The Presidential
Green Chemistry Challenge
Awards Program:
Summary of 201 0 Award
Entries and Recipients
            An electronic version of this document is available at:



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 ...................................... 15


    Each year, chemists, engineers, and other scientists from across the United States nominate
 their  technologies for a Presidential Green Chemistry Challenge Award. This  prestigious
 award highlights and honors  innovative  green chemistry technologies,  including cleaner
 processes; safer raw materials; and safer, better products. These awards recognize and promote
 the environmental and economic benefits of developing and using novel green chemistry.
    The U.S.  Environmental  Protection Agency  (EPA)  celebrates this  year's   innovative,
 award-winning technologies selected from among scores  of high-quality nominations. Each
 nomination must represent one or more  recently developed  chemistry  technologies that
 prevent pollution through source reduction. Nominated technologies are also meant to succeed
 in the marketplace: each is expected to illustrate the technical feasibility, marketability, and
 profitability of green chemistry.
    This is a special year — 2010 marks the 15th year of the Presidential  Green  Chemistry
 Challenge Awards. Throughout the 15 years of the program, EPA  has received  more than
 1,300 nominations and presented awards to 77 winners. By  recognizing  groundbreaking
 scientific solutions to real-world environmental problems, the Presidential Green  Chemistry
 Challenge has significantly reduced the hazards associated with designing, manufacturing,
 and using chemicals. Winning technologies  alone  are responsible  for  reducing  the  use  or
 generation of more than 198 million pounds of hazardous chemicals, saving 21 billion gallons
 of water, and eliminating 57 million pounds of carbon dioxide releases to air. Collectively,  all
 of the nominated technologies  have produced far greater benefits.
    This booklet summarizes entries  submitted for the 2010 awards that fell within the scope of
 the program. An independent panel of technical experts convened by the American Chemical
 Society Green Chemistry Institute judged the entries for the 2010 awards. Judging criteria
 included health and environmental  benefits, scientific innovation, and industrial applicability.
 Five of the nominated technologies were selected as winners and were nationally  recognized
 on June 21, 2010, at an awards ceremony in Washington, D.C.
    Further information about the Presidential Green Chemistry Challenge Awards and EPA's
 Green Chemistry Program is available at www.epa.gov/greeiichemistry.
 Noie: The summaries provided in this documeni were obtained from the entries received for the 2010 Presidential Green
 Chemistry Challenge Awards. EPA edited the descriptions for space, stylistic consistency, and clarity, but they were not written
 or officially end.orsed by the Agency The summaries are intended only to highlight a fraction of the information contained, in
 the nominations. These summaries were not used in the judging process; judging was conducted, on all information contained
 in the entries received. Claims made in these summaries have not been verified, bv EPA.



Recycling Carbon Dioxide to Biosynthesize Higher
   Innovation and Benefits

   Ethanol made by fermentation can be used as a fuel additive, but its use is limited
   by Its low energy content.  ''Higher" alcohols (those with more than two carbons in
   the molecule) have higher energy content, but naturally occurring microorganisms
   do not  produce them. Dr.  James Liao has genetically engineered microorganisms to
   make higher alcohols from glucose or directly from carbon dioxide. His work makes
   renewable higher alcohols available for use as chemical building blocks or as fuel.
   Higher alcohols, especially those with 3—8 carbon atoms, are useful as chemical feedstocks
and transportation fuels. The efficient biosynthesis of these alcohols directly from carbon
dioxide (CC>2) or  indirectly from carbohydrates  would  reduce net carbon  emissions.
Unfortunately, native organisms do not synthesize these alcohols.  Until now, none of these
alcohols have been synthesized directly from CO2, and alcohols above five carbons have never
been synthesized in the biosphere.
   Dr.  Liao, an Easel Biotechnologies board member and professor  at the University of
California, Los Angeles (UCLA), has developed a microbial technology to produce alcohols
with 3—8  carbon  atoms from COo. His technology leverages the  highly active  amino acid
biosynthetic pathway, diverting its 2-keto acid intermediates toward alcohols. With this
technology. Professor Liao and his  group  have  produced isobutanol from glucose in near-
theoretical yields  with high efficiency and  specificity. They  also  transferred the pathway
into  a  photosynthetic microorganism, Synechococcus elongatus PCC7942, which produces
isobutyraldehyde  and isobutanol   directly  from CC>2. The engineered strain produces
isobutanol at a higher rate than those  reported for ethanol, hydrogen, or lipid  production
by cyanobacteria or algae. This productivity is also higher than the current  rate of ethanol
production from corn. The technology shows promise for direct bioconversion of solar energy
and CC>2 into chemical feedstocks.
   Higher alcohols are also good fuels. As  fuel substitutes, they have several advantages over
ethanol, including higher  energy density, lower hygroscopicity, and  lower  vapor pressure
leading to better air quality. After excretion by the cells as aldehydes, the products are readily
stripped from the bioreactor, avoiding toxicity to the microbes.  Chemical catalysis  then
converts the harvested aldehydes to alcohols or other chemicals.
   If 60 billion gallons of higher alcohols were used each year as  chemical  feedstocks and
fuel  (replacing 25  percent  of gasoline),  Dr.  Liao's technology could  eliminate about
500 million  tons  of CC>2 emissions or about 8.3 percent of the total U.S. COo emissions.
Easel Biotechnologies is commercializing the CCb-to-fuels technology under exclusive license
from UCLA.
James C. Liao, Ph.D.,
Biotechnologies, LLC
     University of


LS9, Inc.
Microbial Production of Renewable Petroleum ™ Fuels
                                 Innovation and Benefits

                                 Industrial microbes usually make single substances, such as triglycerides like those in
                                 vegetable oil. Each single substance is then purified and converted into other chemicals,
                                 such as biodicscl fuel. LS9, Inc. has genetically engineered a variety of microorganisms
                                 to act  like  refineries. Each microbe makes a specific, final chemical product. Among
                                 these products is UltraClean™ diesel. This fuel, produced from biomass, eliminates the
                                 benzene, sulfur, and heavy metals found in petroleum-based diesel.
                                 The renewable, scalable fuels  and chemicals with the greatest potential for  rapid and
                               widespread adoption by consumers are those that are both cost-competitive with  petroleum
                               and compatible with the existing distribution and consumer infrastructure. LS9 has developed
                               a platform technology to produce a wide variety of advanced biofuels and renewable chemicals
                               cost-effectively by a simple,  efficient,  one-step  fermentation process. LS9 has engineered
                               established industrial  microorganisms to convert fermentable sugars selectively to alkanes,
                               olefins, fatty alcohols, or fatty esters, each in  a single-unit operation. The process enables
                               precise genetic control of the molecular composition and  performance characteristics  of
                               each  resulting fuel or chemical product. LS9's  technology leverages the natural efficiency
                               of microbial  fatty acid metabolism to  biosynthcsizc long hydrocarbon chains. It combines
                               this with new biochemical pathways engineered into  microorganisms to convert the long-
                               chain intermediates into specific  finished, fuel and chemical products that are secreted,  by
                               the cells. The products are immiscible with the aqueous fermentation medium and form
                               a  light organic phase  that is both  nontoxic to  the whole-cell catalyst and easily recoverable
                               by centrifugation. LS9 is actively developing the technology for the production  of alkanes
                               (diesel, jet fuel, gasoline), alcohols (surfactants), esters (biodiesel, chemical intermediates),
                               olefins (lubricants, polymers), aldehydes (insulation, resins), and fatty acids (soaps, chemical
                               intermediates). Specific product performance is enabled through the genetic control of each
                               product's chain length, extent of saturation, and degree of branching. Unlike the competing
                               biofuel processes, LS9's process does not require any metal catalysts.
                                 LS9 has successfully scaled up  its technology to produce UltraClean'" diesel at the pilot-
                               plant level. UltraClean™ diesel meets or exceeds all of the ASTM 6751 specifications for on-
                               road  vehicle  use. It eliminates the environmental pollutants benzene, sulfur, and the  heavy
                               metals found in petroleum-based diesel and will result in an 85 percent decrease in greenhouse
                               gas (GHG) emissions according to the GREET model for life cycle analysis (LCA). Without
                               subsidy,  UltraClean Diesel™ will be competitive in the market with diesel from oil priced at
                               $45—50 per barrel. LS9 is advancing toward commercial scale with its Renewable Petroleum™
                               facility, which will come on  line in 2010. Initially, this  facility will produce  UltraClean™
                               diesel; other  products will follow.  LS9 has achieved some success in direct biomass-to-fuel
                                 LS9  is applying  this  technology  platform  through  a  strategic   partnership   with
                               Procter & Gamble to produce surfactants for consumer chemical products. These and other
                               LS9 drop-in, renewable  products are on target to facilitate broad  environmental benefits
                               through rapid product adoption. The efficiency, affordability, and product performance bodes
                               well for the LS9 technology to become one of the keys to sustainable fuels.


