optimizing surface energies, ABC products activate natural bacterial metabolism by the
partial, nonlethal, uncoupling of bio-oxidation from biosynthesis. This accelerates the bio-
processing of organic contaminants to carbon dioxide, with lower accumulation of
biomass. Increased nutrient uptake includes reduction of biochemical oxygen demand
(BOD) in wastewaters due to digestion and prevention or reduction of biofilming (for
example, in wastewaters, cross-flow membranes, and porous surfaces) to enhance cleaning
efficiency.
The protein system directs natural microflora metabolism to convert hydrophobic
contaminants such as grease and oil into additional surfactants, creating an autocatalytic
effect. The key benefit is a significant decrease in the volume of surfactants, organic sol-
vents, or chemicals required. For example, in coating hydrophobic diaper linings to achieve
acceptable strike-through, the ABC product reduced the amount of surfactant by over 90
percent. By reducing BOD, ABC cleaners start digestion of organic nutrients at the point
of use, greatly reducing the volume of both grease in sewer lines and sludge in wastewater
treatment systems. These products also save a substantial amount of energy.
ABC products have many current and potential uses including enhanced oil recovery,
degreasing, cleaning, wastewater sludge reduction, and control of odor and biofilm. Several
cities currently use ABC's Clean 'N Green™ Cleaner/Odor Remover and major hospital
chains have approved it for use. In 2007, ABC commercialized its Accell Clean™ for
cleaning tanks of marine ships. The U.S. Coast Guard has approved Accell Clean™ for
marine applications, as have numerous international ship lines.
EHC™ for a Greener Groundwater Treatment Technology
The patented EHC™ technology is a remediation product used for the in situ treat-
ment of groundwater and saturated soil contaminated with persistent organic compounds.
EHC™ is an injectable material composed of microscale zero-valent iron (ZVI) and food-
grade organic carbon (solid or liquid) that ferments slowly to release fatty acids and
nutrients in situ. The product supports rapid and complete destruction of chlorinated sol-
vents, explosives, pesticides, and many other persistent compounds that may be present as
contaminants in soil, sediment, and groundwater.
EHC™ works through a number of mechanisms: (1) direct abiotic reduction due to
contact with the zero-valent iron; (2) enhanced thermodynamic conditions due to lowered
redox potential; (3) indirect chemical reduction by reduced metals; and (4) biostimulation
of dehalogenating bacteria down-gradient from injection locations.
Because it is, in part, a plant-based material, EHC™ can provide safe, renewable, cost-
efficient, and effective remediation for many sites. Compared to some in situ chemical
oxidation (ISCO) technologies, EHC™ is nonhazardous and much less disruptive of nat-
Advanced
BioCatalytics
Corporation
The Adventus
Group
17
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ChK Group, inc.
ural ecosystems. Compared to conventional organic substrates, ZVI and the complex car-
bon source in EHC™ minimize the production of potential fermentation end-products,
such as methane. ZVI provides a substantial pH-buffering capacity, whereas conventional
organic substrates can lead to aquifer acidification that adversely influences the natural
attenuation mechanisms. EHC ™ supports the complete dechlorination of trichloroethyl-
ene, tetrachloroethylene, and carbon tetrachloride without the accumulation of
metabolites; this is a key factor differentiating EHC™ from competitive groundwater
treatment technologies such as molasses, lactates, and vegetable oils. An EHC™ injection
is typically required only once and is complete in one to two weeks with an active lifespan
of three to five years in groundwater, minimizing its carbon footprint.
Since the first field-scale project in 2004, EHC™ has been used to treat approximately
100 locations around the globe.
Nanophase Mn(VII) Oxide: Synthesis using Green Technology
and Applications
The formation and stabilization of nanophase Mn(VII) oxide (i.e., NM70) is central
to the ChK Group's innovative technology. The starting material is a beige-colored miner-
al, hydrated Mn(II); upon addition of 1,4-phenylenediamine (PDA), it forms NM70,
which is violet-colored. The mechanism appears to be the oxidation of PDA to 1,4-benzo-
quinone in the presence of air, which then oxidizes the hydrated Mn(II) to NM70.
Scanning electron microscope (SEM) analysis shows a globular NM70 mass with particle
sizes of 50—100 nm. Cyclic voltammetry and optical spectroscopy confirm the Mn7+ oxi-
dation state.
NM70 is a safe product compared to harsh, toxic competing products. It is nonflam-
mable and is safe for disposal in municipal landfills after use. NM70 is a super Lewis acid:
it attacks compounds with lone pairs of electrons, such as cyclohexylamine and cyclohexa-
none. It removes odors by destroying amine compounds and converting thiol groups to
disulfides. It also neutralizes surrogates for chemical warfare agents (CWAs) such as
2-chloroethyl ethyl sulfide (CEES, a mustard gas analog) and dimethyl methylphos pho-
nate (DMMP, a sarin gas analog). In addition, it makes a good polish for silver.
ChK recently discovered that NM70 is good algaecide and bactericide; it does not,
however, destroy aquatic fauna or flora. After reduction, the violet-colored NM70 changes
to brown-black-colored, environmentally safe Mn(IV) oxide, allowing its use as an optical
sensor. ChK has coated NM70 on and impregnated it into nonwoven and melt-blown
fabrics. The treated fabrics can be incorporated into wipes and liners for consumer and
industrial uses, clothing, and materials for military and homeland security uses.
The NM70 manufacturing process has received a U.S. patent; another patent is pend-
ing on its use to destroy CWAs; and ChK has filed provisional patents on
NM70-coated fabrics and the use of NM70 to destroy nuisance and pathogenic microor-
ganisms. ChK has successfully manufactured clay-coated NM70 on a pilot scale.
18
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Greening Atorvastatin Manufacture: Replacing a Wasteful,
Cryogenic Borohydride Reduction with a Green-by-Design,
Economic Biocatalytic Reduction
The key advanced chiral intermediate in the manufacture of atorvastatin is £-butyl
(47?,67?)-6-cyanomethyl-2,2-dimethyl-l,3-dioxane-4-acetate (i.e., ATS-8, also known as
TBIN). It is the first isolated intermediate comprising both of atorvastatin's chiral alcohol
centers. Pfizer's ATS-8 process uses a sodium borohydride (NaBLL) reduction of the cor-
responding (5i?)-hydroxy-3-ketoester (ATS-6, HK) enantiomer under cryogenic
conditions to give, after quenching, the (3i?,5i?)-dihydroxyester (ATS-7, diol). The ATS-6
is converted in situ to a diastereodirecting boron chelate using hazardous diethyl-
methoxyborane, which is then reacted with NaBLLj at or below -85 °C to further promote
diastereoinduction. After reaction, the bo ran e reagent is regenerated and recovered by
repeated methanol quenches and vacuum distillations. Still, the diastereoinduction is inad-
equate, as several percent of the wrong (3S) diastereomer is formed. Subsequently, the
ATS-7 diol, an oil, is protected as its acetonide, ATS-8, whose diastereopurity must be
upgraded by crystallization, with concomitant product loss.
Codexis developed a greener, more economical process for reducing ATS-6 to dia-
stereopure ATS-7. Codexis used advanced, recombination-based directed evolution to
modify a ketoreductase biocatalyst so that it would reduce ATS-6 with perfect diastereo-
selectivity. This evolved ketoreductase exhibits high activity and stability. It works well at
high substrate loading under greener, ambient, neutral aqueous conditions in conjunction
with a previously evolved, process-tolerant, glucose dehydrogenase biocatalyst. It obviates
the use of hazardous boron reagents, reduces solvent use by 85 percent, reduces waste by
60 percent, lowers energy use dramatically, and provides a higher yield of more stereopure
ATS-7. Before any crystallization, the ATS-7 diol from this reaction and the ATS-8 pro-
duced from it are more diastereopure than the atorvastatin in Pfizer's Lipitor® pills.
Codexis's biocatalytic process is already supplying over five metric tons per month of high-
quality ATS-8 to generic atorvastatin manufacturers at shut-down prices compared to the
captive production costs of Pfizer's original synthesis.
Greening Montelukast Manufacture: Replacing a Stoichiometric
Chiral Boron Reagent with a Green-by-Design, Economical
Biocatalytic Reduction Enabled by Directed Evolution
Methyl (5,J£)-2-(3-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-hydroxypropyl)-
benzoate (MLK-III) is the key chiral intermediate in the manufacture of montelukast sodi-
um, the active pharmaceutical ingredient in Merck's bronchodilator, Singulair®. The
innovator's ketone reduction to this chiral alcohol requires at least 1.8 equivalents of the
expensive, hazardous reductant (—)-(3-chlorodiisopinocampheylborane ((—)-DIP-Cl) in
tetrahydrofuran (THF) at -20 to -25 °C. After quenching, an extraction is required to
remove spent borate salt waste. The reduction produces the S-alcohol in 97 percent enan-
tiomeric excess (e.e.) and requires crystallization to give 99.5 percent e.e. in 87 percent
isolated yield.
Codexis developed a green, more economical biocatalytic reduction to manufacture
MLK-III with a ketoreductase biocatalyst evolved to reduce MLK-II, its ketone precursor.
No naturally occurring or commercially available ketoreductase shows activity toward
MLK-II. Codexis used a minimally active ketoreductase it had evolved previously and
Codexis, Inc.
Codexis, Inc.
19
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evolved it further to increase its activity and stability by over 2,000-fold, replacing one-
third of the amino acids in its active site in the process.
The evolved ketoreductase produces MLK-III with essentially perfect enantioselectiv-
ity under greener reaction conditions: 100 g/L in isopropanol—water—toluene and 45 °C.
Isopropanol is the reductant, which the ketoreductase uses to regenerate its catalytic cofac-
tor NADPH, producing acetone as the coproduct. The process runs as a slurry-to-slurry
conversion with product precipitation driving the reaction to completion. The precipitat-
ed chiral alcohol is of high chemical purity and exquisite stereopurity. (The distomer is
undetectable.) Filtration and washing then recover MLK-III. The process replaces the haz-
ardous boron reagent, greatly reduces organic solvent use, essentially eliminates inorganic
salt waste, uses less energy, and provides a higher yield of MLK-III in higher stereopurity.
With its commercial manufacturing partner, Arch Pharmalabs, Codexis has scaled up
the manufacture of MLK-III using this biocatalytic reduction and has provided samples of
MLK-IV to manufacturers of generic montelukast. Codexis has scheduled commercial
manufacture on the multi-ton scale in 2008.
Codexis, Inc.
Rapid Enablement of Green-by-Design Economic Processes for
Chiral Alcohols by a Platform of Recombinant, Robust,
Divergent Evolvants of a Single Ancestral Ketoreductase
Chiral secondary alcohols are intermediates in syntheses of numerous chiral active
pharmaceutical ingredients (APIs). They are commonly produced from the corresponding
ketones using hazardous boron-based reducing agents or asymmetric catalytic reduction.
Typically, these reduction methods give imperfect stereoselectivity and require additional
purification with concomitant losses in yield.
Biocatalytic reduction of ketones has long been recognized as an attractive greener
alternative to hazardous reagents and energy- or mass-intensive processes for manufactur-
ing chiral alcohols. This promise went largely unfulfilled, however, because available
ketoreductase (KRED) biocatalysts had drawbacks including narrow substrate-specificity,
low activity, poor in-process stability, inadequate stereoselectivity, and productivity-limit-
ing product inhibition.
Codexis's widely applicable platform of pre-evolved, diverse KREDs from a common
wild-type ancestor successfully meets industry's needs for greener processes for chiral alco-
hols both for launched active pharmaceutical ingredients and for new candidates under
development. The Codex™ KRED Panel comprises 180 variants of one wild-type KRED
that are pre-evolved for in-process thermal and solvent stability as well as efficient manu-
facture. The amino acid sequence of each variant is known. As a population, the variants
contain combinatorial mutations that confer activity on a wide variety of ketones and
selectivity to either alcohol stereoisomer. The variants are arrayed on microtiter plates for
rapid screening to find the desired activity on a new ketone substrate and to obtain amino
acid sequence versus activity data for further rapid evolution if needed. Codexis has evolved
KREDs for activity on a wide structural variety of ketones, including some for which the
wild-type ancestor showed no detectable activity and some in which the stereoselectivity of
the evolved KRED is reversed from that of the natural enzyme.
Codexis has evolved ketoreductases to manufacture the chiral intermediates for a num-
ber of drugs. During 2007, Codexis launched its Codex™ KRED Panel as a development
tool on a subscription basis; Merck is now using it successfully.
20
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Elimination of Hexavalent Chromium Used in Hydraulic and
Pneumatic Tubing
Chrome-plated rods and tubes are the backbone of hydraulic and pneumatic cylinders.
Chrome plating produces an excellent wear surface, great lubricity, and good corrosion
resistance. Chrome-plated cylinders are economical, time-tested, and readily available. The
fluid power market relies heavily on chrome-plated tubes to manufacture pneumatic and
hydraulic cylinders, but the hexavalent chromium (Cr(VI)) used in the plating process is
carcinogenic.
Commercial Fluid Power is taking steps to help reduce the use of industrial hard
chrome or engineered chrome in the fluid power market. Together with MACSTEEL's
NitroSteel Division, Commercial Fluid Power has developed Nitro-tuff tubes, a product
that replaces chrome-plated interior diameter (CPID) tubing and chrome-plated outside
diameter (CPOD) tubing used to manufacture hydraulic and pneumatic cylinders. Nitro-
tuff tubes are made by the ferritic nitro-carburizing of steel in ammonia and a carrier gas,
followed by treatment with an oxidizing atmosphere to produce a thin, corrosion-resistant,
black-colored surface film. A light polishing of the nitrided surface gives the product a
more acceptable chrome-like surface that maintains its corrosion resistance. This improved
appearance has opened new markets, especially in high-cycle cylinder applications such as
shock absorbers.
The nitro-carburizing and oxidizing process can reduce the mechanical strength of the
steel base material. Commercial Fluid Power and MACSTEEL selected a suitable base
material, St52.3 SRA DOM, which maintains the mechanical strength of their tubing.
This base material also exhibits better ductility under a severe side load. The two compa-
nies now recommend their chromium-free, St52.3 SRA DOM nitride-treated tubing for
pneumatic cylinder applications.
Commercial Fluid Power will promote these environmental benefits actively during
2008. The journey for a safer more environmentally friendly replacement product at
Commercial Fluid Power is ongoing.
Corrosion - Con trol Chemicals Based on Sustainable Resources
Corrosion of metals is a natural process during which metals oxidize, returning to their
natural state. Selected chemicals can prevent, control, and slow down the corrosion of met-
als. The chemistry of preventing, cleaning, and retarding corrosion differs for each task.
Cortec (corrosion technology) develops and provides products for corrosion control.
Eight years ago, Cortec began a program to use chemicals derived from sustainable
resources whenever possible in developing new products and changing old ones. For exam-
ple, Cortec can use ^/-limonene as a replacement solvent and can replace a petroleum
product with a vegetable oil.
Cortec now sells eleven corrosion control products based on soybean oil, canola oil,
and castor oil, six based on gluconates, and one based on soy protein. It also sells three films
with vapor corrosion inhibitor properties based on polylactic acid. Its most successful prod-
uct uses gluconic acid derivatives from sugar beets as components of migratory corrosion
inhibitors to protect the reinforcing steel (rebar) in concrete.