Innovative, Environmentally Benign Production of
Propylene Oxide via Hydrogen Peroxide
   Innovation and Benefits

   Propylene oxide is one of the biggest volume industrial chemicals in the world. It is a
   chemical building block for a vast array of products including detergents, polyurcthancs,
   de-icers, food additives,  and personal care items. Its manufacture creates byproducts,
   including a significant amount of waste. Dow and BASF have jointly developed a new
   route to make propylene oxide with hydrogen peroxide that eliminates most  of the
   waste and greatly reduces water and energy use.
   Propylene oxide (PO) is among the top 30 largest-volume chemical intermediates produced
in the world; its annual worldwide demand is estimated to be over 14 billion pounds. It is
a key raw material for manufacturing a wide range of industrial and commercial products,
including polyurethanes, propylene glycols, and glycol ethers, which are used in a diverse array
of applications including automobiles, furniture, and personal care. Historically, manufacturing
propylene oxide either produced significant volumes of coproducts or required recycling of
organic intermediates. Traditional PO production uses chlorohydrin or one of a variety of
organic peroxides, which lead to coproducts such as  £-butyl alcohol, styrene monomer, or
curnene. In each case, there is a substantial amount of coproduct and waste. Although most
of the coproducts arc recovered and sold, demand for these coproducts does not  necessarily
parallel the demand for PO, leading to imbalances in supply and demand.
   Dow and BASF have developed the Hydrogen Peroxide to Propylene Oxide (HPPO) process,
a new, innovative route to PO based on the  reaction  of hydrogen peroxide and  propylene.
It has high yields and produces only water as  a coproduct. The  Dow—BASF catalyst  is a
ZSM-5-typc zeolite with channels of about 0.5 nm in diameter. In this catalyst, titanium
replaces several percent of the  silicon of the zeolite in a tetrahedral coordination environment.
With this novel catalyst, the  HPPO  process  is relatively straightforward. Propylene is
epoxidized by hydrogen peroxide in a fixed-bed reactor at moderate temperature and pressure.
The reaction occurs in the liquid phase in the presence of methanol as a solvent. The process
is characterized by both high conversions of propylene and high selectivity for propylene
oxide. Hydrogen peroxide is  completely  converted to product. In contrast with processes
using organic peroxides, the HPPO process uses substantially less peroxide and eliminates the
need to recycle peroxide. Production facilities arc up to 25 percent cheaper to build because
there is no need for equipment to collect and purify the coproduct.
   The HPPO process also  provides substantial environmental  benefits.  It reduces  the
production of wastewater by as much as 70—80  percent and the use of energy by  35 percent
over traditional technologies. BASF performed an Eco-Efficiency Analysis of the various
PO processes and found the  HPPO process is cheaper and has substantially lower  negative
impacts than alternative processes. The first commercial process based on this technology was
successfully commissioned in  2008 at the BASF production facility in Antwerp, Belgium. A
second PO plant based on this technology is scheduled to begin production in Map Ta Phut,
Thailand in 2011.
The Dow Chemical


        & Co., Inc.
Codexis, Inc.
Greener Manufacturing of Sitagliptin Enabled by an
Evolved Transaminase
                                 Innovation and Benefits

                                 Merck and Codexis have developed a second-generation green synthesis of sitagliptin,
                                 the active ingredient in Januvia™, a treatment for type 2 diabetes. This collaboration
                                 has lead to  an enzymatic process that reduces waste, improves yield and safety, and
                                 eliminates the need for a metal catalyst. Early research suggests that the new biocatalysts
                                 will be useful in manufacturing other drugs as well.
                                Sitagliptin is the active ingredient in Januvia®', an important treatment for type 2 diabetes
                              that is in high demand worldwide. The current manufacturing process includes a novel and
                              efficient asymmetric catalytic hydrogenation of an unprotected enamine. The process has
                              some inherent liabilities however: inadequate stcrcoselcctivity requires a crystallization step,
                              and high-pressure hydrogenation (at 250 psi) requires expensive, specialized manufacturing
                              equipment, and a rhodium catalyst.
                                Merck and  Codexis were independently aware  that transaminase  enzymes could,  in
                              principle, improve the manufacturing process for sitagliptin by converting a precursor ketone
                              directly to the desired chiral aminc. Merck's tests of available transaminases failed to  identify
                              an enzyme with any detectable activity on the sitagliptin ketone.
                                Collaboration between Merck and Codexis has lead to an improved, greener route for the
                              manufacture of sitagliptin. Starting from an ^-selective transaminase with some slight activity
                              on a smaller, truncated methyl ketone analog of the sitagliptin ketone,  Codexis evolved a
                              biocatalyst to enable a new manufacturing process to supplant the hydrogenation route. The
                              evolved transaminase had a compounded improvement in biocatalytic activity of over 25,000-
                              fold, with no detectable amounts of the undesired, 5-enantiomer of sitagliptin being formed.
                              The streamlined, enzymatic process eliminates the high-pressure hydrogenation, all metals
                              (rhodium and iron), and the wasteful chiral purification step. The benefits of the new process
                              include a 56 percent improvement in productivity with the existing equipment, a 10—13
                              percent overall increase in yield, and a  19 percent reduction in overall waste generation.
                                Evolved  transaminases are proving to be a general tool  for the synthesis of J?-amines
                              directly from ketones, constituting an important new green methodology  one of  the key
                              transformations identified by the American Chemical Society Green Chemistry Institutes
                              Pharmaceutical Roundtable. Merck and Codexis have used scientific innovation to benefit the
                              environment, meet the manufacturing demands of an important drug in growing demand,
                              and potentially enable a broad  class of chemistry.  During 2009, Merck  scaled up the new
                              process to pilot scale.  Plans to commercialize this technology arc moving forward.


Natular™ Larvicide: Adapting Spinosadfor
Next-Generation Mosquito Control
   Innovation and Benefits

   Spinosad is an environmentally safe pesticide but is not stable  in  water and so
   therefore cannot be used  to control mosquito larvae. Clarke has developed  a way to
   encapsulate spinosad in a plaster matrix, allowing it to be released slowly  in water
   and provide effective control  of mosquito larvae. This pesticide, Natular'™, replaces
   organophosphates and  other traditional, toxic pesticides and is approved for use in
   certified organic farming.
   Spinosad, a 1999 Presidential Green Chemistry Challenge Award winner, is an effective
insecticide with  excellent  control in many terrestrial applications. Its instability in water,
however, renders it ineffective for extended application in aquatic environments.
   Clarke has created a "sequential"  plaster matrix that protects the spinosad molecule from
water and releases it slowly, allowing extended performance of spinosad formulations for up
to 180 days. This matrix is insoluble calcium sulfate hemihydrate plaster and water-soluble
polyethylene glycol (PEG) binders fine-tuned for varying durations of insecticide release. The
PEG dissolves slowly, exposing the spinosad and calcium sulfate to water. The calcium sulfate
takes up the water to form the mineral gypsum and releases spinosad. Clarke formulated the
plaster matrix for Natular™ larvicide  entirely with approved pesticide inerts that also meet the
U.S. Department of Agriculture's (USDAs) National Organics Standard (NOS).The resulting
formulations of Natular™ larvicide provide excellent control of mosquito larvae in a range  of
aquatic environments from catch basins to salt marshes.  Clarke manufactures the dustless,
extended-release tablets with a solventless process that increases the environmental benefits.
   Natular™ larvicide is effective at application rates 2—10-fold lower than traditional synthetic
larvicidcs. It is 15-fold less toxic than the organophosphatc alternative, does not persist  in
the environment, and is not toxic to wildlife. Its manufacture eliminates hazardous materials
and processes. Natular™ is the first new, chemical larvicide for mosquito control  in decades;
it  meets  the highest standards for environmental stewardship and offers a new choice for
Integrated Pest Management (1PM). It is especially useful in environments with intermittent
water, such as tidal pools and flood  plains. These intermittently wet areas provide excellent,
short-term pools for mosquito breeding; the transient nature of the pooling makes traditional
mosquito control difficult. The Natular™ larvicide can be applied in dry or wet conditions,
however, and only releases the active ingredient when water is present.
   The benefits of using Clarke's new formulations extend beyond the reduced environmental
impact. Traditional larvicides require up to three applications per season. In contrast, Natular™
tablets require just one or two applications.
   Altogether,  Natular"" larvicide demonstrates  green  chemistry innovation  through the
development  and design of its controlled-release matrix. With the projected adoption  of
Natular'™ larvicide by local and federal agencies, Clarke anticipates a shift in the mosquito-
borne disease management industry toward reduced overall synthetic load in the environment
and improved health and quality of life in treated areas. In 2009, Clarke began commercial-
scale production of Natular™ larvicide in the United States. This patent-pending formulation
has been accepted for use domestically and abroad. Clarke also expects its slow-release matrix
will enable controlled release of other active ingredients, including herbicides and veterinary



 Template-Controlled Reactivity in the Organic

Solid State

   Subtle changes in molecular structure can profoundly influence the solid-state packing
and, thus, reactivity of molecules. Problematic crystal packing can prevent closely related
molecules from exhibiting homologous, solid-state structures and reactivity patterns.
   Professor  MacGillivray has developed a  general  method  to  control organic  chemical
reactivity in the solid state. He uses small organic molecules as templates to assemble olefins
into position for chemical reactions. The templates, not long-range crystal packing, control the
solid-state arrangements of the olefins. The templates assemble the olefins via hydrogen bonds
within stoichiometric solids known as co-crystals. The olefins then undergo intermolecular
[2+2] photodimerizations. This pioneering work has the potential to  open new avenues of
organic synthesis  because the solid-state medium allows molecules to react in geometries and
orientations that can be inaccessible in solution.
   Professor MacGillivray has used his solid-state method to synthesize molecules known as
ladderanes with regiospecificity, 100-percent yield, and no byproducts. Ladderane structures
are building blocks for many natural products that previously had presented a major synthetic
challenge for chemists. Recently, Professor MacGillivray received a patent for his solid-state
preparation of ladderanes; he and the University of Iowa Research Foundation arc working
toward commercialization.
   In 2008, Professor MacGillivray discovered that the co-crystals used for his solid-state
reactions  can form via solvent-free, mortar-and-pestle dry grinding.  Previously, co-crystal
formation had required solvent. In addition to synthesizing unique organic molecules, he has
used his methods to synthesize ligands in inorganic chemistry. Specifically, his molecules  can
be used as building blocks for self-assembled metal—organic architectures and porous materials
with structures akin to zeolites. His work opens the solid state as a general solvent-free medium
in synthetic organic chemistry with applications in inorganic chemistry and materials science.
Professor MacGillivray received the highly prestigious Arthur C. Cope Scholar Award of the
American Chemical Society in 2007 in recognition of his solid-state methodology.

High-Yield Conversion ofBiomass into a New

Generation ofBiofuels and Value-Added Products

   The prevailing, worldwide petroleum-based economy is  making way  for alternative
technologies. This transformation is creating an extraordinary  need for bioenergy research.
Consequently, researchers have developed several schemes to exploit lignocellulose, the most
abundant organic material on the planet. Although  these schemes vary considerably, each
one has the basic objectives of cleaving the glycan into its monosaccharide components and
deriving useful products from them efficiently and inexpensively. Researchers are continually
developing new schemes, but the  most successful will be those that produce the highest yields,
minimize capital and operating expenses, and allow the most feedstock flexibility.
   In 2008,  Professor  Mascal described a process to  convert cellulose into a mixture of
5-(chloromethyl)furfural (CMF)  and three minor furfural-derived products in a remarkable
85-percent overall yield. The method involved  acidic digestion of cellulose  in a biphasic
aqueous—solvent reactor in which the organic products, once formed, could be separated from
the acid before they decomposed. Subsequently, Professor Mascal discovered that his method
works equally well on raw biomass: it produces not only CM F in high yield from the cellulose
Professor           R.
Department of
Chemistry,  University
of         University of

Professor IVIark
Mascal, Department
of Chemistry,
University of
California, Davis;

Professor Satomi
Tech University;
USA, Inc.; Kishida
Chemical Co., Ltd.
Professor Phillip E.
Savage, Chemical
University of
of biomass, but also furfural itself from the Cs-sugar (hemicellulose) fraction. Thus, it uses all
of the carbohydrate of biomass.
  Recently,  Professor Mascal and his group  have refined  their process so  that the only
products they obtain from cellulose are CMF (84 percent) and levulinic acid (LA) (5 percent)
in an overall  89-percent yield. From sucrose their process gives CMF and LA in a combined
95-percent yield. Their method  also works well on biodiesel feedstocks to produce a hybrid
lipidic—cellulosic biodiesel that increases the yield of fuel from oil seeds by up  to 25 percent.
No  other known process gives simple organic products from cellulose in comparable yields.
Professor Mascal is currently partnering with an experienced biofuels developer to commission
a 2  million gallon per year production facility by 2011.

Highly Efficient and Practical Mono hydrolysis of

Symmetric Diesters

  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 conversions because the  starting symmetric compounds
are  typically  available commercially at low cost or are produced easily  on a large scale  from
inexpensive precursors. Water-mediated desymmetrization of symmetric organic compounds
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.  They are
frequently applied to the synthesis of polymers, dendrimers, and hyper-branched polymers.
Because the  two ester groups in the symmetric diesters are  equivalent, it is challenging to
distinguish these ester groups chemically. Classical saponification usually produces complex
mixtures of dicarboxylic acids,  half-esters, and the starting  diesters, which are difficult to
separate. As  a result, saponification yields a large amount of undesirable, dirty waste. The
most common method  for effective monohydrolysis uses enzymes, which provide no  basis
for  predicting reactivity. Ring-opening reactions of cyclic acid anhydrides require hazardous
organic solvents.
  Professor Niwayama pioneered water-mediated desymmetrization and has been developing
monohydrolysis of symmetric  diesters  to form half-esters  with  remarkable success. She
discovered a  highly  efficient, practical ester monohydrolysis of symmetric diesters. In this
reaction, aqueous sodium hydroxide or potassium hydroxide is added to a symmetric diester
suspended in water with or  without a small amount of a cosolvent such as THF at 0 °C.
The reaction produces pure half-esters in high to near-quantitative yields  without producing
dirty waste and without hazardous organic solvents. This reaction, which is  anticipated to
contribute significantly to green  chemistry and be useful in both industry and academia, has
been licensed by Wako Chemicals USA and Kishida Chemical Company. Several half-esters
produced by this reaction have been commercialized.

Terephthalic Acid Synthesis in High-Temperature

Liquid Water at High Concentrations

  Terephthalic  acid  (TPA) is  a monomer  used  to  produce polyethylene terephthalate
(PET), a plastic material used  for disposable water bottles and beverage containers. The
main commercial  route to TPA is the partial  oxidation of/nxylene in  acetic  acid with a
manganese—bromine—cobalt  catalyst. The environmental profile of this route is poor. Acetic
acid is  flammable; it also reacts  with the bromide catalyst to produce high levels of methyl
bromide emissions. (According to EPAs Toxics Release Inventory, a single terephthalate acid
plant can  release approximately 45,000  pounds of methyl  bromide annually.) Water is a

byproduct of terephthalic acid synthesis. Separating the water byproduct from the acetic acid
solvent for recycling requires an expensive, energy-intensive distillation. Further, acetic acid
oxidizes during the reaction so that approximately 4 billion pounds of makeup acetic acid are
required each year. Manufacturing this makeup acetic acid requires substantial raw materials
and energy. It also creates pollutant emissions.
   Professor Savage and his group have discovered reaction conditions and a reactor strategy to
synthesize terephthalic acid by the catalyzed partial oxidation of^-xylene at high concentrations
in high-temperature  liquid water. This reaction  has  high yields  and nearly 100-percent
selectivity. Replacing acetic acid with water has many benefits. Water is not flammable. Using
water eliminates methyl bromide emissions and the oxidative solvent losses  that require make-
up acetic acid. Because water is both the byproduct  and the  solvent, the large  distillation
column is unnecessary, saving associated costs and energy.
   Professor Savage has also developed and analyzed  conceptual designs for his chemical
process  to  show quantitatively  that  it is competitive on  the bases of economics, energy
consumption, and environmental impacts. He has also developed processing strategies so that
his greener reaction conditions would accommodate  the high concentrations needed  for a
commercial process. The University of Michigan has filed a provisional patent application for
this technology.

Green  Process  of Unfolding Soy Protein Polymers for

Green Adhesives

  About  20 billion  pounds of  adhesives are used  annually in  the   United States for
applications including wood products, foundries,  packaging, and labeling. These adhesives
are mainly petroleum-based. Industry is seeking biobased adhesives and coatings, but enabling
technologies are lacking. On the other hand, the byproducts of the current  annual production
of soybean biodiesel and corn ethanol include  about 90 billion pounds of low-cost, protein-
based meals aside from food and feed uses.
   Most proteins contain both hydrophobic and hydrophilic regions. Hydrophobic interactions
are a dominating factor in protein  folding, unfolding, aggregation, gelling, self-assembly,
adhesion, and cohesion. Hydrophobic regions are often buried inside the complicated protein
molecule, however.
   Professor Sun's technology unfolds protein molecules with  0.5-5 percent nonhazardous
agents such as urea, detergents,  organic—inorganic salts, and pH-adjustment agents such as
sodium hydroxide (NaOH) and hyrdrochloric acid (HC1). As the proteins unfold, some of their
covalent and hydrogen bonds break and form individual polypeptides. Because hydrophobic
groups are now exposed on their  surfaces,  the  resulting polypeptides become surface-
active and  interact with other hydrophobic polymers, cross-linking agents, and chemicals.
Potential applications include adhesives; surfactants; coatings; medical materials such as tissue
engineering, drug delivery, and pharmaceuticals; thickeners and binders for food and animal
feed; and cosmetic products. This technology makes high-value products from the coproducts
of biofucl  production  and, thus, can have great impacts on bioenergy and the environment.
It will replace at least  6 billion pounds of hazardous materials  including adhesives based on
formaldehyde, vinyl acetate, isocyanine, and acrylic acid. The performance of Professor Sun's
adhesives is superior or similar to urea—formaldehyde, phenol—formaldehyde, and many other
synthetic, latex-based adhesives.
   Dr. Sun's adhesive technologies arc in the pipeline for commercialization.  Biodegradable,
edible feed containers  for livestock were commercialized in 2007. One company has licensed
the technology for pet food binders; others are  evaluating samples for a variety of uses.
                of Grain
Science      Industry,
Uni¥ersity; Soy Resin,

Professor Yi Tang,
University of
Los Angeles
Professor Robert
M.      mouth,
University; Dr.
James L. Hedrick,
An Efficient, Biocatalytic Process for the Semisyntbesis