Cortec has received nine U.S. patents for its new systems. Most recently, Cortec pub-
lished a paper on water-treatment products formulated from biodegradable raw materials.
Commercial Fluid
Power LLC
Cortec Corporation
21
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Cutting Edge
Formulations, inc.
Natures Avenger® Organic Herbicide: A Fast-Acting, Highly
Effective, Organic Alternative to Synthetic and Natural
Herbicides
Nature's Avenger® Organic Herbicide (NAO) is a GRAS (generally recognized as safe),
highly biodegradable, extremely effective, nonselective, post-emergent herbicide that is
approved by the EPA for organic agricultural production. Its active ingredient, ^/-limonene
(citrus oil), is found naturally in more than 300 herbs, edible plants, and fruits.
^/-Limonene is used in many soaps, detergents, commercial cleaners, deodorizers, sham-
poos, and mouthwashes. It has proven to be a strong, natural, degreasing agent that acts by
stripping away the waxy cuticle from weeds, subsequently dehydrating and killing them.
^/-Limonene is also a flavoring agent in many foods.
The volatility of ^/-limonene makes it a relatively weak herbicide. Cutting Edge
Formulations (CEF) has spent considerable resources to develop proprietary emulsions
that reduce the volatility of ^/-limonene substantially. Their emulsions ensure that
^/-limonene remains on plant surfaces longer and thus eradicates weeds more quickly. CEF
research showed that increasing the pH significantly enhances the herbicidal efficacy. A
mixture of proprietary inert ingredients also contributes to activity. NAO is comparable in
effectiveness to glyphosate and paraquat, which are synthetic, non-organic herbicides.
NAO also acts faster.
In consumer and professional markets, the availability of a safe, efficacious, organic
herbicide provides an important alternative to both synthetic products and less-effective
natural products. In the organic agricultural market, organic growers control weeds pri-
marily with mechanical tillage and hand labor, which is extremely expensive at
approximately $ 1,000 per acre. Combining mechanical tillage with NAO in areas that can-
not be mechanically tilled would bring an organic grower's cost for NAO into a range of
$45—80 per acre, which is within the range that traditional, non-organic growers pay for
weed control. The availability of an easy-to-use, effective, cost-effective organic herbicide
will revolutionize how organic growers control weeds.
During 2007, NAO received listing by the Organic Materials Review Institute
(OMRI).
DuraBan
International, Inc
En vi ron men tally Friendly Antimicrobial Surface Treatment
DuraBan International has improved upon 3-(trimethoxysilyl)propyldimethylocta-
decyl ammonium chloride (Si-QAC), an amino-functional silane developed originally by
the Dow Chemical Company. Dow's product had antimicrobial activity, but was unstable
and polymerized in water; it required methanol for stability as well as certified applicators.
DuraBan International developed the first water-stabilized Si-QAC that does not
incorporate any chemical stabilizer and, thus, does not leach off treated surfaces. Unlike
other antimicrobials that can leach toxic chemicals into the environment, DuraBan is vir-
tually nontoxic. DuraBan does not release any toxic gases, volatile organic chemicals
(VOCs), heavy metals, formaldehyde, or phenol. Either standing alone or built into prod-
ucts during manufacture, DuraBan's Si-QAC inhibits the growth of microbes (e.g.,
bacteria, mold, and mildew) that can cause stains, odors, and product deterioration.
Once applied, DuraBan bonds chemically to the product surface, creating a perma-
nent antimicrobial barrier that destroys microorganisms upon contact by rupturing their
cell membranes. DuraBan's proprietary, patented antimicrobial technologies deliver
22
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unmatched performance, durability, and efficacy through a unique formulation based on
surface-modifying nanotechnology.
Dura Ban products serve as powerful antimicrobial barriers for consumer, industrial,
and medical products. This technology can be engineered into many surfaces and materi-
als including coatings, polymers, textiles, lumber, plastic, and adhesives. DuraBan
antimicrobials have never been shown to allow or cause microbial adaptation, resistance,
mutation, diffusion, or migration. When incorporated into everyday products that often
encounter bacteria, DuraBan can positively benefit the environment and prevent the
spread of superbugs, including MRS A (methicillin-resistant Staphylococcus aureus) and
VRE (vancomycin-resistant enterococcus). Henry Ford Hospital recently completed an
extensive study in which DuraBan reduced MRSA and VRE contamination by over
85 percent compared to untreated surfaces. The hospital also found that clothing treated
with DuraBan remained 94 percent effective after 50 washes.
Four of DuraBan's products are registered as pesticides by the EPA: MicrobeGuard,
DuraBan I, DuraBan, and Mold Shield.
Enabling Technology for Methacrylic Acid Production using
Isobutane as the Feedstock
Methacrylic acid (MAA) and its methyl ester, methyl methacrylate (MMA), are high-
volume commodity chemicals that are building blocks for polymers used widely in the
construction, automobile, appliance, and coating industries. Since the 1930s, the produc-
tion of MAA and MMA in the United States has used the conventional
acetone—cyanohydrin (ACH) process, whose feedstocks are acetone and highly toxic
hydrogen cyanide (HCN). The production of one ton of MAA requires at least 0.31 ton
of HCN along with 1.6 tons of concentrated sulfuric acid as both solvent and catalyst. It
also generates 1.2 tons of ammonium bisulfate requiring disposal. In 2005 alone, the U.S.
production of 1.82 billion pounds of MAA and MMA consumed at least 558 million
pounds of HCN, used and regenerated about 2.88 billion pounds of concentrated sulfuric
acid, generated and disposed of 2.16 billion pounds of ammonium bisulfate, and generat-
ed tens to hundreds of billion pounds of aqueous waste discharges.
EverNu has developed a patent-pending technology that uses proprietary, stable, metal
oxide catalysts to produce MAA from isobutane and air as the only feedstocks. This tech-
nology has a significant economic benefit because isobutane costs only a fraction of the
cost of acetone and HCN. It also saves tens of trillion Btu of energy per year because the
partial oxidation of isobutane to MAA is an isothermic reaction. The environmental ben-
efits are enormous. They include (1) completely eliminating the use of large quantities of
HCN and sulfuric acid; (2) avoiding the generation and disposal of toxic, corrosive wastes
from HCN and sulfuric acid; and (3) substituting the nontoxic feedstock isobutane, which
is inherently much safer than HCN and sulfuric acid with regard to worker exposure and
accident potential. Recent research indicates that isobutane can be obtained from renew-
able sources in the future.
Everdex-Enhanced Alowood
Deforestation of old-growth forests and rainforests is of growing concern given today's
far-ranging debates on climate change. Although only 22 percent of the world's old growth
forests remain intact, consumers still want the look of exotic hardwoods in products such
as flooring and furniture.
EverNu Technology,
LLC
EverTech LLC
23
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Alowood offers an environmentally friendly alternative: an exotic look and perfor-
mance using fast-growing plantation softwoods impregnated with the Everdex
formulation, an innovative green chemistry Everdex is a polymeric formulation made from
urea, glyoxal, and starch in water along with environmentally friendly dyes and pigments;
it does not contain any formaldehyde. Softwoods, particularly sustainably grown, planta-
tion softwoods, are impregnated with dilute solutions of Everdex by a vacuum-pressure
treatment. Next, the impregnated wood is heated, causing the starch polymer to cross-link
with the wood cellulose through the urea-glyoxal groups. This creates Alowood: a denser,
harder, more workable wood product akin to a natural hardwood. During 2007, Alowood
received GREENC U ARD Indoor Air certification and class A fire retardant certification.
EverTech is currently selling Everdex-enhanced Alowood to the building industry as
an alternative to natural hardwood. This innovative product is making a significant posi-
tive environmental impact: every piece of Alowood sold replaces a piece of hardwood
lumber or exotic wood that can remain a part of the ecosystem. Alowood, made from plan-
tation wood grown in 10—20 years, is preferable to exotic hardwoods that often
take hundreds of years to grow. In the time it takes a hardwood forest to rejuvenate, a soft-
wood plantation of the same size could be harvested up to 100 times for use in Alowood.
To date, over 2 million board feet of Alowood are on the market, saving over 10,000 hard-
wood trees.
Fluorochemicals are used in many consumer products such as stain-resistant clothing,
upholstery, carpets, paper, and non-stick coatings and paints. Certain fluorochemicals,
however, persist in the environment, bioaccumulate, and have been deemed probable car-
cinogens by the EPA. Fluorochemical pollution from consumer products represents a
significant environmental problem.
G3 Technology Innovations (G3i) has commercialized SZ
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Recently, Scientific Certification Systems certified this technology and its high perfor-
mance at low fluorochemical loadings. G3z currently sells products based on its technology
in the textiles market as GreenShield™.
Electrochemical Control of Mineral Deposition in Open
Evaporative Cooling Water Systems: H-O-H Chemicals Green
Machine
Cooling tower systems use hundreds of billions of gallons of water annually in the
United States. These systems are subject to at least three significant challenges: mineral
scaling, corrosion, and microbiological growth. Traditional chemical treatments to control
deposits either (1) eliminate calcium carbonate by removing one of the scale-forming com-
ponents (calcium by ion exchange or carbonate by adding acid) or (2) slow the rate of
formation of calcium carbonate by treatment with other, less-hazardous chemicals. The lat-
ter treatment, however, uses 25—50 percent more water because it requires removing
mineral-saturated water from the system and replacing it with fresh water.
The inspiration for a replacement technology was the fouling of cathodes by dissolved
calcium salts that interferes with metal plating and water electrolysis operations.
For H-O-H Chemicals, this classical nuisance suggested a mechanism to control trouble-
some deposition throughout large, real-worid recirculating water systems.
Electrolysis of a meta-stable, supersaturated solution forms slow-to-precipitate, insol-
uble salts such as calcium carbonate. This technology may be employed to control deposit
formation on heat exchange and other surfaces in systems such as industrial process water
and evaporative cooling water loops. Hydroxyl ions formed at the cathode greatly acceler-
ate the formation of calcium carbonate, such that the formation of ion clusters and
crystalline calcium carbonate in the bulk phase cooling water is selectively diverted to the
cathode. Properly engineered, side-stream electrolysis of recirculating cooling water can
create a deposition gradient more than 1,000 times greater than anywhere else in a cooling
system and, thereby, force deposition to occur within the electrolysis unit and nowhere else
throughout an evaporative cooling water system. This technology also has implications for
environmental and economic benefit. Potential water savings are substantial. Over 50 cool-
ing systems in the United States now use electrolytic deposit control.
En i'i ron men tally Friendly Antacid Formulations for Wastewater
Treatment
For centuries, humans have used limestone and milk of magnesia (magnesium hydrox-
ide) for medicinal antacid relief in their digestive systems. More recently, people have been
using commercially formulated antacids that contain blends of metal hydroxides and metal
carbonates. Despite these well-known medicinal benefits, no one thought until recently of
using formulated antacid products for large-scale municipal and industrial wastewater
treatment processes, which typically use hazardous alkaline chemicals such as caustic soda,
lime, or soda ash.
Inland Environmental Resources, Inc. (IER) has invented antacid slurry formulations
to treat wastewater on an industrial scale. These formulations use chemicals that are non-
hazardous, environmentally friendly, and safe to handle. Each of IER's formulations (called
Amalgam® products) contains a blend of hydroxides or carbonates of magnesium, alu-
minum, calcium, or potassium. Amalgam® products reduce phosphorous, total suspended
H-O-H Chemicals,
Inc.
Inland
Environmental
Resources, Inc.
25
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solids (TSS), and biological oxygen demand (BOD) in wastewater, simultaneously boost-
ing the pH of acidic wastewater streams. The reuse of Amalgam®-treated wastewater for
land irrigation provides mineral nutrients to the soil, as opposed to the negative environ-
mental impacts of irrigating crops with reclaimed water containing caustic or soda ash.
Finally, Amalgam® formulations are less expensive to use than caustic soda, the industry
standard.
With products that are much safer to handle, environmentally beneficial, better per-
forming, and less expensive, IER has been growing very rapidly into the wastewater
treatment market. Currently, IER is exploring other processes that require pH buffering as
markets for its green chemical antacid formulations. It is developing new Amalgam® for-
mulations to replace caustic soda in the recovery of chromium in the tanning process and
to increase the yield of ethanol in the fuel ethanol industry. Since 2004, IER has con-
structed two manufacturing plants and a pilot plant. It has also filed a patent for its
technology.
The world market for glycols is approximately 20 million metric tons per year. The
world's glycols are derived from natural gas or naphtha, except for those glycols derived
from renewable feedstocks using a process developed by I PCI and its partners. The IPC!
process converts G-G, monomer sugars continuously to alditols (e.g., glucose to sorbitol;
fructose to mannitol) using a proprietary nickel-based catalyst in aqueous solution at pH
above 10, pressure in the range of 2,000 psi, and 200 °C. A second hydrogenolysis step
converts alditols continuously to glycols in excess hydrogen using a proprietary catalyst
developed by Siid-Chemie Inc. The products include propylene glycol, ethylene glycol,
and butanediol isomers. I PCI can shift its process to vary the products and allow market
flexibility. Glycerin (G; a lower-valued byproduct of biodiesel production) can be directly
subjected to hydrogenolysis, producing predominantly propylene glycol and ethylene gly-
col. Similarly, xylose and arabinose (G-sugars) can be hydrogenated to xylitol or arabinitol,
respectively, and then converted to glycols. I PCI has also developed technology to separate
close-boiling glycols using extractive and azeotropic distillation.
Overall conversions of sugars to glycols exceed 85 percent, which is about twice the
yield of bioethanol from fermentation. Also, glycols are over twice as valuable as ethanol.
One key product is 1,4-butanediol, the acetylene-based glycol used in engineering plastics
and as an important precursor. Byproducts other than glycols are low-molecular-weight
alcohols (ethanol, methanol, and propanol).
The I PCI process is inherently safer than other glycol manufacturing processes. Edible
sugars are safe for the environment and humans. Water is the only solvent and both process
catalysts and byproduct hydrogen are recyclable.
I PCI holds five sugar-to-glycol process patents and six glycol separation patents. Siid-
Chemie holds two patents for the catalysts used in this process. Following completion of
two smaller plants in the United States, a 200,000-metric-ton-per-year plant was complet-
ed in China in 2007.
International
Polyol Chemicals,
Inc. (IPCI)
Production of Diverse Industrial Glycols from Renewable Six-
and Five-Carbon Sugars and Glycerin, the Byproduct of
Biodiesel Manufacture
26
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Biodegradable Starch Foams for Protective Packaging
NOTE: This project is the result of a partnership between Professor Ramani Narayan
of Michigan State University and KTM Industries. The project was judged in both the aca-
demic and small business categories. The abstract appears in the academic section on
page 12.
Microbial Production of Renewable Diesel Fuel
Developing large-scale, sustainable replacements for petroleum is a national priority
for environmental, political, and economic reasons. In 2007, the United States consumed
5.5 billion barrels of transportation fuel, increasing its reliance on foreign petroleum and
releasing 2.5 billion tons of carbon dioxide and other pollutants into the atmosphere.