   Statins are important drugs for treating cardiovascular diseases. Lovastatin, a secondary
metabolite produced by Aspergillus terreus, was the first FDA-approved statin. Simvastatin
is an important semisynthetic derivative of lovastatin; it has two methyl groups (not one) at
the C2' position of the side chain. Simvastatin has become the second-highest-selling generic
drug since 2007 when it went off-patent as Merck's Zocor". In 2008, simvastatin had sales of
approximately $2 billion.
   Adding the methyl group to convert lovastatin into simvastatin requires a multistep chemical
synthesis that includes  protecting then dcprotccting other functionalities in the lovastatin
molecule. Two main routes have been described.  In the first route, lovastatin is hydrolyzed
to the triol, monacolin J, followed by  protection by selective silylation, esterification with
dimethyl butyryl chloride, and deprotection. The  other route involves protection of the
carboxylic acid  and alcohol  functionalities,  followed  by methylation  of C2' with methyl
iodide and deprotection. Both routes are inefficient: they have less than 70 percent overall
yield despite considerable optimization. Both are mass-intensive as a result of protection and
deprotection. Variations on these routes have been patented, but none have overcome the
limitations of the current multistep process.
   Professor Tang and his group  have  developed a route that circumvents protection and
deprotection, is more efficient, and  results in  greater  atom economy, reduced waste, and
overall less hazardous reaction conditions.  First, they cloned and identified  LovD, a natural
acyltransferase in Aspergillus terreus that is involved in the synthesis of lovastatin and can accept
low-cost, non-natural acyl donors. They recognized that LovD might be a type of simvastatin
synthase and a starting point for  developing a  biocatalytic  process. They then evolved this
enzyme toward commercial  utility.  Codexis has licensed  the technology, engineered the
enzyme further, and optimized the process to accomplish pilot-scale simvastatin manufacture
in 100 kilogram batches. Commercial-scale manufacturing is planned in 2010.

Organic Catalysis:  A Broadly Useful and

Environmentally Benign Strategy to Synthetic Polymer


   The discovery of highly active, environmentally benign, catalytic processes is a central
goal of green chemistry. The  team of Dr. Hedrick and Professor Waymouth has  developed
a broad class of highly active, environmentally benign organic catalysts for the synthesis
of biodegradable and biocompatible plastics. Their technology applies metal-tree, organic
catalysts to the  synthesis and recycling of polyesters. The team has discovered several new
families of organic catalysts that rival or exceed metal-based alternatives for polyester synthesis
in both activity and selectivity. These new synthetic strategics provide an environmentally
attractive, atom-economical,  low-energy alternative  to traditional metal-catalyzed processes.
This technology includes organocatalytic approaches to a variety of polymerization techniques
such as ring-opening, anionic, zwitterionic, group transfer, and condensation polymerization.
Their mechanistic and theoretical  investigations have provided new insights into the diversity
of mechanistic  pathways for organocatalytic polymerization reactions and  opportunities
for the synthesis of well-defined  macromolecular architectures. The novel mechanisms of
enchainment of their catalysts provide  access to polymer architectures that are difficult to
access by conventional approaches.
   Their monomer feedstocks  focus  primarily  on those from  renewable resources such as
lactides derived from biomass, but  also include those from petrochemicals. Dr. Hedrick

and Professor Waymouth have designed and implemented organic catalysts to depolymerize
petrochemical-based polymers such as  poly(ethylene terephthalate) (PET)  quantitatively,
allowing a bottle-to-bottle recycling of PET to mitigate the millions of pounds of PET that
plague landfills. Their catalysts are tolerant to a wide variety of functional groups, enabling
them to synthesize well-defined biocompatible polymers for biomedical applications. Because
these catalysts do not remain bound to polymer chains, they are effective at low concentrations.
These results, coupled with cytotoxicity measurements in biomedical applications, highlight
the environmental and human health benefits of their approach. The team has received eight
patents on this work; since 2002, their work has received over 1,000 citations in the scientific


Safer,  Sustainable, Biodegradable, Solid-State

Chemistry for Treating Cooling Water Systems

   Scale and corrosion inhibitors for liquid cooling water typically contain 10—15 percent
active ingredients in an aqueous solution. Because many of the active ingredients are insoluble
at neutral pH at these concentrations, sodium hydroxide (NaOH) is added to increase the pH
and stabilize the solution. Typical formulations contain 10—30 percent NaOH,
        APTech Group has developed  chemistry so that only the active ingredients are
mixed,  heated, filled into recyclable containers, cooled, and  allowed to cure, resulting in a
unique, noncorrosive, solid-state concentrate. At the point of use, the solid-state product is
reconstituted with system makeup water into a dilute solution (approximately 0,5 percent
or less). NaOH is not needed because the low concentrations of the active ingredients in the
dilute solution are below the solubility limits for these chemicals,
       The solid-state product  is not a  compressed series of raw materials or physical
mixtures, but a true homogenous solid state comprised of both liquids and powders blended
in a proprietary process. "When made into solution on demand, the product contains the
same reproducible ratio of active ingredients needed to prevent scale and corrosion in water
systems. This technology not only eliminates the discharge of NaOH into wastewater streams
but also eliminates the potential for spills of this corrosive chemical. At present sales  levels,
this technology is eliminating the use of almost 280,000 pounds of NaOH each year. It is also
saving 462,000 gallons of production water and 660,000 gallons of rinse water annually.
       APTech Group has recently improved its technology so that its products consist of
totally biodegradable materials. Potentially, this could eliminate the 106 million pounds per
year of non-biodegradable  materials. Finally,  new energy-efficient eductor dosing systems
can reduce energy consumption by 90 percent over conventional pumping systems. APTech
Group  has filed a patent for its eductor system.

HCR-188C1: An All-New,

Hydrocarbon Refrigerant with No Impact on Global

Warming or the Ozone Layer

   Chlorofluorocarbons (CFCs) have been used  as  refrigerants in air conditioners and
refrigerators since the 1930s. Although CFCs have the advantages of incombustibility, high
stability, and low toxicity, they contribute heavily to ozone-layer depletion, languishing as
chlorine atoms in the stratosphere for up to a century. As a  result, the production and use
of CFCs have been virtually abolished. CFCs have been  systematically replaced by various
hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), Although HCFCs and
HFCs are less destructive to the ozone layer, they are powerful greenhouse gases with their
own environmental risks.
   A.S. Trust &  Holdings  has  developed HCR-188C1,  a  substitute hydrocarbon  (HC)
formulation that has been independently shown to have zero ozone depletion potential (ODP)
and zero global warming potential (GWP). HCR-188C1 is a proprietary blend made strictly
from naturally occurring substances approved for common use and available from any gas
manufacturer: propane, butane, isobutene, and ethane. This blend can be used independently
of CFCs, HFCs, and HCFCs. It cools so effectively that the mass of HCR-188C1 needed in
a refrigerator or automotive  air-conditioning system is only one-quarter that needed for CFC
R-12 or the high-GWP formula, HFC R-134a. HCR-188C1 is the only approved alternative
refrigerant that can substitute in systems designed for both CFC R-12 and HFC R-134a.
    APTech Groyp, Inc.
    A.S. Tryst & Holdings,

BCR Environmental
   HCR-188C1 also features major safety improvements over other HCs, including reduced
charge rates. It solves  the problem of decomposition upon leakage that causes HFCs to
become less efficient and require more frequent replacement. The higher molecular weight of
HCR-188C1 makes it less apt to leak through joints or o-rings; HCR-188C1 also retains its
cooling properties longer, which extends the lifetimes of units that run on it. A.S. Trust has
been successfully using its original HCR-188C formulation for  automotive and refrigerator
cooling for more than ten years. The company launched  HCR-188C1  in the summer of

Recovering and Using a Formerly Incinerated Sodium

Nitrite Waste Stream to Disinfect and Stabilize

Municipal Biosolids

   Municipal wastewater treatment plants use biological processes to break down human waste.
Sewage sludge, the residue left after biological treatment, contains innumerable pathogens
that can harm humans, animals, and the environment. The treatment and disposal of sewage
sludge has become an increasing problem. Municipal landfill space is limited;  alternatively,
applying sludge to land may restrict the land use for years, depending on how the sludge was
   BCR Environmental developed its Neutralizer* process as an effective, safe, verifiable, and
economical solution to disinfect and stabilize municipal sludge, making  it safe for use as a
fertilizer. The Neutralizer* process destroys the pathogens in sewage sludge and  stabilizes the
sludge so that it does not attract vectors. This process generates  its two principal chemicals,
chlorine dioxide and nitrous acid, onsite at the wastewater treatment plant. During the process,
sludge at up to 4-percent solids is treated with chlorine dioxide. Next, sodium nitrite and an
acid are added; at pH 2.3, the sodium nitrite is converted to nitrous acid, which destroys any
remaining pathogens and their eggs. Finally, the pH is returned to near-neutral and the treated
sludge is dewatered for use as a fertilizer.
   BCR collaborated with SABIC Innovative Plastics to  use a waste stream from SABIC's
production of thermoplastic resin as the source of sodium nitrite for the Neutralizer* process.
The resulting commercially viable, biologically safe fertilizer frees up landfill space, offsets the
production of commercial fertilizer, reduces  the production of greenhouse gasses, and  saves
the energy required to incinerate millions of gallons of SABIC's nitrite-bearing waste stream.
In December 2009, EPA notified BCR that it had successfully completed the process for
approval of its Neutralizer" Process, the first process to receive this approval in the last sixteen

Spray-Dried Dispersions  Based on Hydroxypropyl

Methylcellulose Acetate Succinate for Delivery of

Low-Solubility Drugs

   Increasingly, drug candidates emerging from drug-discovery programs have low water
solubility. Indeed, approximately 40 percent of all new drug candidates and 70 percent of
new anticancer drug candidates in development are not well-absorbed orally, principally due
to low water solubility. These candidates frequently have low oral bioavailability and require
high doses to achieve therapeutic effects.
   Bend Research has developed a novel, green, drug-delivery technology using hydroxypropyl
methylcellulose acetate succinate (HPMCAS), a low-toxicity, renewable material. Spray-dried
dispersions  (SDDs) of low-solubility drugs and HPMCAS dissolve rapidly. They disperse

ill the body to enhance the bioavailability of low-solubility drugs by 10-fold or more and
to reduce the dose of active pharmaceutical ingredients  required for  therapeutic results.
Currently, the pharmaceutical industry generates an estimated 25—100 kilograms  of waste
per kilogram of product. If all low-solubility drugs were formulated as HPMCAS SDDs,
the enhanced bioavailability could eliminate more than 27,000 tons of toxic pharmaceutical
waste annually.
   The HPMCAS SDD manufacturing process uses green chemistry and renewable materials.
Typically, only the drug and HPMCAS are dissolved in an organic solvent, such as acetone,
methanol, or mixtures of these with water. The dispersion is spray-dried and the solvent is
recovered for reuse.
   HPMCAS is an amphiphilic polymer. Its hydrophobic regions interact with low-solubility
drug molecules and its hydrophilic regions allow the drug—HPMCAS structures to form stable
colloids in aqueous solution. HPMCAS forms amorphous dispersions with a broad range of
structurally diverse low-solubility drugs for use in solid, oral dosage forms. Bend's technology
can enable the development of many promising drug candidates that would otherwise be
halted due to low solubility. Over 400 candidate  drug compounds have been successfully
formulated as HPMCAS SDDs; 28 have advanced to human clinical testing, including one to
Phase 3- In 2007,  Bend constructed a $90 million commercial SDD production facility.

Supercritical—Solid Catalyst Reaction  Process for

Converting Waste Fats,  Oils,        Greases into  Premium


   BioFuelBox    has    developed   and    successfully   operated    a   process    for
continuous-flow production of ASTM-quality biodiesel without using toxic  consumable
catalysts or post-reaction purification reagents. The technology, patented by Idaho National
Laboratory and licensed  by  BioFuelBox,  uses heat and pressure in  a  closed system with
heterogeneous  catalysis  and  nontoxic gaseous  cosolvents  at  supercritical  conditions.
The simplistic combination of these factors  allows the  use of historically unsuitable lipid
feedstocks, including those containing microbial degradation products, heavy metals, organic
sulfur, extreme fatty acid levels, and water, to produce 100-percent biodiesel (B100). The
continuous-flow supercritical—solid catalyst (NovoStream'") process does not  require added
acid or  base catalyst or the subsequent neutralization and water-washing steps typical of
traditional biodiesel production.
   By implementing this  technology  at its  American Falls, Idaho  facility  over  the past
year, BioFuelBox  has demonstrated the feasibility  of converting over 10,000 liters per day
of previously landfilled lipid waste (such as grease trap sludge)  to quality, consumer-ready
methyl ester fuels  in high yields.  Further, the NovoStream™ process makes fuel without the
significant chemical waste and massive water use that are typical of traditional biofuel synthetic
   The BioFuelBox technology reduces environmental impacts  not only by  the chemistry
involved, but also  by using the lowest grades of municipal and industrial waste as feedstocks.
These materials, with volumes of nearly 4 billion gallons annually in the United States alone,
are currently destined for disposal in landfills, where they subsequently undergo microbial
degradation to form potent greenhouse gases. The patented technology has proven successful in
the energy-efficient, rapid conversion of these wastes to fuels. The benefits include eliminating
this portion of our nation's waste burden as well as reducing the use of food-oil seeds for non-
food uses. In August 2009, BioFuelBox produced 50,000 gallons of BlOO biodiesel fuel.
BioFuelBox, Inc.

Chemgyard Ltd.
Commercial Flyid
Power LLC
Elimination of Perfluorinated Alkyl Surfactants from
Fire-Fighting Foams

   Traditional fire-fighting foams for use on Class B (i.e., flammable liquid) fires,  known as
Aqueous Film-Forming Foams (AFFFs),  typically contain perfluorinated alkyl surfactants,
which extinguish fires quickly and resist re-ignition. Foams are used extensively in a wide variety
of fire-fighting  applications, including fixed systems  (fuel loading docks,  aircraft hangers,
fuel  storage tanks, etc.) and hand-line applications (municipal  fire fighting trucks, airport
emergency response, etc.). In general, fire-fighting foams are applied to quickly extinguish an
                                     fuel fire and to suppress re-ignition. Water alone cannot accomplish this.
   When possible, containment systems capture residual foam liquid to prevent its release.
Often, however, foam is applied to an unignited fuel spill as a safety precaution to prevent a
flash fire while rescue workers perform their duties in and near the flammable fuel. In many
cases, it is not feasible to contain the foam once applied. It is well-known that perfluorinated
alkyl chains used  in AFFFs are persistent in nature. There is an ongoing debate as to the
human health and environmental effects of such chemicals  released into the environment
during normal use.
   Chemguard developed ECOGUARD and its principle surfactant component in response
to market requests for an organofluorine-free, alternative AFFF. ECOGUARD uses a novel
hydrocarbon polymer  surfactant  (Chemguard  HS-100) to  substitute for and  eliminate
perfluorinated alkyl surfactants. The convergent, three-step synthesis of HS-100  has no
byproducts and produces only water from the condensation polymerization. Because the
properties of HS-100 eliminate the need for polysaccharide thickeners, the ECOGUARD
formulation does  not require a biocide. ECOGUARD is readily biodegradable and has a
"low concern" for  toxicity. ECOGUARD is registered by Underwriters Laboratories (UL) for
hand-line operations and for use in sprinkler systems. Among organofluorine-free foams, only
ECOGUARD has passed the UL sprinkler test. Chemguard was recently awarded two patents
related to its organofluorine-free fire-fighting foam formulations.

Elimination of Hexavalent Chromium from Hydraulic

       Pneumatic Tubing

  The fluid power market relies heavily on  chrome-plated tubes to produce pneumatic and
hydraulic cylinders. Chrome  plating provides an excellent wear surface, great lubricity, and
good corrosion resistance; it  is  economical, time-tested, and readily available. The plating
process is problematic. Plating produces a mist containing hexavalent chromium (Cr(YQ) ions
that are carcinogenic. Although  most large chrome-plating facilities currently meet or exceed
EPA, OSHA, and  other government standards for air quality, disposal, and containment of
waste, the trend toward tighter controls will continue. Stringent regulations will continue to
drive up the cost of chrome plating.
  Commercial Fluid  Power is taking steps  to reduce the use of industrial hard  chrome or
engineered  chrome in the fluid power market. The  company is developing and marketing
Nitro-tuff tubes as safe, environmentally friendly  replacements for  chrome-plated tubes.
Nitro-tuff tubes are ferritic nitro-carburized steel. During their manufacture, the surface of the
steel is converted to a non metallic epsilon iron nitride (e-Fe3N) in an atmosphere of ammonia
and carrier gas. Following nitriding, an oxidizing atmosphere is introduced to produce a thin,
corrosion-resistant, black surface film  of Fe3NC>3_4. The iron  nitride layer is the basis for the
steel's extraordinary wear and corrosion resistance. Advances in mechanical properties, size,
and finish control  now allow Nitro-tuff tubes to substitute for chrome-plated tubes without
loss of quality or strength. These efforts are reducing the use of hexavalent chromium and its
release into  the environment.

   In  conjunction with  MACSTEEL's  NitroSteel Division,  Commercial Fluid Power
continues to strive to bring an eco-friendly, cost-effective solution to the fluid power market.
Recent research, development, and testing have overcome past challenges and opened new
markets for Nitro-tuff tubes and bars. The journey for safer, more environmentally friendly
replacement products at Commercial Fluid Power  is ongoing. During 2009, Commercial
Fluid Power developed a process for nitriding stainless steel.