To realize the greatest potential for rapid, widespread adoption, a replacement fuel
must be renewable, scalable, domestically derived, cost-competitive with petroleum, and
compatible with the existing distribution and consumer infrastructure. LS9 has developed
an efficient fermentation process to produce diesel fuel that meets these criteria. LS9 cre-
ated metabolically engineered industrial microbes with a novel biosynthetic pathway: these
microorganisms produce fatty esters and secrete them into the fermentation medium. The
fatty esters are immiscible with the fermentation medium, obviating the need for distilla-
tion. LS9's biosynthetic pathway enables precise genetic control of the molecular
composition and, hence, the performance characteristics of the resulting end products. LS9
can produce its biodiesel from diverse plant-based feedstocks. LS9 is now producing fuel
that is superior to other plant-derived biodiesels in performance, yield, and cost.
Substituting LS9 diesel for petroleum-based diesel will reduce greenhouse gas emis-
sions substantially; LS9 estimates that emissions from its diesel are as low as 20 percent of
emissions from petroleum-based diesel. Unlike petroleum-based diesel, LS9's renewable
diesel does not contain the environmental pollutants sulfur or manganese.
At current sugar prices, LS9 estimates that its diesel can compete with diesel made
from $45-per-barrel petroleum without government subsidy. The LS9 technology antici-
pates bringing fundamental change to the biofuels landscape, setting the stage for rapid
product adoption and widespread displacement of the petroleum-based diesel currently
consumed by both households and industry. During 2007, LS9 filed several patent
applications, demonstrated its technology in a 10-liter fermentor, and obtained over
$20 million to finance further product development.
On-Site Generation of Mixed Oxidants as a Safe, Green
Alternative to Chlorine Gas and Concentrated Bulk Bleach
Although chlorine gas and bulk bleach have been used for 100 years to disinfect water
and have saved countless lives in the process, these hazardous chemicals are now pervasive
around the world. MIOXhas developed on-site generation (OSG) of chlorine-based mixed
oxidant solution (MOS) using low-cost salt brine (aqueous NaCl). This technology con-
verts a brine solution electrolytically on-site and on-demand to produce MOS, which is a
0.4 or 0.8 percent chlorine-based disinfectant that is stored and metered at concentrations
of less than one percent. This process is superior to bulk bleach and chlorine gas in safety,
effectiveness, and cost. It eliminates the hazards associated with traditional technologies,
KTM Industries, Inc.;
Professor Ramani
Narayan, Depart-
ment of Chemical
Engineering &
Materials Science,
Michigan State
University
LS9, Inc.
MIOX Corporation
27
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Nanomaterials and
Nanofabrication
Laboratories,
LLC (NN-Labs);
Professor Xiaogang
Peng, Department
of Chemistry and
Biochemistry,
University of
Arkansas
Organic Recovery,
LLC.
reduces energy outputs, and inactivates water-borne pathogens immune to chlorine disin-
fection. Further, transporting salt rather than fresh bulk liquid bleach reduces the addition
of carbon to the atmosphere by 3—6-fold. MIOX's technology is scalable from individual
use to large cities. It offers significant chemical benefits including reducing the byproducts
of chlorine disinfection, reducing disagreeable tastes and odors, reducing maintenance
required by residual chlorine in water distribution systems, and eliminating biofilms.
MIOX equipment produces a safe solution with capital payback periods of approximately
three to five years.
MIOX's technology replaces hazardous chlorine gas and bulk sodium hypochlorite
with OSG of MOS using sodium chloride, water, and electricity as the feedstocks. Salt is
a harmless, renewable green chemical feedstock. More important, however, MOS is safer
with regard to accident potential, has low operating costs, and produces treated water that
is safer for humans because the MOS disinfectant kills microorganisms more effectively
and produces fewer harmful chlorinated byproducts. The removal of biofilms from heat
exchangers, piping systems, and other surfaces by MOS increases the efficiency of this
equipment, which also reduces carbon footprints.
During 2007, MIOX launched RIO, its product line to generate industry-leading, on-
site, on-demand disinfectant.
Doped Semiconductor Nanocrystals as Heavy-Metal-Free
Quantum Dots
NOTE: This project is the result of a partnership between Professor Xiaogang Peng of
the University of Arkansas and Nanomaterials and Nanofabrication Laboratories, LLC.
The project was judged in both the academic and small business categories. The abstract
appears in the academic section on page 13.
Biochemical Hydrolyzation of Organics in Food Wastes into a
Liquid Fertilizer and Soil Amendment
Most agricultural growers use a variety of petrochemical fertilizers, pesticides, and
fungicides. There is, however, growing concern that these chemicals in the air, soil, and
groundwater are harming the health and safety of humans and wildlife.
Organic Recovery has developed a rapid, batch process to convert food waste into
organic-based liquid fertilizers as a less-expensive, environmentally safe alternative to petro-
chemical fertilizers. The process uses a proprietary mixture of enzymes that may include
xylanase, asparaginase, cellulase, urease, protease, lipase, and carbohydrase. The enzymes
degrade the lignocellulosic cell walls, proteins, lipids, and starches present in the food
wastes. Food-grade phosphoric acid or other acid is added to stop the enzymatic digestion
before completion; this stabilizes the enzymes and nutrients in the concentrated fertilizer.
For use, the fertilizer is mixed with water, adjusted to neutral pH, and applied to soil. The
enzymes resume activity, breaking down proteins and releasing the nutrients and trace
minerals that are locked up in the soil. The liquid fertilizer is biodegradable; applied to
soils, it adds nutrient- and water-holding capacity. The biochemical hydrolyzation process
requires significantly less effort and energy than other methods of recycling food and other
organic wastes or producing petrochemical fertilizers.
28
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Organic Recovery's process prevents the formation of carbon dioxide and methane; it
is the only known way to sequester carbon from food waste. This technology can be used
in communities needing to minimize carbon emissions, improve their recycling rate, and
increase the capacity of their waste disposal facilities. The technology requires significant-
ly less space than competing technologies. Because it is scaled to meet community needs,
it keeps the procurement of feedstock and selling of the liquid fertilizer products local, fur-
ther minimizing adverse impacts on the environment.
During 2007, Organic Recovery constructed a 60-ton-per-day, full-scale processing
facility in Florida. It also filed for a patent on its technology.
Perchlorate-Free Pyrotechnic Composition for Military Training
Munitions
The U.S. Department of Defense uses many types of nonlethal training munitions on
its installations and ranges. Two of the most widely used devices are Mil 6A1 hand grenade
simulators and M115A2 ground-burst simulators. Both simulators have traditionally
employed a pyrotechnic composition based on potassium perchlorate and flaked alu-
minum, which react to produce the spectacular visual and auditory effects (i.e., flash and
bang) required to prepare soldiers, sailors, airmen, and marines for combat.
Recently, there has been increasing awareness of the environmental and human health
impacts of perchlorate compounds and concern for uses that release them into the envi-
ronment. Perchlorate is both highly soluble in water and persistent; it has now been found
in drinking water in at least 34 states.
Grucci, Inc. (the manufacturer of the simulators) joined a team of U.S. Army scien-
tists and engineers to design a chemical composition that is less toxic, but still produces the
same pyrotechnic effects. The team formulated, tested, and evaluated several perchlorate-
free compositions. They used a unique environmental health assessment strategy to predict
the toxicity and other hazards of the candidate compositions and to ensure that any poten-
tial environmental risks were reduced to an acceptable level.
The selected formulation consists of black powder and flaked aluminum. This com-
position has passed all qualification, hazard classification, and production testing, and the
U.S. Army has approved its use in hand grenade and ground-burst simulators. In early
2008, Grucci will change all production of Ml 15A2 and Ml 16A1 simulators to this per-
chlorate-free, black powder based composition. This change will reduce the use of
potassium perchlorate by approximately ten tons per year across the Department of
Defense. Work is now underway to eliminate perchlorate from other munitions, including
booby trap simulators, nonlethal stun grenades, and training rocket warheads.
Pyrotechnique by
Grucci, Inc.
The Mcgyan Process: A New, Heterogeneous, Fixed-Bed Catalyst
Tech no log)' for Continuous-Flow Biodiesel Production from
Waste Fats and Oils
NOTE: This project is the result of a partnership between Professor Arlin E. Gyberg of
Augsburg College and SarTec Corporation. The project was judged in both the academic
and small business categories. The abstract appears in the academic section on page 9.
SarTec
Corporation-
Professor Arlin E.
Gyberg, Augsburg
College
29
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Specialty Fertilizer
Products
Biodegradable, Water-Soluble Anionic Polymers, Prepared in an
En i'i ron men tally Benign Process, Enhance the Efficiency of
Phosphorus Use by Plants
Historically, fertilization of crops with phosphorous has been problematic. When phos-
phorous is applied to the soil, reactions with various cations including calcium,
magnesium, aluminum, and iron fix 75—95 percent of the phosphorus. Because this leaves
only 5—25 percent of the phosphorus available to crops, farmers must apply excess phos-
phorus. Erosion washes residual phosphorus into waterways, where it causes
eutrophication.
Specialty Fertilizer Products (SFP) engineered and patented a family of dicarboxylic
copolymers that increase the efficiency of phosphorous fertilizers and reduce the environ-
mental impact of fertilization. The technology includes manufacturing low-molecular-
weight itaconic—maleic copolymers for use with phosphorous fertilizers. The high negative
charge of these polymers sequesters the cations that would otherwise fix the applied phos-
phorus. SFP sells these polymers under the trade name AVAIL®.
SFP uses a green process to synthesize its nontoxic, water-soluble, biodegradable poly-
mers. Itaconic acid, the main component in these polymers by weight, is produced by
fermentation of renewable agricultural products. Polymer synthesis occurs in water, with
oxygen gas as the main byproduct. The process is highly atom-efficient and does not use
organic solvents. Using AVAIL® polymers with granular or fluid phosphorous fertilizers
greatly increases phosphorous availability in soils, resulting in 80—90 percent of the phos-
phorous being available to crops. Benefits include reduced phosphate accumulation in soil,
reduced phosphate runoff, and reduced contamination and eutrophication of waterways.
AVAIL® produces an average increase of 10—15 percent in crop yields at minimal cost.
This technology lowers the environmental impact of biomass-derived fuel such as
ethanol, butanol, and biodiesel. Because the phosphorus supply is much more energy-
efficient, far less fuel is consumed to grow useful biomass and produce plant-derived liq-
uid fuels. AVAIL® has been marketed in the United States and Canada since 2004.
Currently, SFP is selling 40 million tons of AVAIL® per year internationally.
Steward
Environmental
Solutions, LLC
Development and Commercial Application of SAMMS ™» a
Novel Adsorbent for Reducing Mercury and Other Toxic Heavy
Metals
SAMMS™ (self-assembled monolayers on mesoporous silica) was developed and com-
mercialized to adsorb toxic metals such as mercury and lead. SAMMS™ replaces
commonly used adsorbents such as activated carbon and ion exchange resins whose man-
ufacture and use are less environmentally friendly. SAMMS™ is a nanoporous adsorbent
that forms strong chemical bonds with the target toxic material. It provides superior
adsorption capacity and cost economics; it also reduces the volume of hazardous waste.
Compared to activated carbon, SAMMS™ can reduce the volume of adsorbent waste by
30-fold.
The original functionalization of SAMMS™ used toluene as the solvent. The resulting
waste stream included water, methanol, toluene, and traces of mercaptan. It is impractical
to separate the components of this mixture; therefore, it was usually disposed of as haz-
ardous waste. This process was improved by substituting a green solvent, supercritical
carbon dioxide (sc CO2), which allows complete silane deposition. With this patented
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process, SAMMS™ manufacturing is faster and more efficient. The sc CO.- process also
results in a higher-quality, defect-free silane monolayer with no residual silane in solution.
When the reaction is complete, the only byproduct is the alcohol from the hydrolysis of
the alkoxysilane. The CO.- and the alcohol are readily separated and captured for recycling,
eliminating the waste stream in the traditional synthesis. The combination of a green man-
ufacturing process for SAMMS™ and the superior adsorption characteristics of
SAMMS™ materials results in a long-term reduction in release of toxic metals into the
environment.
The SAMMS™ technology and its commercialization represent collaboration between
researchers at Pacific Northwest National Laboratory and Steward Environmental
Solutions, which licensed the technology and scaled up the manufacturing process. In
2006, Steward applied for two patents covering its green synthesis. SAMMS™ in powder
form is now being used on liquid and mixed waste streams in the chemical, waste man-
agement, and petroleum industries.
Manufactured Firelogs Based on Whole Timber
The market for conventional manufactured firelogs is 110 million logs per year.
Conventional manufactured firelogs offer lower emissions than cordwood. They are typical-
ly made of recycled materials such as sawdust bound together with petroleum wax from fossil
fuel, which is a solid fuel additive.
Torch Technologies has developed an alternative to conventional manufactured firelogs
using cleaner-burning, inexpensive, bioderived materials that are waste streams from vari-
ous industries. Torch firelogs are made from whole timber and crude glycerol by a simple
timber treatment process. The timber is cutoff parts of plantation-grown trees that have
only minimal commercial value as a feedstock for the paper industry. Because the timber
is whole, Torch can use a liquid fuel additive, glycerol, which is a low-value byproduct of
biodiesel production. Torch firelogs contain no fossil fuel components.
Torch firelogs are a sustainable fuel option. They are 20—40 percent less expensive to
produce than conventional manufactured firelogs, depending on the raw materials. They
burn with emissions that are 50 percent lower than conventional manufactured firelogs.
Torch firelogs are structurally stronger than conventional manufactured firelogs, which
makes them safer to burn and easier to package and transport (saving cost and energy).
Their structure also allows consumers to burn multiple logs at one time, similar to a con-
ventional cordwood fire, but with an extended burn time.
Torch Technologies LLC is a joint business venture between Torch Innovations and
Chemco Inc., established to market the new Torch firelog for use in domestic fireplaces,
stoves, and outdoors. During 2007, the company continued development and raw mater-
ial sourcing. It validated the combination of a wide range of waste streams from the
logging, sawmilling, biodiesel, papermaking, and other industries.
Greening Insecticides and Parasiticides
Synthetic chemicals are the current primary means of abating and controlling invertebrate
pests, but these products are flawed due to the development of insect resistance, environ-
mental concerns, and adverse health and environmental effects. Natural plant oils are safer
and have various degrees of pesticidal activity, but historically have not been as effective as
nor offered as broad a spectrum of control as products based on synthetic chemicals.
Torch Technologies
LLC
TyraTech, Inc.
31
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TyraTech is developing proprietary insecticide and parasiticide products that incorpo-
rate unique blends of natural active ingredients. TyraTech's proprietary development
platform enables them to identify potent mixtures of plant oils that are active as insecti-
cides and parasiticides. Their screening platform currently includes three chemoreceptors
that they cloned into Drosophila cell lines: the tyramine neurotransmitter receptor
(expressed solely in invertebrates) and two insect olfactory receptors. Compounds that
bind to and activate these receptors have been shown to be powerful insecticides. With this
platform, TyraTech can rapidly select blends of individual oils that have synergistic ability
to activate multiple insect neurological and olfactory receptors.
TyraTech's products use natural, volatile oils as the main active ingredients, ensuring
that toxic chemicals do not persist in the environment and also drastically limiting the
potential for unintended adverse health effects for humans and other animals. By targeting
multiple chemical receptors simultaneously with natural ingredients, TyraTech's products
decrease the incidence of insect resistance that is characteristic of the synthetic chemical
pesticides currently in use. Their products are highly effective and inherently safer than
other current products.
TyraTech is targeting diverse pesticide markets including agricultural and horticultural
applications, consumer and institutional markets, professional pest control, vector control,
and human and animal healthcare applications. During 2007, TyraTech commercialized its
first product, a ready-to-use broad spectrum Crawling Insect Spray for the institutional
market.
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Entries from Industry and
Government
Replacement of Perfluorinated Alkyl Surfactants with
Nonfluorinated Surfactants in Polymer Manufacturing
All manufacturers, including Arkema, had always used perfluorinated alkyl surfactants
(PFOA) and related chemicals for emulsion polymerizations of fluorinated monomers,
such as vinylidene fluoride. The high reactivity of the fluorinated monomers had led to the
widely accepted belief that only perfluorinated surfactants are inert and stable enough to
function in these polymerizations. PFOA and related chemicals are both persistent and
widely distributed at low concentrations throughout the environment. In 2006, the EPA
and major companies in the industry created the 2010/15 PFOA Stewardship Program to
reduce and eventually eliminate emissions and product content of PFOA and related
chemicals. Although other participating companies pursued containment, recycling, or
substitution of alternative perfluorinated surfactants, Arkema targeted the complete elim-
ination of fluorinated surfactants from its products.
Since 2002, Arkema has worked to eliminate perfluorinated alkyl surfactants from the
manufacture of polyvinylidene fluoride (PVDF) resins. Arkema researchers first identified
several hydrocarbon-based, nonfluorinated surfactants that worked well in the polymeriza-
tion reaction. These surfactants have been used in consumer products such as shampoos
and cleaning formulations; extensive data show that they are of low toxicity, do not bioac-
cumulate, and do not persist. Subsequently, an Arkema team identified fluoro-
surfactant-free polymerization conditions in the laboratory, optimized the reactions on a
pilot scale, and successfully implemented the new processes at Arkema's commercial man-
ufacturing site. Under optimized process conditions, these new surfactants allow the
production of PVDF products with properties virtually identical to those of existing
products.
Arkema is currently replacing its traditional approach with these new manufacturing
processes for all 40 grades of its PVDF resins. During 2007, Arkema reduced its use of per-
fluorinated alkyl surfactants at its U.S. manufacturing site by roughly one-half. Its goals are
95 percent reduction by 2010 and complete elimination thereafter. This technology will
reduce fluorinated surfactants in air emissions, wastewater discharges, and finished goods.
BioBased Tile™ with BioStride™ — A Revolutionary New
Flooring Made with Rapidly Renewable Resources
Historically, commercial flooring has been manufactured using binders derived from
petroleum and fossil fuel feedstocks. These binders combine polyvinyl chloride (PVC),
polyolefin, ethylene acrylic, or synthetic rubber with plasticizers, stabilizers, and process-
ing aids. The binders hold together a filler matrix of limestone and pigment.
Approximately one billion square feet of vinyl composition tile are installed in North
America each year.
After two and half years of research and development, Armstrong is the first manufac-
turer in over 100 years to develop a new biobased polymer as a binder to make a new hard
surface flooring product, BioBased Tile™ with BioStride™. The only other biobased,
Arkema, Inc.
Armstrong World
Industries, Inc.
33
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Ashland inc.
hard surface flooring products are natural rubber and linoleum. The latter, introduced by
Armstrong in 1903, has linseed oil as its key binder ingredient.
BioStride™ is the breakthrough patent-pending polymer used in BioBased Tile™ with
BioStride™, a new category of composition tile that provides enhanced environmental
attributes, improved performance, a classic look, and affordability. The proprietary
BioStride™ polyester contains ingredients from rapidly renewable, domestically grown
corn, resulting in reduced reliance on petroleum and fossil fuels, and, therefore, a lower
carbon footprint. Armstrong continues its efforts to increase the renewable content of
BioStride™. With 13 percent biobased content by weight and 10 percent preconsumer
recycled content, BioStride™ provides the same or better performance as traditional poly-
mer binders based on PVC. Armstrong BioBased Tile™ contains 14 percent BioStride™,
75 percent locally mined limestone, 10 percent preconsumer recycled material, and one
percent pigment. BioBased Tile™ includes 10 percent limestone fragments from quarries
that would otherwise go to landfills.
Compared to vinyl composition tile, a 20,000 square foot installation of Armstrong
BioBased Tile™ saves energy and natural resources equivalent to 72 gallons of petroleum.
Armstrong completed the manufacturing scale-up of the BioStride™ polymer and began
producing its BioBased Tile™ during 2007.
GEOSET NEC)®: Low Emission Technology for the Metal
Casting Industry
Foundries in the metal casting industry typically use organic polymers, known as
binders, on sand to produce a variety of cores and molds. Although these organic binders
allow high productivity, they also emit volatile organic compounds (VOCs) and hazardous
air pollutants (HAPs). Because the binders cause problems with worker health and safety,
foundries must use expensive abatement equipment such as odor control filters and scrub-
bers. Inorganic binders can address these problems, but previous inorganic binders
performed poorly, produced more core and mold scrap, and reduced productivity. Most
were limited to nonferrous applications.
Ashland has developed a low-emission, inorganic binder technology for both ferrous
and nonferrous applications in the metal casting industry. Their GEOSET NEO*'
(Negligible Emissions and Odor) inorganic binders are aluminosilicate gels that are water-
based and heat-cured. They have excellent core and mold rigidity, good dimensional
stability, and high hot strength. There is little concern for human exposure to VOCs or
HAPs before, during, or after the casting process. GEOSET binders release virtually no
nuisance odors during core or mold production. During the casting process, the decom-
position products from GEOSET binders are water vapor and carbon dioxide (CO2). As a
result, foundries can both reduce or eliminate their costly abatement equipment and pro-
vide a cleaner atmosphere for employees and the environment nearby.
Ashland expects GEOSET NEO® binders to have a profound impact not only on
foundries, but also on the environment. Substituting organic binders with inorganic
binders can reduce a foundry's emissions by up to 90 percent and assist in compliance with
environmental regulations. GEOSET can eliminate most nuisance odors and smoke that
would otherwise drift into communities near a foundry. Due to the rising price of petro-
leum, inorganic binders are comparable in cost to organic binders. During 2006 and 2007,
Ashland implemented and cultivated joint development programs with customers.
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Reducing the Environmental, Health, and Safety Impact of
Cooling Water Treatment Programs
Typical conventional cooling water treatment programs require corrosion control, scale
inhibition, and microbiological control. Common water-treatment chemicals include
potentially hazardous and toxic materials. Ashland developed a turnkey application that
significantly reduces the negative environmental, health, and safety impacts of cooling
water treatment programs without sacrificing performance. The unique combination of
SONOXIDE® ultrasonic treatment for microbiological control, ENVIROPLUS® cooling
water treatment products for corrosion and scale control, and the Ultra-Serv® solid chem-
ical inventory management program delivers a high-performance, environmentally
responsible program and enhances safety by eliminating the need for liquid chemicals.
Ultra-Serv® is a solid chemical feed system that reliably dissolves and delivers a solid,
concentrated form of ENVIROPLUS® corrosion and scale control product to recirculat-
ing cooling systems. The ENVIROPLUS® series of cooling water treatment products
includes a patented, complex, synergistic blend of multifunctional components that pro-
vide exceptional multimetal corrosion inhibition and scale control in alkaline cooling water
systems. The blend includes polymeric antiscalants (biodegradable carboxylic antiscalants),
ph osphonocarboxylates (including PSA, a low-P phosphonate), and other organic and
inorganic components. ENVIROPLUS® products reduce the environmental impact of
treated water discharge because they are inherently biodegradable and contain very low
ph osphorous, but no heavy metals. This profile enables plants to comply with increasing-
ly stringent discharge limitations and allows cooling towers to operate at higher cycles of
concentration, thereby reducing water consumption.
SONOXIDE® ultrasonic water treatment for microbiological control enhances health,
safety, and environmental benefits even further. SONOXIDE® ultrasonic treatment pro-
vides total-system microbiological control by applying low-power, high-frequency
ultrasound plus micro-bubble aeration. SONOXIDE® treatment controls total bacteria
and biofilm in recirculating cooling systems, virtually eliminating the need for chemical
micro bio cides. SONOXIDE® is currently in use in over 500 cooling systems worldwide.
Ashland introduced its newest component, Ultra-Serv®, in 2006. Ashland holds a number
of recent patents for this technology.
Solventless, Low- Toxicity, Thermosetting Oligomers that Require
Only Low Energy to Cure
An important technical achievement in the last 40 years has been the development of
coatings, inks, and adhesives that cure essentially instantly with UV light or electron beam
radiation. Equipment and processes cured these materials very efficiently without solvents
or energy-intensive ovens. Although this produced a dramatic net reduction of pollution,
the technology was not risk-free. The acrylic monomers and photoinitiators in traditional
formulations for UV-curable coatings can be very toxic (e.g., corrosive or skin sensitizers)
and odiferous; as a result, they require stringent safety controls.
Ashland's resin technology uses facile chemical conversion to reduce the toxicity of tra-
ditional formulating monomers and resins, resulting in novel compounds that cure
without additional photoinitiators. Ashland's DREWRAD ™ radiation-curable acrylate
oligomer resins are manufactured as 100-percent-reactive liquid resins to be formulated
into radiation-curable coatings, inks, and adhesives. These products allow the application
of coatings to substrates without releasing solvents into the environment. Radiation curing
Ashland Inc.
Ashland Inc.
35
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eliminates large, energy-intensive processing steps such as baking in gas-fired ovens.
Emissions from the use of this resin product are expected to be nearly zero.
To produce DREWRAD™, Ashland selected the same essential formulation building
blocks according to performance requirements. These chemicals are then reacted with
(3-diketones or (3-ketoesters (or amides, anilides, etc.) in a base-catalyzed Michael addition
to produce oligomers of higher molecular weight and viscosity. The product is typically of
higher acrylic bond functionality and, more important, the oligomeric product possesses a
photolabile ketone moiety that can initiate free-radical polymerization upon exposure to
UV light. These novel compounds have virtually unlimited architectural design flexibility,
enabling changes to be made that maximize the green character of each product. Ashland
Water Technologies, a division of Ashland Inc., has commercialized this novel green tech-
nology. Ashland received its most recent patent for DREWRAD™ in 2007.
ATK Lake City
Ammunition
Division
Primer™: A Non-Toxic, Heavy-Metal-Free Primer Fueled by
Red Phosphorus for Small Arms Cartridges
Small arms primer designs have not undergone major changes since 1949, when the
U.S. Army Ordnance Department (USAOD) introduced formulations based on lead
styphnate as noncorrosive primers. These primers release considerably more lead during a
typical training session in an indoor firing range than recommended under current expo-
sure guidelines set by the U.S. military. Red phosphorous (RP) has been patented as a
substitute for use in percussion caps, but RP primers are unstable and tend to produce cor-
rosive byproducts. After limited use, they were eventually abandoned.
The chemical stability of RP remained an issue until manufacturers began using polymers
to microencapsulate water-sensitive oxidizing agents. Encapsulating the hygroscopic lighter
alkali and alkali earth metal nitrates in polymers greatly reduces the rate at which they take
up water. Encapsulated in polymers, the abandoned phosphorous primer formulas have
proven to be effective primer mixtures without the stability and hygroscopicity issues.
Primer™ is a unique combination suitable for use as a percussion priming composition. It
contains phosphorus, potassium nitrate, pentaerythritol tetranitrate (PETN, a high explo-
sive), aluminum, and a polymer-based binder. Primer™ is encapsulated during manufacture
with an epoxy coating that reduces the active catalytic sites for conversion into phosphoric
acid. It is less hazardous, less explosive, more thermally stable, and less costly than formula-
tions based on lead styphnate. Its combustion products are bioavailable and recyclable. It
maintains the necessary chemical energy to ignite propellant efficiently.
At the Lake City Army Ammunition Plant alone, a formulation containing 26 metric
tons of RP and 64 metric tons of potassium nitrate can now replace 71 metric tons of lead
nitrate, 49 metric tons of barium nitrate, and 22 metric tons of antimony sulfide. According
to a 2002 survey by the U.S. Department of Commerce, there are seven other large com-
mercial U.S. cartridge sites manufacturing formulations based on lead styphnate.
Baker Hughes
Incorporated
AuRACOR™ C-101 Encapsulated Time-Release Oilfield
Corrosion Inhibitor
Corrosion-induced leaks in hydrocarbon-producing equipment threaten safety, health,
and the environment. Corrosion-inhibiting chemicals are among the highly effective
means of preventing corrosion in oil and gas wells, tanks, and pipelines and of eliminating
the risk of a petroleum release or spill due to corrosion. The two traditional methods of
36
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delivering corrosion inhibitors are batch treatment and continuous injection: the former
often requires excess chemicals to ensure adequate protection between treatments, where-
as the latter requires storing chemicals at each injection point and is more prone to
chemical spills. Although the industry has used corrosion inhibitors in oilfields for decades,
only recently has anyone focused on the environmental effects of inhibitors.
Baker Petrolite, a U.S. technology center of Baker Hughes, recently developed
AuRACOR C-101 Encapsulated Corrosion Inhibitor, one of their most ambitious efforts
in their long-standing pursuit of safer oilfield products. Their encapsulation technology is
a step-change concept that is more environmentally friendly than either traditional batch
or continuous treatments. By encapsulating judiciously selected chemicals, Baker Petrolite
achieved a safe, nonhazardous corrosion inhibitor that can substantially reduce the amount
of chemicals needed to treat corrosion effectively. AuRACOR C-101 is based upon for-
mulated fatty acid amide and imidazoline. Baker Petrolite engineered the encapsulated
inhibitor to float at the brine—hydrocarbon interface in the well; here, it releases its corro-
sion inhibitor for months at a time. Because AuRACOR C-101 is a solid, nonhazardous
product, it does not require reporting in case of a spill. Further, its time-release properties
mean fewer well-site interventions, which translate into less risk of mechanical damage or
personal injury during chemical application. By eliminating the need for chemical storage
at each wellhead, AuRACOR C-101 greatly reduces the potential environmental impact of
corrosion protection programs.
During 2006, Baker Petrolite received a patent for this technology and commercialized
AuRACOR C-101 as the first "floating" encapsulated corrosion inhibitor.
Green Works1" Natural Cleaners from the Makers of Clorox:
Home Cleaning Products
GreenWorks™ Natural Cleaners set a new standard for natural cleaning. These prod-
ucts perform as well as conventional cleaners and are composed of over 99 percent natural,
plant-based ingredients from renewable sources and minerals.
GreenWorks™ products include plant-based ingredients derived from such sources as
coconut and lemon oil. The formulas optimally blend natural ingredients and naturally
derived surfactants to achieve excellent cleaning performance. One key to the
GreenWorks™ technology was Clorox's development of a novel, nanoemulsion that dis-
solves ingredients such as essential oils in the formulation as well as dirt or soil, while
maintaining phase stability in a clear product. The products are formulated to be
biodegradable and non-allergenic, are not tested on animals, and come packaged in recy-
clable containers. The manufacturing facilities used to produce GreenWorks™ have zero
emissions discharge. Further, all GreenWorks™ products perform as well as or better than
leading conventional cleaners in laboratory and blind in-home consumer tests. This level
of cleaning is important to convince consumers to switch from their traditional cleaning
products. The EPA Design for the Environment initiative recognized four of five
GreenWorks™ products, representing a significant level of achievement.
Fossil fuels contribute significantly to greenhouse gas emissions. By switching from
petrochemicals to natural source ingredients in the GreenWorks™ line, Clorox calculates
that approximately 250,000 gallons of petroleum will be saved in the United States every
year. Compared to using petrochemicals that can contribute to the production of carbon
dioxide (CO2, a greenhouse gas), plant-based renewable sources capture CO.- during their
growth.