Corrosion  Control with  a  Greener Pathway
a survey commissioned by the Federal government estimated the cost
   Several years ago
of corrosion in the United States at $275 billion annually. Corrosion of metals is a natural
process during which metals oxidize. Selected chemicals can prevent, control, and slow down
the corrosion of metals. Traditional chemicals used for corrosion control include cyclohexyl
ammonium benzoate and other amine salts.
   Cortec Corporation  (derived from corrosion technology)  began to  evaluate sugar beet
glucoheptonate as an  anti-icing road  additive in  1994 when electrochemical  screening
indicated it could prevent metal corrosion in salt water. Cortec hypothesized that gluconic
acid derivatives could protect rebar in concrete from corrosion; after tests were successful, the
company began to develop this product. Cortec now sells eleven corrosion-control products
based on natural oils, six based on gluconates, one based on soy protein, and three films based
on polylactic acid. Its most successful product uses gluconic acid derivatives from sugar beets
as components of migratory corrosion inhibitors to protect the reinforcing steel (i.e., rebar) in
concrete from corrosion by salt.
   An independent study by American  Engineering Testing concluded that MCI 2005, a
product derived from gluconates, delayed the onset of corrosion in steel embedded in concrete
beams; when corrosion  developed, MCI 2005 reduced the corrosion current and the extent
of corrosion. The study involved 56 cycles of 3-percent sodium chloride (NaCl) ponding,
drying the concrete beams for two weeks, and  repeating the 3-percent NaCl ponding. The test
measured corrosion by electrochemical measurements on the embedded rebar in the concrete
blocks midway through each cycle.
   Cortec has been awarded six patents covering the use of gluconates to  protect rebar in
concrete and has been successful in selling these products worldwide. In 2008, sales of these
products were 6 percent of Cortec's total sales; this figure increased to over 7 percent in

Safer, Less  Toxic,  Sustained Release  Chemistry: Green

Water Treatment with Smart Release9 Technology

   Smart Release* Technology is a patented, controlled-release coating process for chemistries
used to treat water in cooling towers to prevent corrosion, scale, and fouling. It takes advantage
of existing  nontoxic, water-based suspension chemistries that  are free of volatile  organic
compounds  (VOCs) and  creates a semipermeable membrane coating that can be  used to
control the release of neutralized water-treatment chemistries. The polymeric coating includes
poly(vinyl acetate), vinyl versatate, and others. Smart Release™ Technology has demonstrated
that it can improve cooling tower efficiency; this promotes more reliable cooling and saves
   Because the solid. Smart Release* product contains 95-percent active ingredients compared
with 10-percent active ingredients for liquid products, Smart Release* requires less packaging
and shipping, which reduces its carbon footprint  by 74 percent. It reduces energy consumption
during application because it uses a feeder made  of recycled material that has no moving parts,
uses no energy, and requires no maintenance.  Smart Release" provides safer handling  because
                                                                      Cortec Corporation
                                                                      Dober Chemical

FRX Poly       Inc.
workers handle tablets with an inert outer coating that prevents contact with active chemistry.
Primarily because it is a pH-neutral solid, the active Smart Release* chemistry is less toxic
than competing liquid products. Smart Release* Technology also reduces accident potential
because solids are less prone to spills than are liquids.
   Smart Release'8' has applications in other aqueous treatment applications including potable
water,  biocides, biodispersants,  and  reverse osmosis  membranes.  Cool-N-Save'0', Dober's
recent  retail product line, provides safe, effective precooling water treatment for both light
industrial and private cooling units, permitting maintenance-free precooling. This technology
has been shown to reduce air conditioning costs by as much as 30 percent with a corresponding
reduction in energy consumption. A case study showed reductions of 15,000—50,000 kWh
per month in light industrial applications. In 2009, Dober sold more than 40,000 pounds of
Smart Release™'Technology for industrial cooling towers, which eliminated 1.5 million metric
tons of carbon dioxide (CO2) releases.

Green Chemistry to Replace Bromine-Based Flame


   Flame-retardant materials are a legal requirement globally for many plastics in electrical,
building, construction,  fiber,  and textile applications. Flame-retardant plastics and additives
comprise a worldwide materials market of over $15  billion with annual growth  rates of 5—6
percent. Over 60 percent of all current plastic formulations include a class of flame-retardant
additives known as brominated hydrocarbons. This popular class of flame retardants is, however,
being shown to have severe,  undesirable effects including persistence in  the environment,
bioaccumulation, and toxicity in rodent studies. In addition, the burning or thermal disposal
of these additives can result in highly toxic dioxins and furans. These problems combine to
place great pressure on companies to eliminate brominated agents as flame  retardants.
   FRX Polymers  has developed green chemistry that allows diphenyl methyl phosphonate
to polymerize  effectively with an aromatic diol  into either an oligomer or polymer with a
phosphorus content of greater than 10 percent. This unique polymer has the highest limiting
oxygen index measured for a thermoplastic material. FRX Polymers has also developed a
low-cost, green synthesis for the diphenyl methyl phosphonate monomer. Yields from both
the monomer  and polymer processes are essentially quantitative. The phenol coproduct of
polymerization is reused, so that little or no waste (less than 5 percent) is generated from the
production of  FRX polymers and copolymers. Eliminating bromine in favor of phosphorus
in flame-retardant additives is expected to allow  greater recovery and recyclability of plastics
after use.
   FRX Polymers is currently scaling up its synthesis of this  material and  plans  to reach
1,000 metric tons per year by the end of 2010. Customers have reported favorable results in
several applications  including biobased  polymers in carpeting, transparent flame-retardant
lenses  in LED lighting, electrical  connectors and  switches, and electronic and electrical
housings. To date, FRX Polymers has commercialized applications for two customers.
Sustainable Chemicals from Renewable Resources:
A Breakthrough for Biomanufacturing

   Genomatica develops and commercializes novel biomanufacturing processes to produce
industrial chemicals that impact all major industry sectors. The company produces sustainable
chemicals through proprietary technology that transforms the way in which natural processes
can be used to convert low-cost, renewable feedstocks into high-value  chemicals. It defines
sustainable chemicals as those that are designed and manufactured using efficient, effective,

safe, and more environmentally benign raw materials and processes. Petrochemical processes
generally are not sustainable because they are energy- and capital-intensive. They also  use
nonrenewable, hydrocarbon-based raw materials and solvents that are  often toxic. Finally,
they release large amounts of harmful waste and greenhouse gases.
   Genomatica's  breakthrough process  uses  an engineered  microorganism (E.  colt)  and
100-percent-renewable materials (i.e., sugar  and water) in  an anaerobic fermentation  to
produce 1,4-butanediol (EDO), a large-volume chemical used in many polymer applications.
Genomatica's technology platform  combines  computational modeling  and design with
experimental engineering  of  microorganisms and  overall  processes.  Genomatica used
proprietary  metabolic models  and simulation  algorithms to test all possible pathways  to
produce EDO from sugar inside microorganisms. It selected optimal paths and implemented
them in the  laboratory to produce a microorganism and. fermentation process for EDO.
   Compared to petroleum-based EDO processes, this new  bio-EDO process will produce
less waste and lower emissions, use  less energy, and reduce  per-unit capital investment. A
preliminary  life cycle analysis (LCA) indicates  that Genomatica's process to  convert sucrose to
EDO will require at least 59-percent less fossil energy and emit up to 68 percent less carbon
dioxide (CC>2) than do current, petrochemical  EDO processes. The most recent analysis shows
that biobased EDO will compete economically against petrochemical EDO if oil prices are
as low as $50 per barrel. Genomatica has  established a complete, cost-effective downstream
process and  recovered EDO from  30-liter fermentation broths at greater than 99.5-percent

Zequanox™, an Environmentally Safe Solution for

Controlling Invasive Zebra        Quagga Mussels

   Invasive mussels have a billion-dollar impact on the North American economy. Because
there are no environmentally responsible  pesticides on  the  market for selective control  of
invasive mussels, power generation and industrial facilities are treated regularly with chlorine
or other nonselcctive  biocidcs. Although  these chemicals are approved for this use, their
nonspedficity and toxidty raise concern for worker safety and the environment.
   Zequanox™ is  a microbial pesticide  comprised  of Pseudomonas fluorescens CL145A
(PfCL 145 A) discovered in North American soil. It represents the first selective, environmentally
friendly product to control invasive zebra and quagga  mussels (Dreissena polymorpha and
Dreissena rostriformis bugensis). In earlier  work, the  New York State Museum found  that
Pf CL145A was highly selective and efficacious for killing dreissenid mussels.  Extensive
nontarget ecotoxicity testing shows that it does not harm other species.
   Recently,  Marrone  Bio Innovations (MBI) has been working to realize the commercial
potential of Pf CL145A. MBI  isolated, identified, and  quantified some of the novel
chemicals in Pf CL145A responsible for its selective activity  against invasive mussels. These
novel chemicals have potential as a newr family of specific mollusdcides. MBI optimized its
fermentation process to produce high concentrations of active compounds within P/"CLl45A.
Nowr, they are developing stable formulations of killed Pf CL145A cells that are cost-effective
and user-friendly.
   In 2009,  MBI  began manufacturing Zequanox"" for field  trials at hydropowcr facilities.
MBI is working with its customers to guide product development. Zequanox™ meets EPA's
criteria for registration as a reduced risk pesticide; MBI expects EPA registration in June 2010.
Although product development is continuing, MBI is prepared to provide Zequanox™ to initial
customers after EPA registration to replace  current, less-selective mollusdcides. In early 2010,
MBI will provide Zequanox™ to the U.S. Bureau of Reclamation to treat its  facilities along the
Colorado River under an EPA FIFRA Section 18 Emergency  Use Exemption registration.
Inno¥ations, Inc.