The Clorox
Company
37
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Clorox will launch GreenWorks™ Natural Cleaners in January 2008. The
GreenWorks™ line of products sells at only a modest premium to conventional cleaning
alternatives, despite the inclusion of the costlier plant-based renewable ingredients, the
environmentally friendly manufacturing process, and the innovative science, which togeth-
er offer the consumer the most natural, powerful cleaning on the market.
Cytec Industries
Inc.
Cylinderized Phosphine as a Safer, More En viron men tally
Friendly Altemative to Traditional Fumigants for Stored
Products
Agricultural fumigants are used to control pests that infest stored products, such as
dried fruits and nuts; grains such as wheat, rice, and corn; and nonfood commodities such
as tobacco.
For over 50 years, stored products have typically been fumigated with methyl bromide
or metallic phosphides. Because methyl bromide is being phased out in accordance with
the Montreal Protocol on ozone-depleting substances, an alternative fumigation method is
needed.
Metallic phosphides (typically aluminum or magnesium phosphide) release phosphine
gas when exposed to the ambient moisture in the air. Phosphine gas by itself is a very effec-
tive fumigant with no known chronic toxicity. The efficient release of phosphine gas from
the metallic phosphides, however, requires certain temperature and humidity levels that
may not be reached in practice; unreacted phosphide residues are often left after fumiga-
tion. These residues must be deactivated and disposed of in a time-consuming and often
dangerous process; typically, they are hazardous waste.
Cytec Industries has developed and commercialized a new technology for fumigating
stored products. Cytec supplies phosphine gas in recyclable cylinders. With cylinderized
ph osphine, workers can easily adjust phosphine concentrations from outside the fumiga-
tion space, applying only the amount necessary for complete fumigation. As a result,
fumigation requires less phosphine. Further, cylinderized products leave no unreacted
residue or byproducts.
Cytec's cylinderized phosphine products are inherently safer than traditional fumigants:
they require less worker exposure and do not significantly impact the environment. Cytec's
two products, ECO; FUME and VAPORPH3OS, are currently used by some of the largest
food processing, milling, and storage facilities.
Cytec Industries
Inc.
Cytec Innovation Management System: Sustainable
Development of New Products
Cytec Industries Inc., led by its Innovation Group, has established a process called the
Cytec Innovation Management System (CIMS). This process guides development chemists
and engineers in evaluating the safety, health, and environmental (SH&E) as well as eco-
nomic aspects of products under development. Cytec chemists and engineers use the CIMS
web-based process management software from the earliest stages of product development
through commercialization and production. This process includes a series of stages and gates
in which users assess aspects related to SH&E. CIMS requires varying degrees of data before
it grants approval for subsequent stages. Cytec created the CIMS process by benchmarking
best practices from other companies' New Product Development (NPD) processes, review-
38
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ing published NPD benchmarking studies, and surveying Cytec employees about earlier
NPD processes. Cytec developed the SH&E questions after consultation with the American
Institute of Chemical Engineers' Center for Sustainable Technology Practices.
CIMS puts in place common best-practice processes and tools that help drive com-
mercialization by designing safe, energy-efficient, and environmentally sound products
and processes. A critical component of CIMS is the Stage-Gate® process, which drives sus-
tainable development. The Stage-Gate® process incorporates SH&E questions into the first
stages of the new product development process, allowing researchers to evaluate the sus-
tainability of a product early in the development process. Additional tools built into CIMS
include Sustainable Futures models developed by the EPA and Cytec's Solvent Selection
Guide, which includes hazard information on 120 common solvents. Cytec incorporated
EPA tools for screening at the early stages of the process to drive commercialization of
greener, safer, more environmentally friendly products. Cytec has implemented the CIMS
process across functional areas and business units throughout the company.
Revolutionizing Energy-Curing Resins for Food Packaging
Applications
Solvent-free, energy-curing technologies have recently emerged as mainstream tech-
nologies in printing human food packages. These technologies are energy-efficient
processes that use accelerated electrons or UV photons to polymerize acrylate resins into a
branched network of large polymers. In contrast to solvent- or water-based technologies,
these solvent-free technologies do not require prolonged energy-intensive heating and dry-
ing cycles or expensive solvent abatement systems. Overall, radiation-curing systems save
an estimated 85 percent of the energy required for traditional systems. In addition, these
technologies can also improve production speed and print quality.
Following the principles of green chemistry and sustainability, Cytec Industries Inc. has
developed a new range of low-extractable, low-odor (LEO) acrylate resins for use in ener-
gy-curing packaging inks and overprint varnishes. Renewable resources such as tall oil
derivatives and glycerol account for 15 percent of the starting materials in the LEO prod-
uct line. The LEO resins are characterized by enhanced size and complexity, lower
migration from the packaging matrix, and frugal synthetic processes using nontoxic and
preapproved building blocks. When formulated in inks, varnishes, or adhesives, these new
acrylate resins are able to meet the most stringent regulatory safety requirements. In addi-
tion, Cytec has also developed testing protocols streamlined for the study of migration of
acrylates at the part-per-billion level to confirm minimal potential human exposure. Cytec
launched the LEO project commercially in 2006. During that year, LEO resins eliminat-
ed 20 tons of waste. Cytec anticipates even greater savings in the future.
Novel Process for Producing Polyols Based on Natural Oils
In recent years, the gradual shift of industry away from petroleum-based feedstocks
toward less price-sensitive, renewable resources has focused on the polyurethane industry.
These opportunities spawned a new generation of bio refineries that are bringing new prod-
ucts and processes to market. The Dow Chemical Company started exploring the use of
seed oils as raw materials in the late 1990s and subsequently envisioned a seed oil refinery
as a new source of monomers and polymers.
Cytec Industries
Inc.
The Dow Chemical
Company
39
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Several technologies emerged to enable the use of renewable feedstocks in
polyurethanes. One of these, Union Carbide's hydroformylation and reduction technolo-
gy, is critical for enabling the practical use of seed oils to produce polyols for polyurethane
applications. The strategy adopted by Dow involves the methanolysis of triglycerides to
discreet fatty acid components followed by the selective functionalization of the fatty acid
methyl esters in a controlled fashion to prepare designed polyols. Fatty acid methyl esters
with a tightly controlled functionality enable the preparation of polyols with a range of
molecular weights, polydispersities, and functionalities that are similar to conventional
polyols. The process creates very little waste; its only byproduct is glycerol. The Dow
process allows the preparation of key intermediates and final products from a variety of
seed oils ranging from commodity soybean oil to high-oleic seed oils such as Natreon™
sunflower oil.
RENUVA™ technology is Dow's commercial implementation of natural oils to produce
polyols for the polyurethane industry. This novel technology enables the production of high
quality, oil- and odor-free polyols. These polyols have the broadest range of applicability and
the possibility of the highest natural content in the final polymer structure achievable in the
industry. Compared with the chlorohydrin process for preparing conventional polyols, the
Dow process reduces fossil fuel use by approximately 74 percent. Dow began commercial
implementation during 2007.
The Dow Chemical
Company; BASF AG
Innovative Industrial Process for Synthesizing Propylene Oxide
via Hydrogen Peroxide
Propylene oxide (PO) is among the top 50 largest-volume chemical intermediates pro-
duced in the world. It is a key raw material for a wide range of industrial and commercial
products, including polyurethanes, propylene glycols, and glycol ethers. Historically, the
synthesis of propylene oxide has required either producing significant volumes of coprod-
ucts or recycling organic intermediates.
Dow and BASF jointly developed a new, innovative route to propylene oxide based on
the reaction of hydrogen peroxide and propylene, referred to as HPPO. Hydrogen perox-
ide is a clean, versatile, environmentally benign oxidant that substitutes for chlorinated
oxidants, which present environmental challenges in many manufacturing operations. In
the HPPO process, propylene is epoxidized by hydrogen peroxide in a tubular reactor at
moderate temperature and low pressure. A proprietary catalyst facilitates the reaction,
achieving both high conversion and product selectivity. The reaction occurs in liquid phase
using methanol as a solvent. Hydrogen peroxide is completely converted and the
propylene conversion is nearly quantitative. The crude propylene oxide is purified by dis-
tillation and the methanol solvent is recycled. The reaction of hydrogen peroxide and
propylene is high in yield and produces no significant coproducts except for water.
HPPO also provides environmental benefits. Dow and BASF expect this technology to
reduce wastewater production by as much as 75—80 percent and energy use by 35 percent
over current technologies. During 2007, Dow constructed a pilot plant in Freeport, Texas
to support development of this technology. The first commercial process based on this
technology is scheduled to begin operation in early 2008 at a BASF production facility in
Antwerp, Belgium.
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Water and Energy Conservation in Denim Finishing
Traditionally, the processing and finishing of denim to achieve the popular, well-worn,
soft look and feel requires large amounts of water and energy. To provide a faded look,
processors traditionally use silicones, particularly amino-silicones, as softeners in wet fin-
ishing. Often the enzymes and other chemicals used in denim garment and fabric
processing do not have good compatibility with silicones. Consequently, most processors
use silicones and enzymes only in different processing steps when they desire a faded look.
The conventional denim garment process requires from 7 to 10 steps and uses large quan-
tities of water in each step. Typically, a basic denim wash that includes desizing and fading
with enzymes can consume as much as 70 to 110 liters per kilogram of denim garments.
Dow Corning® CP 8000 Eco Softener is a granulated, modified polysiloxane textile
enhancer. Its nonionic formulation contains four to five ingredients. It has the potential to
reduce the amount of water consumption needed for traditional methods of denim pro-
cessing by as much as 30—50 percent, to as little as 20 liters of water per garment
containing 500 grams of denim. Used in different stages of denim garment or fabric wet-
finish processing to achieve a natural, soft hand, this water-dilutable, ready-to-use granular
silicone material has a unique formulation and delivery that provides good compatibility
with fabric finishing enzymes and washing stones. This novel combination of properties
enables previously incompatible steps to be combined, thus eliminating separate washing
requirements and conserving significant amounts of water and energy. Combining pro-
cessing steps using Dow Corning® CP 8000 Eco Softener also results in improved
productivity, reduced utility costs and processing time, and improved environmental sus-
tainability without sacrificing performance or fabric characteristics. Dow applied for a
patent for this technology and expects the patent to be published in June 2008.
DuPont™ Cerenol™ — A New Family of Renewably Sourced,
High-Performance Polyether Glycols
Cerenol™ is a proprietary new family of high-performance poly(trimethylene ether)
glycol polymers manufactured in a sustainable process using the renewably sourced ingre-
dient, 1,3-propanediol (Bio-PDO™). Bio-PDO™ is made from corn-derived glucose by
fermentation and is an inherently safer raw material; it replaces 1,3-propanediol derived
from petroleum. The Cerenol™ family of products includes homo- and copolyether
glycols and their ester derivatives with 50—100 percent renewable content and molecular
weights ranging from 500 to 3,000. Cerenol™ polymers can replace synthetic poly-
alkylene glycols that rely on high-cost crude oil and natural gas feedstocks.
Cerenol™ polymers are ether-linked long-chain molecules with an odd number of
carbon atoms in the repeating unit. These carbon-ether linkages give Cerenol™ polymers
unique attributes, such as better flexibility at low temperatures and tougher soft segments
when incorporated into elastomers. Unlike traditional synthetic polyether glycols (which
are made from ring-opening polymerization of cyclic ethers), these new environmentally
friendly polymers are produced through a novel route by polycondensation of Bio-PDO™
in the presence of a soluble acid catalyst. The process uses less material and energy and
reduces greenhouse gas emissions compared to such traditional processes as polytetra-
methylene ether glycol.
This unique combination of properties makes Cerenol™ exceptionally attractive for a
variety of end-use applications that include performance coatings, inks, lubricants, func-
tional fluids, and personal care products. In addition, Cerenol™ polymers are ideal
Dow Corning
Corporation
E. I. du Pont de
Nemours and
Company
41
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building blocks for several value-added thermoplastic elastomers such as polyurethane,
spandex, copolyether ester, and copolyether ester amide. Cerenol™ combines uncompro-
mising product performance with renewable sources, resulting in a reduced environmental
footprint and less dependence on petroleum.
During 2007, DuPont launched Cerenol™ and began batch manufacturing in
Pascagoula, Mississippi. It plans to scale up the facility from a 500-gallon reactor to a
6,000-gallon reactor in early 2009, increasing its annual production capacity to 5—10 mil-
lion pounds.
Eastman Chemical
Company
IntegRex Technology
In conventional manufacturing processes, poly (ethylene terephthalate) (PET) is pro-
duced in the melt phase at high temperature, formed into pellets and cooled, reheated for
solid-state polymerization, and cooled again. Eliminating the slow, costly, solid-state phase
had not been feasible because problems arose during polymerization entirely in the melt
phase.
Eastman's innovative reactor design and integrated process chemistry have solved the
problems of making polymers entirely in the melt phase, enabling the production of melt-
phase polymers that are superior to those made in conventional processes. In the IntegRex
process, the polymer is heated to a lower maximum temperature, cooled only once, and,
thanks to intensified reactor technology, made with less equipment. Other advances
include the innovative use of pipe reactors in polyester processes and novel catalyst systems.
The viscosity of the in-process polymer is about three times higher than that encountered
in conventional PET processes, in which much of the viscosity of the final product is
achieved in the solid-state operation. The higher melt-viscosity makes it more difficult to
move polymer through the process and also significantly impedes the mass transfer neces-
sary to remove the ethylene glycol and water released during polymerization.
Eastman's IntegRex Technology produces recyclable PET resin in a way that reduces
energy consumption by 54 percent, reduces associated greenhouse gas emissions by more
than 47 percent, occupies a smaller environmental footprint, and eliminates the need for
wastewater treatment. Eastman uses the IntegRex process to manufacture its ParaStar
resins. These resins are a drop-in replacement for standard PET in bottle-manufacturing
equipment; they can be recycled along with traditional PET resins.
In late 2006, Eastman opened a new 350,000-metric-ton PET plant at its Columbia,
SC site. The facility is now home to the world's first PET plant that uses IntegRex
Technology: Eastman's proprietary breakthrough process for producing PET resin that
completely eliminates the solid-state process.
Eli Lilly and
Company
A Practical and Green Chemistry Strategy for the Manufacture
of Neurokinin 1 Antagonist, LY686017
Eli Lilly and Company developed an innovative, environmentally benign route for the
commercial production of an investigational new drug candidate. This candidate,
LY686017, is an antagonist of the Neurokinin 1 (NK1) subtype of tachykinin receptor. It
has undergone Phase II clinical trials for the treatment of anxiety and irritable bowel syn-
drome (IBS). LY686017 is Lilly's name for {2-[l-(3,5-bis-trifluoromethyl-
benzyl)-5-pyridin-4-yl-li7-[l ,2,3]-triazol-4-yl]-pyridin-3-yl}-(2-chlorophenyl)-
methanone. The improved route of manufacture delivers LY686017 in exceptionally high
purity (greater then 99.9 percent), despite its complex structure.