Modular Genetics,
Orono Spectral
An AcylAmino Acid Surfactant Produced by

Sustainable Chemistry

   Surfactants  are  generally composed of both  hydrophobic and hydrophilic  regions.
Their amphiphilic nature enables them to reduce either the surface tension of a liquid or
the intertacial  tension between two liquids. These properties enable wide commercial use
of surfactants as foaming agents, cmulsifiers, and dispersants. Globally each year, petroleum
is the feedstock tor about 7.4 million metric tons of surfactants; seed oils such as palm or
coconut oil are feedstocks for about 3-3 million metric tons. Manufacturing surfactants from
petroleum releases approximately 31-6 billion kilograms of carbon dioxide (COi)  into the
atmosphere annually. Manufacturing  them from seed oil releases  less COa, but rainforest
preservation limits the available amounts of palm and coconut oils. Sustainably manufactured
surfactants have the potential to reduce rainforest destruction and eliminate annual emissions
of atmospheric CC>2 equivalent to combusting 3.6 billion gallons of gasoline.
   One of the  most powerful known biosurfactants is surfactin, a lipopeptide produced by
some strains of the soil bacterium Bacillus subtilis. Surfactin has only limited use in consumer
products, however, because it is not water-soluble. Using genetic techniques. Modular Genetics
engineered a B, subtilis strain and its pep tide synthetase enzyme. The engineered bacterium now
produces a novel acyl amino acid surfactant by fermentation of ccllulosic carbohydrates such
as soybean hulls, an abundant agricultural waste. The new surfactant is a fatty add-glutamate
(FA-Glu) that  is very similar to myristoyl glutamate, a  commercial surfactant widely used
in consumer product formulations. FA-Glu has higher water solubility and a lower critical
micelle concentration (CMC) than myristoyl  glutamate. Like surfactin, FA-Glu is secreted
into the fermentation broth,  enabling partial purification by foam fractionation. This novel
approach should enable the sustainable manufacture of many new useful surfactants.
   During 2009, Modular  Genetics distributed samples to potential customers and filed a
patent application for its technology.

Device  and Method for Analyzing Oil and Grease in

 Wastewaters without Solvent

   Oil and grease are grouped together as one of five conventional  pollutants covered by the
1974 Clean Water Act. They rank second only to pH as the most-enforced-against pollutant.
All National Pollution Discharge Elimination Systems (NPDES)  permits,  all pretreatment
permits, and all Industrial Effluent Guidelines require measurements of oil and grease. Millions
of analyses for oil and grease are done each year in the United States alone.
   As a result of the Montreal Protocol in 1989, EPA moved  from  a  Freon extraction
method (EPA 413) to an w-hexane extraction mass-based determination method (EPA 1664
in 1995; EPA 1664a in  1999). This  created several  new problems: (1) w-hexane methods
require personal exposure,  handling,  and transportation of a hazardous, flammable liquid;
(2) w-hexane is a known neurotoxin; (3) each analysis takes longer; and (4) millions of liters per
year of w-hexane waste now require disposal. Thus, the current methodology is inconsistent
with the intent of the Clean Air Act and Clean Water Act, both of which consider w-hexane
a hazardous pollutant.
   The ''solid phase infrared  amenable extractor" technology developed by Orono Spectral
Solutions (OSS) solves the problems above by eliminating solvents from oil and grease
analysis. It also provides  more economical, accurate analyses. OSS's extractor unit is small,
economical, robust,  and disposable (or partially recyclable). It contains no toxic substances.
It includes a polymeric membrane that captures and concentrates oil and grease from water, a
metal-membrane support,  and  a polypropylene  housing designed for pressurized water

samples. The polymeric membrane does not absorb IR light in the spectral regions of interest;
after drying, the device can be put into an IR spectrophotometer to determine the amount of
oil and grease.
   This patent-pending technology has successfully completed  ASTM  multi-laboratory
validation studies and has been assigned ASTM method number D7575- OSS  is actively
commercializing this technology for worldwide markets.

2-Metbyltetrahydrofuran: A Green Alternative to

Oil-Derived Ethers and Chlorinated Solvents

   2-Methyltetrahydrofuran (2-MeTHF) is  the only aprotic solvent derived from renewable
resources. The pentoses from agricultural waste such as corncobs cyclize to furfural in aqueous
solution; furfural is further dehydrogenated  to 2-MeTHF. As the largest producer of corn in
the world, the United States provides a dependable supply of corncobs as waste from the food
and bioethanol industries.
   Pennakem initiated and developed the global market for 2-MeTHF as a green alternative
to petroleum-derived ethers  and  volatile chlorinated solvents. Pennakem's proprietary
technology  produces 2-MeTHF with hydrogen from natural gas and water as the solvent.
2-MeTHF can reduce process mass intensity (PMI) to facilitate greener processes in chemical
manufacturing. Substituting 2-MeTHF for tetrahydrofuran (THF) can lead  to (1)  higher
reaction yields (reducing PMI for organometallics by  15—30 percent); (2) increased solubility
of organomctallic reagents (reducing PMI  by 30—50 percent); (3) higher extraction yields
during workup (reducing PMI by 15—30  percent); (4) one-pot  reactions due to cleaner
reactions, increased solvent stability, and easy phase separation (reducing PMI by 50 percent
for 2 steps); and (5)  elimination of hydrophobic cosolvents (reducing PMI by 30 percent).
Switching to 2-MeTHF could eliminate 30,000 metric tons of THF per year along with
30,000 metric tons of hydrophobic cosolvents from Grignard workups. Because THF and
cosolvent mixtures are often incinerated, substituting 2-MeTHF may reduce carbon dioxide
(CC>2) emissions up to 90 percent.
   2-MeTHF is easier to dry and recycle due to  its rich azeotrope with water (10.6 percent)
and simple distillation at atmospheric pressure. The energy savings for 2-MeTHF recycling are
approximately 70 percent compared to THF. Other advantages for 2-MeTHF are improved
process safety lower chemical oxygen demand (COD) in effluent waters, and lower emissions
of volatile organic compounds (VOCs).
   Recently, CPS-Chirotech in the United Kingdom  reported the first industrial application
that substitutes 2-MeTHF for dichloromethane; this expands the potential for 2-MeTHF to
substitute for chlorinated solvents.

PRE-TEC3000®: An  Environmentally Friendly Wood


   Preventive  Technology  developed PRE-TEC 3000* to  protect wood products against
fire,  termites, mold, fungus,  and moisture without using  toxic  or dangerous chemicals.
PRE-TEC 3000* contains a silicate—borate mixture that forms an insoluble borosilicate gel
upon drying. This treatment protects against termites and fire at the usual  levels in borate-
treated wood. The insoluble silica gel combats leeching. The carbonates, silicates, and borates
in the treatment provide exemplary fire retardation, termite repulsion, mold inhibition, and
decay prevention. PRE-TEC 3000*  contains no metals. The disposal of wood treated with
PRE-TEC 3000* will pose no threat to the  environment.
   Various species of trees produce vastly different types of lumber. Unfortunately, traditional
wood-treatment technology is not effective for all types of lumber such as  red  pine,  the
    Pennakem LLC
    Technology, Inc.

Soy Resin, LLC;

Grain Science
preferred lumber in the Midwest, PRE-TEC 3000® has successfully  treated  many wood
products that had previously been untreatable. This allows the opening of new markets to
the building industry.
   PRE-TEC 3000™'  will work  with  the  system  of ''green" pressure-treating wood  that
is  already  established.  It  is  currently being tested  and  cleared  by  the  International
Code Council  (ICC) using  their "green" process  for approval of  treated lumber for
the building industry  If PRE-TEC 3000*  replaces only  one billion board  feet  of
copper-based wood treatments next year, over 7,000 tons of copper would not  contaminate
the environment through leeching or eventual disposal of copper-treated wood. PRE-TEC
3000* is currently undergoing further testing by independent certified test laboratories.

Renewable Oil Production from Algae

   Certain species of algae produce lipids, mainly triglyceride oils, as a  way to  store energy.
These algae can store more than 75 percent of their total cell mass as lipids. Using proprietary
strains of heterotrophic algae, Solazyme has, for the first time, created a practical bridge from
carbohydrates, sugars, and  cellulosic biomass  to the production of low-carbon lipids and
hydrocarbons, compounds critically important to humankind's need for fuels and chemicals.
Solazyme developed its algal strains through a combination of strain  selection, screening,
classical mutagenesis, and metabolic engineering.
   Solazyme has pioneered the development and commercialization of renewable algal oil to
replace conventional petroleum-based  products. Solazyme has used 100-percent algal oil to
produce a broad range of renewable, green fuels including (1) Soladiesel BD™ fuel, a fatty acid
methyl ester biodiesel that meets the ASTM D6751 and EN14214 standards; (2) Soladiesel
RD™ fuel, a hydro treated diesel fuel that meets the ASTM D-975 standard; and (3) SolaHRje,™
fuel, a jet fuel that meets the most-challenging specifications for aviation turbine fuel, ASTM
D1655- In addition, Solazyme algal oils and biomass have been incorporated into a variety of
food  products and converted into important chemicals such as polyols and soaps.
   Solazymes algal oils provide  a number of environmental and human health benefits
including efficient use of land and water resources, reduced air pollution, compatibility  with
the existing infrastructure, and reduced greenhouse gas emissions. An outside analysis of the
total  life cycle greenhouse gas emissions of Solazyme's fuel technology using  the GREET
model yielded estimated 89- and 169-percent reductions in global warming index (GW1)
for Soladiesel™ fuels made from sugarcane and municipal green waste, respectively. Solazyme
is currently operating continuously in commercial facilities to  produce over 2,200 gallons
(15 tons) of algal oil per week. During 2009, Solazyme established plans and obtained funds
for an integrated biorefinery to produce renewable fuel and chemical feedstocks.