42
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Eli Lilly and Company uses a metric called "e-factor" internally that is similar, but not
identical to, Sheldon's E-factor. The e-factor measures the total mass of all raw materials
(including water) that are used to produce each kilogram of active pharmaceutical ingre-
dient (API). Overall, the new route for LY686017 has a net e-factor of 146 kilograms per
kilogram API, which is an 84 percent reduction relative to the original route designed for
Phase I clinical trials. Key technology developed includes a chemoselective SnAt reaction
that has potential broad impact within the pharmaceutical industry. For example, indus-
try-leading antidepressants Prozac™ and Cymbalta™ use SnAr chemistry in key
manufacturing steps. In addition, COX-2 inhibitors such as pyrazolopyridines can poten-
tially be prepared by this novel green methodology. Using the novel SnAr chemistry to
manufacture these large-volume drugs could eliminate over 100 million pounds of pro-
cessing waste per year per drug.
Eli Lilly demonstrated the selected commercial route for LY686017 on a pilot plant
scale during 2006 in Indianapolis, IN. Two prior synthetic routes have been executed at
pilot plant scale at Eli Lilly's Indianapolis, IN and Mount Saint Guibert, Belgium facilities,
respectively. Improvement of key green chemistry parameters across the evolution of these
routes demonstrates the power of technical innovations and is a testimonial to the impor-
tance of incorporating green chemistry into the design and definition of synthetic
processes.
Ecomate® — Environmentally Benign Blowing Agent for
Polyurethane Foams
For many years, chlorofluorocarbons (CFCs) were the preferred foam blowing agents
in the manufacture of polyurethane insulating foams. CFCs gave foam good insulating and
structure properties for use in refrigerators, building construction, and spray foam. CFCs
were removed from polyurethane foam in the 1990s, however, due to their potential to
destroy the ozone layer. Alternative hydrochlorofluorocarbons (HCFCs) were lower in
ozone depletion potential (ODP), but still had the potential to deplete the ozone layer. It
was also discovered that some of the foam blowing agents, including CFCs, HCFCs, and
hydrofluorocarbons (HFCs), had very high global warming potentials (GWPs).
Foam Supplies developed ecomate® (trade name for methyl formate) to replace CFCs,
HCFCs, and HFCs as blowing agents for polyurethane foams. Ecomate® is a zero-ODP,
zero-GWP blowing agent. Ecomate® is also volatile organic compound (VOC)-exempt,
which means it does not contribute to the formation of smog. The HCFCs and HFCs that
ecomate® replaces have GWPs of 700—1700. (The G WP of carbon dioxide is defined as
1.00.) Because each pound of ecomate® replaces about two pounds of the alternative blow-
ing agents, one million pounds of ecomate® would be the equivalent of replacing
700 million to 1.7 billion pounds of carbon dioxide emissions.
The cost of ecomate® blowing agent is substantially less than that of HFCs. There are
no significant expenses associated with implementing the ecomate® technology, which
requires little or no modification to existing foaming processes. The insulating and struc-
tural characteristics of ecomate® foam systems are equivalent to those of conventional
polyurethane foams. Ecomate® has been demonstrated in pour-in-place, boardstock, and
spray insulation systems, as well as boat flotation foam. It is a technology with outstand-
ing properties as well as a low environmental impact. Manufacturers who use ecomate®
foaming systems can help the environment without increasing costs.
Foam Supplies, Inc.
43
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GlaxoSmithKline
GlaxoSmithKline s Eco-Design Toolkit™
GlaxoSmithKline (GSK) developed the Eco-Design Toolkit™ to provide bench-level
chemists and engineers with easy access to green chemistry information so they could
design-out hazardous chemicals, identify alternative chemistries and technologies, and
implement best practices. The Eco-Design Toolkit™ allows GSK to bring products to
market more cost-effectively because it enables the company to produce medicines with
fewer environmental, health, and safety (EHS) impacts throughout their lifecycle.
GSK developed its Eco-Design Toolkit™ following state-of-the-art scientific advance-
ments and standards. It currently has five modules: a Green Chemistry and Technology
Guide to applying green chemistry and engineering principles; Materials Guides on a wide
range of solvents and bases with information and EHS rankings that include the lifecycle
impacts of solvent manufacture; Fast Lifecycle Assessment for Synthetic Chemistry
(FLASC™) for streamlining evaluations of environmental lifecycle and measuring green
metrics including mass efficiency; a Green Packaging Guide to evaluating and selecting
packaging that includes an environmental assessment tool; and a Chemicals Legislation
Guide that identifies legislation phasing out hazardous substances (chemicals of concern).
Each module is designed to ensure that GSK considers all EHS impacts from the manu-
facture of raw materials through the ultimate fate of products and wastes. The toolkit is
accessible through the GSK intranet.
Methodologies of most of the tools are published in peer-reviewed scientific journals.
Tools such as the Solvent Guide, FLASC™, or the Green Technology Guide are first in
their class and are recognized by academic and industrial groups for their innovation as
leading the green design of pharmaceuticals. GSK continues to update the toolkit to inte-
grate new scientific advances and regulatory information.
GSK routinely uses the toolkit to develop new products. During 2006, the mass per-
cent of chemicals of concern across all products decreased nine-fold and the estimated
average lifecycle impacts were reduced four-fold as compounds moved to the last stage of
development.
Many nations around the world fluoridate drinking water to reduce tooth decay.
According to the Centers for Disease Control (CDC), roughly two-thirds of Americans are
supplied with fluoridated water. Fluoride added to drinking water must be kept within a
narrow range of concentrations, typically between 0.5 and 1.5 ppm F~ to be both effective
and safe.
SPA DNS is the common abbreviation for sodium 2-parasulfophenylazo-
l,8-dihydroxy-3,6-naphthalene disulfonate. The SPADNS method for measuring fluoride
is a simple spectrophotometric test used worldwide. Unfortunately, the SPADNS method
utilizes high levels of arsenic, a persistent, tightly regulated toxin and carcinogen. Sodium
arsenite in the SPADNS method acts as a reducing agent to prevent interference from
chlorine and other oxidants that are typically present in drinking water. Although this
approach is effective, the arsenic left over from each test is present in sufficient concentra-
tions to be regulated as a hazardous waste in the United States.
Hach Company has developed an arsenic-free SPADNS reagent and commercialized it
as SPADNS 2. In place of sodium arsenite, the new method uses a proprietary, nontoxic
reducing agent. The waste from using SPADNS 2 can be disposed of safely without the
special handling required for arsenic. The arsenic-free SPADNS 2 Hach Method 10225
Hach Company
Arsenic-Free SPADNS Chemistry for Fluoride Analysis in Water
44
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outperforms both EPA-compliant methods (EPA Method 340.1 and Standard Method
4500-F D) in reagent water and matrix spike recovery and precision.
Apart from this change, the core chemistry of the new test is identical to traditional
SPADNS. The new SPADNS 2 reagent can be used with any instrument, test procedure,
and calibration curve currently used to measure fluoride with the original Hach SPADNS
method. Although the SPADNS 2 reagent continues to be acidic and should be handled
with care, its use generates no arsenic hazardous waste and operators have no risk of expo-
sure. Hach commercialized this technology during 2007.
G2 Catalyst for New and Improved S URFONIC® Non-Ionic
Surfactants
Two billion pounds of surfactants are used in the United States annually. Nonionic sur-
factants, which comprise 40 percent of this total, are among the fastest-growing types of
surfactants due to their compatibility in blends and efficacy in liquid formulations. The
desire for nonionic surfactants that have both lower cost and higher efficiency (i.e., lower
foaming) necessitates the use of renewable, low-cost feedstocks.
Ethoxylates of vegetable oils, their esters, and their alcohols are attractive nonionic sur-
factants that meet industry's needs. Detergent-range alcohols (C12—Qs) derived from
vegetable oil are used widely as hydrophobes to manufacture nonionic surfactants, but they
require multiple manufacturing steps. Ethoxylated surfactants derived from vegetable oils
or their esters require fewer manufacturing steps, but making them with standard catalysts
produces slow, low-yield reactions that are impractical for commercial development.
Huntsman's team developed G2, a novel, alkaline earth based catalyst that enables the
direct insertion of ethylene oxide into fatty acid methyl esters (biodiesel) and vegetable oils
in yields over 95 percent for the production of sustainably derived nonionic surfactants.
Huntsman has demonstrated that its catalyst can ethoxylate a wide variety of sustainable,
natural feedstocks from sources including coconut, palm kernel, soybean, linseed, canola,
rapeseed, and palm stearin. The G2 catalyst uses environmentally friendly calcium. After
the batch reaction is complete, the catalyst is neutralized. It remains in the product, so
there is no disposal of spent catalyst.
Biodiesel is a methyl ester of vegetable oil fatty acids. Its production has increased dra-
matically in the last few years to support America's national strategic intent to diversify its
fuels. This catalyst technology is positioned to capitalize on the megatrend toward biodiesel
by using biodiesel to make high-value, high-performance, biodegradable, and safe surfac-
tants. During 2006, Huntsman began manufacturing fatty methyl ester ethoxylates at its
plant in the United States; the product name is S URFONIC* ME530-PS surfactant.
Application of Green Chemistry Principles in the Scale-Up of the
Darunavir Process
Johnson & Johnson used green chemistry principles to scale up the synthesis of
darunavir, the active pharmaceutical ingredient in Prezista™, a new protease inhibitor.
Prezista™ is indicated in the treatment of adults with HIV-1 strains that no longer
respond to treatment with other anti-HIV medicines.
The principal objectives of the scale-up were to reduce the cost to manufacture
darunavir and to reduce the negative safety and environmental impacts of the manufac-
Huntsman
Corporation
Johnson &
Johnson
45
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turing process. By reducing the manufacturing cost, Johnson & Johnson could reduce the
price of Prezista™ to allow more patients to benefit from it.
The company met three objectives. First, it reduced solvent use by replacing a single
reaction in a relatively large volume of solvent with three consecutive reactions in a rela-
tively small volume of solvent. Second, it eliminated the formation of hydrogen gas
originally given off when excess hydride was quenched with hydrochloric acid by separat-
ing the acidification and quenching steps; it replaced hydrochloric acid with methane
sulfonic acid and now adds acetone to react with excess hydride and form isopropanol.
Third, it replaced a solvent system containing methylene chloride and triethylamine with
a more benign solvent system containing acetonitrile and pyridine. It also eliminated a
number of solid-liquid separation steps. Its accomplishments reduced the manufacturing
cost by 81 percent and increased the overall yield by 40 percent.
The U.S. Food and Drug Administration granted accelerated approval to Prezista™ on
June 23, 2006. With its improved, scaled-up process, Johnson & Johnson reduced raw
materials and hazardous waste by 46 tons, reduced hydrogen gas by 4,800 cubic meters,
and eliminated 96 tons of methylene chloride in 2006.
The Lubrizol
Corporation
Novel Green Chemistries Extend the Useful Life of Automobile
Catalytic Converters and Reduce Exhaust Gaseous Emissions
For the last 50 years, phosphorus in the form of zinc dialkyldithiophosphate (ZDDP)
has been the most cost-effective antiwear, antioxidant, and anticorrosion component of
engine oil. When ZDDP fulfills its function in the engine, however, the phosphorus can
enter the exhaust stream, either by consumption or volatilization (released as a vapor). This
ph osphorus interacts with and decreases the effectiveness of catalytic converters used by
automotive manufacturers to reduce exhaust gas emissions. This phenomenon, called
catalyst deactivation, inhibits the ability of auto manufacturers to meet the EPA's require-
ments for a 120,000-mile or 10-year warranty on the catalyst system.
In 1994, the engine oil industry in the United States set an upper limit for phosphorus
in engine oil at 0.08 weight percent. The same limit for phosphorus continues today.
Although a phosphorus limit was set to protect catalysts, the phosphorus still present in the
oil can volatize from the engine, then react with and deactivate the catalyst. Some ZDDPs
are more prone than others to volatilize and, therefore, to deactivate catalysts. Concerns
about losses in catalyst efficiency forced formulators either to design engine oils with lower
concentrations of traditional ZDDP or to develop cost-effective, low-volatility ZDDP
technology.
Lubrizol developed a new, low-volatility ZDDP technology and tested it for two years
and 100,000 miles in New York City taxicabs. Taxicabs using oil with Lubrizol's ZDDP
technology had an average of 46 percent lower volatile phosphorus, 10 percent lower
oxides of nitrogen (NOx), and 15 percent lower carbon monoxide (CO) than taxicabs
using oil containing traditional ZDDP technology. In 2004, the Lubrizol Corporation
introduced its patent-pending, low-volatility ZDDP technology to provide engine oil for-
mulators with an alternative to designing higher-cost engine oils with lower levels of
ZDDP
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An Efficient Green Synthesis of Isentress®: A Breakthrough HIV
Integrase Inhibitor
Isentress® (raltegravir) works by inhibiting the insertion of HIV DNA into human
DNA by the integrase enzyme, which limits the ability of the virus to replicate and infect
new cells. It is the first medicine to be approved in the new class of antiretroviral drugs
called integrase inhibitors.
For launch in the marketplace, Merck had developed a viable synthesis to produce
Isentress®. Because the product is a critical new tool to fight the global HIV/AIDS epi-
demic, Merck pursued a synthetic pathway that was more efficient, environmentally
enhanced, and more economical. Through scientific innovation, atom-economic synthe-
tic design, reduction of byproducts, and the use of greener chemicals, Merck developed an
improved process. The replacement process has a 35 percent increase in overall yield, a
49 percent reduction in production cost, and a reduction in waste byproducts equal to
253 metric tons per metric ton of Isentress® manufactured. The overall E-factor went from
388 for the original process to 121 in Merck's improved process, a 70 percent reduction.
Given the recommended dose of 800 mg per day per patient of Isentress®, this waste reduc-
tion translates to 164 pounds of waste reduced per patient each year compared to the
initial, original manufacturing route. A critically important improvement in the process is
the replacement of the reagent methyl iodide (a carcinogen, neurotoxin, and respiratory
toxicant) with trimethylsulfoxonium iodide, an innovative, less toxic substitute.
In 2007, Merck's innovative HIV Integrase Inhibitor, Isentress®, was approved for use
in both the United Sates and the European Union.
Alternative Green Adhesives Solutions for Textile Cornposites for
Use in Commercial Buildings: TractionBack®
Poor indoor air quality is one of the top five environmental health risks associated
with building interiors. Traditional modular carpet installation requires adhesives and
sealants that contain such volatile organic compounds (VOCs) as formaldehyde and
2-ethyl-1 -hexanol. Carpet installation may also require surface preparation including sand-
ing and removal of old adhesive, which degrades air quality further.
Milliken's TractionBack® anti-skid, adhesive-free backing is a thin coating formulation
applied to the felt on the bottom of carpet tile. The formulation is an amorphous
ethylene—propylene copolymer that is tackified with a hydrocarbon resin and tall-oil rosin,
a biobased component. The raw materials in the formulation have almost no measurable
VOCs in the solid state. TractionBack® high-friction coating for modular carpet eliminates
the need for onsite adhesive applications and repairs traditionally required for new and
replacement installations, thus eliminating related VOCs. Mill ike n estimates that
TractionBack® eliminates the use of 400 tons of sealants and adhesives as well as
16,000 five-gallon containers of adhesive and sealant each year.
TractionBack® eliminates chemical pollutants such as adhesives, floor primers, sealants,
and other VOCs; eliminates biological pollutants such as mold and bacteria; and reduces
the particulate hazards of sanding and surface preparation. Additional environmental ben-
efits include: (1) energy reduction during production; (2) waste reduction during
installation; (3) waste reduction to landfill by extending product life because individual
tiles can be repositioned or replaced easily; (4) reduction of downtime for building spaces;
(5) incorporation of biobased raw materials; and (6) removal of polyvinyl chloride (PVC),
which has environmental issues related to its production, installation, and eventual dis-
Merck & Co.
Milliken &
Company
47
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posal. TractionBack® uses fewer resources in both manufacturing and installation, reduc-
ing waste and eco-footprint. TractionBack® has been on the market since 2003- Milliken
developed the current formulation for TractionBack® to include biobased raw materials in
2005.
Monsanto
Company
NCH Corporation
Revolutionizing Insect Control: Bollgard® Insect-Protected
Cotton Technology and Bollgard II® with Roundup Ready® Flex
Cotton is the most important textile fiber in the world, accounting for more than
40 percent of total fiber production as well as other important cotton products including
cottonseed oil and animal feed. Protecting this important crop from targeted insects in a
way that protects humans and the environment has been a persistent challenge. So, too,
has developing technologies that simultaneously ease strains on the natural, human, and
economic resources that help global agriculture meet the needs of our growing population.
In 1996, Monsanto successfully developed and commercialized the first insect-protect-
ed cotton, Bollgard®. Monsanto produced the technology using Agro bacterium
tumefactions to mediate transfer of the insecticidal Cry 1 Ac protein coding sequence into
the cotton genome. The CrylAc protein is nearly identical to a protein produced by
Bacillus thuringiensis, or Bt. When this protein is introduced into the cotton plant through
biotechnology, insects that feed on the plant stop eating and die. Specifically, Bollgard®
cotton kills bollworm and budworm.
In 2006, Monsanto commercialized Bollgard II® cotton, a second-generation insect-
protected cotton that contains an additional insecticidal protein, Cry2Ab2. The additional
protein provides dual modes of action, creating powerful control of an expanded spectrum
of most leaf- and boll-feeding worm species including budworms, bollworms, armyworms,
and lopers, as well as saltmarsh caterpillars and cotton leaf predators, greatly reducing the
need to spray for worms. Monsanto's Bollgard® and Bollgard II® traits have completely rev-
olutionized insect control in cotton, providing growers with the ability to stop major
cotton pests with fewer chemical sprays, maximize yield potential, and ultimately better
steward natural resources. The National Center for Food and Agriculture Policy (NCFAP)
calculated that Bt cotton planted in the United States alone has reduced insecticide use by
2.7 million pounds per year. During 2006, two million acres of Bollgard II® cotton were
planted around the globe.
System for Bioremediation of Effluents
Traditional remediation of municipal, industrial, and agricultural wastewaters uses
combinations of sulfuric acid, caustic, petroleum-based solvents, and synthetic emulsifiers,
which are toxic or generally not biodegradable. Naturally occurring microorganisms are an
alternative to chemical remediation. They are generally supplied as dormant or resting
spores with low activity levels, however, making it too costly to use enough bacteria for
effective treatment in many systems.
Extensive research and development by NCH Corporation has resulted in a novel,
patented process for on-site fermentation that efficiently generates a renewable feedstock
of naturally occurring strains of Pseudomonas and Bacillus bacteria at 30 trillion vegetative
bacterial cells every 24 hours to treat wastewaters. Every 24 hours, the BioAmp® system
delivers 292 gallons of liquid product, equivalent to 25—50 pounds of commercially avail-
able dry bacterial powdered product, directly into problematic drain lines. The bacteria
degrade the organic matter in the drains, ultimately releasing carbon dioxide (CO2) and
48
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water. This saves energy by producing active bacteria on-site and reducing the energy
required for manufacturing and shipping. It costs less than 10 percent of comparable quan-
tities of dry powdered bacteria. The BioAmp® system reduces the need for commonly used
acid, caustic, and solvent drain maintainers. NCH's BioAmp® system also reproducibly
reduces biochemical oxygen demand (BOD) compared to baseline in a number of case
studies. This type of data generation is new to the industry and demonstrates the efficacy
of the BioAmp® wastewater treatment system.
During 2007, Iowa State University tested the biobased content of BioAmp® pellets to
provide data for the U.S. Department of Agriculture's BioPreferred Program in the cate-
gory of Biological Drain Maintenance. NCH's BioAmp® system has been on the market
since 2003; it is now in use in the food processing and petroleum refining industries with
over 1,500 systems in all parts of the world.
Bromine-Free, TEMPO-Based Catalyst System for the
Oxidation of Alcohols
NOTE: This project is the result of a partnership between Dr. Robert L. Augustine of
Seton Hall University and The NutraSweet Corporation. The project was judged in both
the greener synthetic pathways and academic categories. The abstract appears in the acad-
emic section on page 9.
The NutraSweet
Corporation; Dr.
Robert L.
Augustine, The
Center for Applied
Catalysis, Seton
Hall University
Convergent Green Synthesis of Linezolid (Zyvox™), an
Oxazolidinone Antibacterial Agent
Pfizer has developed a novel, convergent, green, second-generation synthesis of linezol-
id, which is the active ingredient in Zyvox™. Approved by the U.S. Food and Drug
Administration in 2000, Zyvox™ is the only member of the oxazolidinone class of
antibacterials. This is the first new class of antibacterials approved in over 30 years.
Zyvox™ is approved for the treatment of antibiotic resistant gram-positive bacterial infec-
tions, including vancomycin-resistant Enterococcus faecium (VREF), methicillin-resistant
Staphylococcus aureus (MRS A), and multidrug-resistant Streptococcus pneumonia (MDRSP).
These antibiotic-resistant bacterial infections have become an ever-increasing threat to
public health.
Pfizer initially developed a linear synthesis for Zyvox™; the company is currently using
this launch process to manufacture the drug. Rapid growth in global demand for this valu-
able life-saving drug, however, led Pfizer to develop a greener, more efficient, convergent
synthetic process to meet future needs, as well as reduce the cost and environmental impact
of production. The second-generation process will replace the launch process after approval
by appropriate regulatory agencies. It has numerous green chemistry benefits: overall yield
is increased by 8 percent; total waste is reduced by 56 percent; nonrecycled waste is reduced
by 77 percent; methylene chloride waste is reduced by 78 percent; and a pressurized
ammonia step is eliminated. At current production volumes, total waste will be reduced by
1.9 million kilograms per year, and 1.7 million kilograms per year of nonrecyclable waste
will be eliminated.
The greater efficiency of the new synthesis will greatly reduce the use of natural
resources. The greatly reduced waste will significantly reduce the transport of hazardous
waste and consequent potential for accidental exposure of humans and the environment.
Reducing the cost of linezolid production will make this life-saving drug more readily
available to a larger proportion of humanity.
Pfizer, Inc.
49
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Rhein Chemie
Corporation
Roche Carolina inc.
Additives for Optimizing Renewable Resources in the Production
of Polyurethane Systems and Plastics
As the world maintains its heavy reliance on oil, supply and demand are forcing man-
ufacturers and consumers to find alternatives to petroleum-based products. Replacing
petroleum-based polyols with biobased polyols in the polyurethane market is one poten-
tial way to reduce the need for oil.
Significant technical difficulties arose in early biobased polyol systems. The available
acid groups in soy polyols caused hydrolytic degradation and variable reactivity, leading to
polyurethanes with inferior properties. The additive technology from Rhein Chemie over-
came many of these difficulties. Now, these green alternative systems are commercially
viable products that reduce petroleum dependence, engage renewable feedstocks, and
improve the longevity of polyurethane elastomers, adhesives, and foams. Currently, there
are no known competing technologies with the same benefits as biobased polyol systems.
Rhein Chemie's soy-based polyol additives have proven effective for producing low-
density insulated spray foams. These particular soy-based systems use water as a blowing
agent to replace chlorofluorocarbons (CFCs) and use flame retardants to reduce smoke
effects as required for Class I Foams. The combination of these Rhein Chemie technolo-
gies enables their insulation system to be effective in reducing depletion of the ozone layer.
The Rhein Chemie insulation system comprises an ethoxylated soy polyol mixed with
a common polyester, chain-extended with an isocyanate and modified with Rhein Chemie
additives (such as Stabaxol® P 200 and Addocat® 102) to form a "green" polymer. The
Stabaxol® additive, a carbodiimide, scavenges the acid groups on the biopolyols and
improves both the reactivity and the hydrolytic stability of the foam system. The Stabaxol®
additive also minimizes the deactivation of the catalysts by reacting out the acids that lead
to variable reactivity. By 2004, only two years after Rhein Chemie developed this techno-
logy, its additives were being used in low-density insulated spray foams for industrial,
commercial, and residential insulation.
Scalable Non-Aqueous Process to Prepare Water-Soluble
Aminodiol
The p38(4) MAP (mitogen-activated protein) kinase inhibitor is a drug of the
pyridinylimadazole class for the treatment of rheumatoid arthritis and, potentially, asthma
and psoriasis. It blocks the destruction of joint tissue and the production of the tumor
necrosis factor a (TNFa) and interleukin-ip (IL-ip) in monocytes and in animal models
of arthritis.
Roche Carolina employs a convergent synthesis to produce this active pharmaceutical
ingredient (API). One of the fragments involved in the synthetic route is 3-aminopentane-
1,5-diol. Unfortunately, this aminodiol intermediate is highly water-soluble, making it
difficult to isolate from an aqueous reaction mixture. Extraction from the aqueous system
requires a very large volume of the organic solvent, dichloromethane. Purification of the
resulting viscous liquid is either by distillation or via crystalline salt, but requires multiple
operational steps. This process was sufficient to produce the API for Phase I and Phase II
clinical trials, but was not appropriate for manufacturing larger quantities for commercial
use. A non-aqueous isolation and purification of the aminodiol fragment on a larger devel-
opment scale and, subsequently, on a commercial scale, presented important technical
challenges to be overcome to implement a more environmentally appropriate manufactur-
ing process.
-------
Roche Carolina has developed a process addressing these environmental concerns. In
this new process, 3-aminopentane-1,5-diol is synthesized in two isolated steps and four
chemical reactions starting from readily available and inexpensive dimethyl acetone-
1,3-dicarboxylate. The company has optimized the process through significant streamlin-
ing, resulting in the use of a single solvent, which is easily recovered and recycled. The key
operations involve: sodium borohydride reduction of dimethyl S-A^-terf-butoxycarbonyl-
aminoglutarate, a one-pot deprotection, and purification of the 3-aminopentane-l ,5-diol
using an acidic resin under non-aqueous conditions. The overall yield of the new synthe-
sis is 89 percent and the API purity is 99.5 percent. Raw material costs and operating costs
are both greatly reduced.
Traw-norsertraline is an active pharmaceutical ingredient (API) with promising activi-
ty in the central nervous system. Sepracor's Process Research & Development Group
devised a green route to fraw-norsertraline using a catalytic asymmetric hydrogenation that
replaces a process based on a stoichiometric chiral auxiliary. To implement this synthesis,
Sepracor had to identify an effective catalyst for a challenging asymmetric hydrogenation.
The company also had to develop novel chemistry for two steps surrounding the catalytic
transformation.
Because large-scale access to enamides is underdeveloped, Sepracor scientists developed
a novel, nonmetal-based methodology to yield a high-quality substrate for the key reaction.
A chiral catalyst at low loading delivered the desired diastereomer in superb purity and
yield. The amide product was hydrolyzed to yield the drug product.
To improve on its first-generation scale-up and further streamline the process, Sepracor
reevaluated each step, creating a second-generation process. Sepracor refined the enamide
methodology using toluene as the solvent throughout and eliminating both methanol and
the energy-demanding distillation its use required. In partnership with Dow/Chirotech,
Sepracor identified a rhodium catalyst that enhanced the selectivity of the reaction to 98:2.
And finally, because amide cleavage on sensitive substrates is also underdeveloped, Sepracor
designed a facile cleavage of the key intermediate under mild conditions to deliver mater-
ial in good yield and quality. Compared to the first-generation synthesis, the
second-generation synthesis reduces waste by 30 percent, has a 41 percent shorter cycle
time, has a 15 percent higher yield, and uses less energy.
Because Sepracor implemented the more efficient process early during the development
cycle, the company will receive the environmental and economic benefits for the entire prod-
uct lifecycle. Sepracor developed this chemistry during 2006 and 2007; the company
subsequendy used it to produce 75 kilograms of high-quality material at plant scale.
Traditional floor cleaning methods use an automatic scrubber filled with a large volume
of cleaning solution consisting of water and a chemical detergent. Tennant Company's
ech20™ technology eliminates the need for adding a chemical detergent to the automatic
floor scrubber. The ech20™ technology electrically activates tap water, causing it to per-
form like an all-purpose detergent. By removing the need for chemicals in the automatic
scrubber, this technology eliminates the negative environmental and health impacts asso-
ciated with producing, packaging, transporting, using, and disposing of traditional
chemical detergents. Compared to traditional cleaning methods, the ech20™ technology
reduces water use by 70 percent and eliminates the need for chemicals.
Adventures in Green Chemistry
Sepracor, Inc.
echjo ™ — Electrically Charged Water
Tennant Company
51
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The electrically charged ech^™ solution is created in a special unit that is installed in
Tennant's automatic floor cleaning machines. The ech^™ solution attacks the dirt and
suspends it off the floor's surface, enabling the scrubber's pads or brushes to easily remove
the soil. Approximately 45 seconds after the ech20™ cleaning solution is created, it returns
to plain water. What is left in the automatic scrubber's recovery tank is plain water and the
soil removed from the floor. In this process, 100 percent of the water used reverts to neu-
tral tap water and can be handled and disposed of safely.
Tennant is the first in its industry to harness the cleaning power of water for cleaning
hard floor surfaces and to use electrically charged water on a mobile platform. Tennant
plans to make its patent-pending processing units available on several models of its clean-
ing machine platforms. Tennant launched its product during 2007; it has a number of
patents pending.
Thermo Fisher
Scientific
Green pH Electrodes
Glass tubing containing 20—30 percent lead is traditionally used to manufacture pH
electrodes as it has the ideal workability and coefficient of expansion to easily fuse to the
glass pH membrane tips. The solder used to join the electrodes' cables and connectors con-
tains lead as well. Mercury—mercurous chloride reference systems are also currently used in
some pH electrodes. Both lead and mercury create problems with electrode disposal; they
are known to be detrimental to the environment and, thus, products containing these
heavy metals must be disposed of as hazardous waste.
Thermo Fisher Scientific is now using a lead-free glass and lead-free solder to create
completely lead-free pH electrodes. The replacement glass uses a nickel—iron alloy metal
seal instead of lead to achieve the necessary properties. The cost of this lead-free glass
decreased recently so that it became a feasible replacement for lead-containing glass with-
out increasing the cost of the electrode. Eliminating lead from all pH electrodes in the
world market would save more than 2,000 kilograms of lead annually.
Some pH electrodes contain a mercury—mercurous chloride reference junction that is
known to be very stable, even in difficult sample matrices. Testing has shown that a sil-
ver—silver chloride reference held in a stable polymer-based electrolyte gives the same
performance, thus eliminating the need for mercury in the electrode. Eliminating mercury
from electrodes prevents them from requiring disposal as hazardous waste and also prevents
the risk of exposing the user to mercury if the electrode breaks.
These new pH electrodes will have performance and cost comparable to current lead-
and mercury-containing electrodes, but will be disposable as regular trash. Thermo Fisher
Scientific manufactured and tested its first prototype pH electrodes using completely lead-
free glass in 2007.
U.S. Department of
Energy, Argonne
National
Laboratory
Resin Wafer Technology
With technical and financial support from several partners, Argonne National
Laboratory (ANL) developed resin wafer technology to improve the energy and atom effi-
ciency of separations. Resin wafer technology enables electrodeionization (EDI) to be
extended well beyond its conventional applications in ultrapure water production to sev-
eral high-volume applications that also have high environmental impacts. The new
applications include production of biobased chemicals, management of industrial water,
production and purification of chemicals, and, potentially, photocatalytic production of
hydrogen from water or carbon dioxide (CO2) sequestration from flue gases.
52
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EDI is an electrically driven process that separates low-concentration charged species
from process streams at higher efficiency than electrodialysis, its lower-tech counterpart.
Resin wafer technology replaces the loose ion exchange resins that are employed in con-
ventional EDI. The resin wafer offers several performance advantages: (1) controlled
porosity, which makes stream flow more efficient; (2) enhanced ion conductivity, which
reduces power consumption; and (3) reduced leakage, which increases product recovery
and cuts waste stream loss. Compared with conventional EDI, resin wafer technology also
provides new functionalities. These include direct immobilization of biocatalysts, which
allows integrated bioconversion and separations; modification of wafer composition and
format, which increases ion selectivity and direct pH control; and even in situ catalysis.
Resin wafer technology also offers significant green chemistry benefits. It reduces the
cost of producing biobased chemicals, providing economic drivers for emerging biore-
fineries to displace petrorefineries. It decreases the use of fresh water and the release of
waste water in power plants. It reduces energy and chemical use during the production of
organic acids, esters, and other chemicals. Finally, it has the potential to enable enhanced
hydrogen production from water and CO.- capture from flue gases in coal power plants.
AN L has several patents for this technology. During 2007, AN L scaled up the technol-
ogy to a pilot-scale field demonstration.
53
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index
Award winners are indicated with *.
Advanced BioCatalytics Corporation
Changing the Nature of Surfactants: Protein Synergists with Microbial Uncoupling 17
The Adventus Group
EHC™for a Greener Groundwater Treatment Technology 17
Argonne National Laboratory, U.S. Department of Energy
Resin Wafer Technology 52
Arkema, Inc.
Replacement of Perfluorinated Alkyl Surfactants with Nonfluorinated
Surfactants in Polymer Manufacturing 33
Armstrong World Industries, Inc.
BioBased Tile™ with BioStride™ — A Revolutionary New Flooring Made
with Rapidly Renewable Resources 33
Ashland Inc.
GEOSET NEO®: Low Emission Technology for the Metal Casting Industry 34
Reducing the Environmental, Health, and Safety Impact of Cooling Water
Treatment Programs 35
Solventless, Low- Toxicity, Thermosetting Oligomers that Require Only Low
Energy to Cure 35
ATK Lake City Ammunition Division
Pirimer™: A Non- Toxic, Heavy-Metal-Free Primer Fueled by Red
Phosphorus for Small Arms Cartridges 36
Augsburg College, Arlin E. Gyberg; SarTec Corporation
The Mcgyan Process: A New, Heterogeneous, Fixed-Bed Catalyst Technology
for Continuous-Flow Biodiesel Production from Waste Fats and Oils 9
Augustine, Robert L., Center for Applied Catalysis,
Seton Hall University; The NutraSweet Corporation
Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols 9
Baker Hughes Incorporated
AuRACOR™ C-101 Encapsulated Time-Release Oilfield Corrosion Inhibitor 36
BASF AG; The Dow Chemical Company
Innovative Industrial Process for Synthesizing Propylene Oxide via Hydrogen Peroxide ... 40
*Battelle
Development and Commercialization of Biobased Toners 5
Carnegie Mellon University, Department of Chemistry,
Krzysztof Matyjaszewski
Atom Transfer Radical Polymerization with a Low Concentration of Copper
Catalyst in the Presence of Environmentally Friendly Reducing Agents 11
ChK Group, Inc.
Nanophase Mn(VII) Oxide: Synthesis using Green Technology and Applications 18
The Clorox Company
Green Works™ Natural Cleaners from the Makers of Clorox: Home Cleaning Products . . 37
55
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Codexis, inc.
Greening Atorvastatin Manufacture: Replacing a Wasteful, Cryogenic Borohydride
Reduction with a Green-by-Design, Economic Biocatalytic Reduction 19
Greening Montelukast Manufacture: Replacing a Stoichiometric Chiral Boron
Reagent with a Green-by-Design, Economical Biocatalytic Reduction Enabled by
Directed Evolution 19
Rapid Enablement of Green-by-Design Economic Processes for Chiral Alcohols
by a Platform of Recombinant, Robust, Divergent Evolvants of a Single Ancestral
Ketoreductase 20
Colorado School of Mines, Department of Chemistry and
Geochemistry, Thomas Wildeman
Passive Treatment of Metal-Contaminated Water 16
Commercial Fluid Power LLC
Elimination of Hexavalent Chromium Used in Hydraulic and Pneumatic Tubing 21
Cortec Corporation
Corrosion-Control Chemicals Based on Sustainable Resources 21
Cutting Edge Formulations, Inc.
Nature's Avenger® Organic Herbicide: A Fast-Acting Highly Effective,
Organic Alternative to Synthetic and Natural Herbicides 22
Cytec Industries Inc.
Cylinderized Phosphine as a Safer, More Environmentally Friendly Alternative
to Traditional Fumigants for Stored Products 38
Cytec Innovation Management System: Sustainable Development of New Products 38
Revolutionizing Energy- Curing Resins for Food Packaging Applications 39
*Dow AgroSciences
Spinetoram: Enhancing a Natural Product for Insect Control 7
The Dow Chemical Company
Novel Process for Producing Polyols Based on Natural Oils 39
The Dow Chemical Company; BASF AG
Innovative Industrial Process for Synthesizing Propylene Oxide via Hydrogen Peroxide ... 40
Dow Corning Corporation
Water and Energy Conservation in Denim Finishing 41
DuraBan International, Inc
Environmentally Friendly Antimicrobial Surface Treatment 22
E. I. du Pont de Nemours and Company
DuPont™ Cerenol™ — A New Family of Renewably Sourced, High-Performance
Polyether Glycols 41
Eastman Chemical Company
IntegRex Technology 42
Eli Lilly and Company
A Practical and Green Chemistry Strategy for the Manufacture of Neurokinin 1
Antagonist, LY686017 42
EverNu Technology, LLC
Enabling Technology for Methacrylic Acid Production using Isobutane as the Feedstock. . . 23
-------
EverTech LLC
Everdex-Enhanced Alowood 23
Foam Supplies, inc.
Ecomate® — Environmentally Benign Blowing Agent for Polyurethane Foams 43
G3 Technology Innovations, LLC
Surface Functionalized Nanomaterials: Significantly Reducing Fluorochemicals
in Consumer Items 24
Georgia Institute of Technology, School of Chemistry and
Biochemistry, Arthur Ragauskas
Developing Lignocellulosic Biorefineries 14
GlaxoSmithKline
GlaxoSm ithKline's Eco-Design Toolkit™ 44
Gyberg, Arlin E., Augsburg College; SarTec Corporation
The Mcgyan Process: A New, Heterogeneous, Fixed-Bed Catalyst Technology for
Continuous-Flow Biodiesel Production from Waste Fats and Oils 9
Hach Company
Arsenic-Free SPADNS Chemistry for Fluoride Analysis in Water 44
H-O-H Chemicals, Inc.
Electrochemical Control of Mineral Deposition in Open Evaporative Cooling
Water Systems: H-O-H Chemical's Green Machine 25
Huntsman Corporation
G2 Catalyst for New and Improved SURFONIC® Non-Ionic Surfactants 45
Inland Environmental Resources, Inc.
Environmentally Friendly, Antacid Formulations for Wastewater Treatment 25
International Polyol Chemicals, Inc. (IPCI)
Production of Diverse Industrial Glycols from Renewable Six- and Five-Carbon
Sugars and Glycerin, the Byproduct of Biodiesel Manufacture 26
Jiang, Shaoyi, Department of Chemical Engineering,
University of Washington
Development of Environmentally Benign, Nonfouling Materials and
Coatings for Marine Applications 10
Johnson & Johnson
Application of Green Chemistry Principles in the Scale- Up of the Darunavir Process . ... 45
KTM Industries, Inc.; Ramani Narayan, Department of
Chemical Engineering & Materials Science, Michigan State
University
Biodegradable Starch Foams for Protective Packaging 12
Leadbeater, Nicholas, Department of Chemistry,
University of Connecticut
Microwave Heating as an Enabling Tool for Greener Synthesis 11
LS9, Inc.
Microbial Production of Renewable Diesel Fuel 27
The Lubrizol Corporation
Novel Green Chemistries Extend the Useful Life of Automobile Catalytic
Converters and Reduce Exhaust Gaseous Emissions 46
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*Maleczka, Robert E., Jr. and Milton R. Smith, ill.
Department of Chemistry, Michigan State University
Green Chemistry for Preparing Boronic Esters 3
Matyjaszewski, Krzysztof, Department of Chemistry,
Carnegie Mellon University
Atom Transfer Radical Polymerization with a Low Concentration of Copper
Catalyst in the Presence of Environmentally Friendly Reducing Agents 11
Merck & Co.
An Efficient Green Synthesis of Isentress®: A Breakthrough HIVIntegrase Inhibitor 47
Michigan State University, Department of Chemical
Engineering & Materials Science, Ramani Narayan;
KIM Industries, Inc.
Biodegradable Starch Foams for Protective Packaging 12
'Michigan State University, Department of Chemistry,
Robert E. Maleczka, Jr. and Milton R. Smith, III
Green Chemistry for Preparing Boronic Esters 3
Milliken & Company
Alternative Green Adhesives Solutions for Textile Composites for Use in
Commercial Buildings: TractionBack® 47
MIOX Corporation
On-Site Generation of Mixed Oxidants as a Safe, Green Alternative to Chlorine
Gas and Concentrated Bulk Bleach 27
Monsanto Company
Revolutionizing Insect Control: Bollgard® Insect-Protected Cotton Technology
and Bollgard II® with Roundup Ready® Flex 48
*Nalco Company
3D TRASAR® Technology 6
Nanomaterials and Nanofabrication Laboratories, LLC
(NN-Labs); Xiaogang Peng, Department of Chemistry and
Biochemistry, University of Arkansas
Doped Semiconductor Nanocrystals as Heavy-Metal-Free Quantum Dots 13
Narayan, Ramani, Department of Chemical Engineering &
Materials Science, Michigan State University;
KIM Industries, Inc.
Biodegradable Starch Foams for Protective Packaging 12
NCH Corporation
System for Bioremediation of Effluents 48
Niwayama, Satomi, Department of Chemistry and
Biochemistry, Texas Tech University
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters 13
The NutraSweet Corporation; Robert L. Augustine,
The Center for Applied Catalysis, Seton Hall University
Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols 9
Organic Recovery, LLC.
Biochemical Hydrolyzation of Organics in Food Wastes into a Liquid Fertilizer
and Soil Amendment. 28
58
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Peng, Xiaogang, Department of Chemistry and Biochemistry,
University of Arkansas; Nanomaterials and Nanofabrication
Laboratories, LLC (NN-Labs)
Doped Semiconductor Nanocrystals as Heavy-Metal-Free Quantum Dots 13
Pfizer, inc.
Convergent Green Synthesis of Linezolid (Zyvox™), an Oxazolidinone
Antibacterial Agent 49
Pyrotechnique by Grucci, inc.
Perchlorate-Free Pyrotechnic Composition for Military Training Munitions 29
Ragauskas, Arthur, School of Chemistry and Biochemistry,
Georgia institute of Technology
Developing Lignocellulosic Biorefineries 14
Rawlins, James W. and Shelby F. Thames, School of
Polymers and High Performance Materials, University
of Southern Mississippi
Development of Com mercial- Grade Particleboards Based Solely on Soybean
Protein Adhesive 14
Vegetable Oil Based Macromonomers in Emulsion Polymers for High-Performance,
Zero-VOCArchitectural Coatings 15
Rhein Chemie Corporation
Additives for Optimizing Renewable Resources in the Production of Polyurethane
Systems and Plastics 50
Roche Carolina Inc.
Scalable Non-Aqueous Process to Prepare Water-Soluble Aminodiol 50
SarTec Corporation; Arlin E. Gyberg, Augsburg College
The Mcgyan Process: A New, Heterogeneous, Fixed-Bed Catalyst Technology for
Continuous-Flow Biodiesel Production from Waste Fats and Oils 9
Sepracor, Inc.
Adventures in Green Chemistry 51
Seton Hall University, Center for Applied Catalysis,
Robert L. Augustine; The NutraSweet Corporation
Bromine-Free, TEMPO-Based Catalyst System for the Oxidation of Alcohols 9
*SiGNa Chemistry, Inc.
New Stabilized Alkali Metals for Safer, Sustainable Syntheses 4
*Smith, Milton R., Ill and Robert E. Maleczka, Jr.,
Department of Chemistry, Michigan State University
Green Chemistry for Preparing Boronic Esters 3
Specialty Fertilizer Products
Biodegradable, Water-Soluble Anionic Polymers, Prepared in an Environmentally
Benign Process, Enhance the Efficiency of Phosphorus Use by Plants 30
Steward Environmental Solutions, LLC
Development and Commercial Application of SAMMS™, a Novel Adsorbent
for Reducing Mercury and Other Toxic Heavy Metals 30
Tennant Company
ech20™ — Electrically Charged Water 51
59
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Texas Tech University, Department of Chemistry and
Biochemistry, Satomi Niwayama
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters 13
Thames, Shelby F. and James W. Rawlins, School of
Polymers and High Performance Materials, University
of Southern Mississippi
Development of Com mercial- Grade Particleboards Based Solely on Soybean
Protein Adhesive 14
Vegetable Oil Based Macromonomers in Emulsion Polymers for High-Performance,
Zero-VOC Architectural Coatings 15
Thermo Fisher Scientific
Green pH Electrodes 52
Torch Technologies LLC
Manufactured Firelogs Based on Whole Timber 31
TyraTech, Inc.
Greening Insecticides and Parasiticides 31
U.S. Department of Energy, Argonne National Laboratory
Resin Wafer Technology 52
University of Arkansas, Department of Chemistry and
Biochemistry, Xiaogang Peng; Nanomaterials and
Nanofabrication Laboratories, LLC (NN-Labs)
Doped Semiconductor Nanocrystals as Heavy-Metal-Free Quantum Dots 13
University of Connecticut, Department of Chemistry,
Nicholas Leadbeater
Microwave Heating as an Enabling Tool for Greener Synthesis 11
University of Southern Mississippi, School of Polymers
and High Performance Materials, Shelby F. Thames
and James W. Rawlins
Development of Com mercial- Grade Particleboards Based Solely on Soybean
Protein Adhesive 14
Vegetable Oil Based Macromonomers in Emulsion Polymers for High-Performance,
Zero-VOC Architectural Coatings 15
University of Washington, Department of Chemical
Engineering, Shaoyi Jiang
Development of Environmentally Benign, Nonfouling Materials and Coatings
for Marine Applications 10
Wildeman, Thomas, Department of Chemistry and
Geochemistry, Colorado School of Mines
Passive Treatment of Metal-Contaminated Water 16
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