Green Process  of Unfolding Soy Protein Polymers for

Green Adhesives

   NOTE: This project is the result of a partnership between Professor Xiuzhi Susan Sun of
Kansas State University and SoyResin, LLC. The project was judged in both the academic and
small business categories. The abstract appears in the academic section on page 11.

Development and Commercial Application  of

SAMMS9: A Novel Adsorbent for the Removal of

Mercury       Other  Toxic Heavy Metals

   Mercury contamination poses a serious threat to the environment and human health. Many
technologies that remove mercury, however, also produce harmful byproducts or secondary
waste. The  technology using SAMMS'"' successfully adsorbs and removes toxic metals (e.g.,
mercury, cadmium, lead) and replaces less-effective adsorbents currently used in the chemical
industry (e.g., activated carbon, IX resins). Specifically developed to form strong chemical
bonds with targeted toxic heavy metals, SAMMS* has superior adsorption capacity; It also
provides superior cost-effectiveness by significantly reducing the volume of hazardous waste.
   SAMMS'0' is  a mesoporous ceramic substrate  with a single layer of functional sorbent
molecules chemically anchored to the substrate surface. The functional molecules are tailored
to have  high affinity for specific cations or anions. Originally, the manufacture of SAMMS*
required a functionalization process using flammable organic solvents including toluene. The
resulting waste stream consisted of water, methanol, toluene, and traces of me reap tan. This
mixture required disposal as hazardous waste.
   Steward  Advanced  Materials  dramatically improved  the  SAMMS* synthesis  using
nonflammable,  nontoxic supercritical carbon  dioxide  (SCCC^). With  this patented,
commercially viable, green-chemical process, SAMMS* manufacturing is faster and more
efficient; it  also  yields a higher-quality product. The SCCCb process results in a defect-free
silane monolayer with virtually no residual silane. Consequently, the  only byproducts are
carbon dioxide (CC^) and the alcohol resulting from the hydrolysis  of the alkoxysilanc. The
CC>2 and alcohol are readily separated, allowing the CO2 to be captured and recycled. The
pure alcohol can then be captured as a recyclable feedstock, rather than becoming waste as in
the traditional synthesis. The SAMMS* materials emerge from the reactor clean, dry, and ready
for reuse. The benefits of the green manufacturing process for SAMMS*, coupled with the
superior adsorption characteristics of SAMMS* materials currently deployed in the chemical
industry, result in substantial reductions in toxic metals being released to the environment.

Bioil Technology: One-Pot, Catalytic Hydrolysis of

Ligno celluloses

   One  of the biggest challenges society faces is the depletion of fossil fuels. Replacing these
fuels with renewable feedstocks such  as lignocelluloses can address this challenge. During
the last three years, Sun Pharmaceuticals has developed a technology to change biomass
refining from time- and energy-consuming multiple steps to a simple, one-step catalysis. This
technology uses every organic polymer of lignocelluloses  including  cellulose, hemicellulose,
and  lignin; in  contrast, other  biomass-rcfining technologies  use only carbohydrates. The
new technology hydrolyzes lignocellulose polymers into  small organic compounds in  one
step  under  mild conditions without hydrogen. No gas or black tar  forms during hydrolysis,
suggesting that no organic carbon is lost. The product is "Bioil", a mixture of about sixty major
organic compounds including four groups: cyclopentanones and cyclopentanols, a-hydroxyl
carboxylic acids and amino acids, substituted phenols and catechols,  and monosaccharides.
   The  major advantages of Bioil technology over other biomass-refining technologies are
its efficient use  of materials and energy. Bioil technology  saves  more than 70 percent of the
organic carbon  and 60 percent of the energy consumed  by ethanol fermentation. Current
biomass-refining technologies have difficulty becoming profitable, due to the limited products
(e.g., ethanol or gasoline) that they can make from lignocellulose. The Sun Pharmaceuticals
technology will make commercialization more practical by producing green, high-value-added
Syn Pharmaceyticals,

Terrabon, Inc.
Troy Corporation
chemical products, as well as hydrocarbon liquid fuels, food, and food additives. Residues left
after isolating pure compounds from Bioil are easy to convert to gasoline or diesel fuel.
   During 2009, Sun developed isolation methods  for some of these sixty compounds and
successfully completed a pilot run for the Bioil technology and isolation process under a joint
venture in China, The first demonstration plant with a commercial-scale, annual consumption
of 50,000 tons of biomass is being initiated. It can be modified to produce ten million gallons
of gasoline per year in addition to food and food additives,

Conversion of Municipal Solid Wastes to Drop-In Fuels

and Chemicals

   Terrabons MixAlco™ process converts any anaerobically biodegradable material  (e.g.,
proteins, cellulose, hemicellulosc, fats, and pectin) into a wide array of chemicals (e.g., ketones,
secondary alcohols) and fuels (e.g., drop-in biofuels such as gasoline, diesel, and jet fuel). The
conversion  occurs by nonsterile, anaerobic fermentation of biomass into mixed  carboxylic
acids and salts by a  mixed culture of naturally occurring  microorganisms, followed by the
conversion  of the mixed acids and  salts into the desired chemicals or fuels by conventional
   Terrabon uses municipal solid waste (MSW), which typically ends up in  landfills, as the
feedstock for the MixAlco'" process  to make ketones, secondary alcohols, and gasoline. This
process will increase landfill life and  replace nonrenewable petroleum resources. According to
a life cycle analysis (LCA) using the GREET model, it will reduce greenhouse gas emissions
by over 180 percent compared  to conventional gasoline. This process may also use other waste
products of environmental concern  such as leachate from  landfills, raw sewage, and sewage
sludge. When high-water effluents are used as the water sources along with MSW, this process
can export up to 25 gallons of distilled water for every gallon of fuel it produces.
   Terrabon has built a pilot  plant and  a semiworks plant in Bryan, TX  to  confirm the
scalability of this process. The semiworks plant processes the equivalent of about 5 dry tons
of biomass per day and  generates enough fermentation products to produce 100,000 gallons
of biogasoline per year. The conversion to biogasoline at the plant includes dewatering the
fermentation salt product by evaporation and drying, thermally converting  it  into ketones,
and finally catalytically converting  the ketones into  alcohols  and hydrocarbons. Terrabon
successfully completed testing this  process at  the semiworks plant, producing good-quality
gasoline. In 2010, it plans to start designing and constructing a 220 dry ton per day plant to
make 5 million gallons of gasoline per year.

Source Reduction and Sustainability through  Use of

Mergal9 753 Antimicrobial Preservative

   Product innovation is standard with high-volume agricultural products, but is less frequent
with antimicrobial and biocidal preservatives. Troy developed  MergaT" 753  in response
to market concerns  over green  chemistry initiatives, sustainability, and release of volatile
organic compounds (VOCs).  Mergal* 753 is a concentrated aqueous  dispersion of 1,2-
ben/isothia7.olin-3-one (BIT), a widely known biocidal active ingredient; it contains no VOCs
and is compatible with water-based  production processes. Typical  applications  for industrial
biocides like Mergal® 753 include adhesives, paints,  coatings, and metalworking fluids.
   Mergal"  753 meets basic green chemistry parameters. Troy  assessed the carbon footprint
of its product using the methods  and  tools  developed by the Greenhouse Gas Protocol
Initiative, a joint project of the World Business Council for Sustainable Development and
the World Resources Initiative. The basic calculation used to  develop its carbon footprint

included the "functional unit": comparing the amount of product needed by a customer for
a given application. Troy's conventional, dilute product requires 4.5 times the volume as the
concentrated product (Mergal* 753) to treat the same amount of material at the customer's
facility. The primary comparison assumed that  MergaP 753  is diluted by the customer to
the same final concentration as the dilute product and that the use rate per functional unit is
equivalent for the two products. With this approach, Troy estimated that the potential energy
savings through replacement of its dilute product with Mergal* 753 results in a carbon dioxide
(CC>2)  reduction  equivalent to taking 5-3 passenger cars off the  road each year. Additional
savings would occur with increased product use, which effectively reduces worker exposure
to hazardous workplace substances. Troy optimized the formulation of its product to ensure
suitability with current application systems, and EPA formally registered Mergal* 753 on
October 31,2008.

Highly Efficient and Practical Monohydrolysis  of

Symmetric D festers

   NOTE: This project is the result of a partnership between Professor Satomi Niwayama
of Texas Tech University, Wako Chemicals USA, Inc., and Kishida Chemical Co.,  Ltd. The
project was judged in both the academic and small business categories. The abstract appears
in the academic section on page 10.
Department of
Chemistry      Bio-
chemistry,       Tech
Chemical Co., Ltd.



RegenSi™: A Wafer Reclaim Solution with a Low

Carbon Footprint that Extends the Life Cycle of Silicon

Test Wafers

   Because a prime silicon wafer costs approximately $300, semiconductor manufacturers
use test wafers, at over $100  apiece, to optimize their manufacturing processes. One large
fabricator might  spend $2 million monthly on test wafers. The industry uses more than
27 million prime and test wafers annually. Because silicon is the greatest material expense for
fabricators, they are eager to improve their reclamation and reuse of test wafers.
   Traditional wafer reclamation processes involve chemically stripping unwanted films from
the wafer surface, surface planarization (i.e., mechanical polishing to remove damage  or
impurities), and cleaning. Wafer reclamation has been limited because each cycle of stripping
and polishing reduces the thickness of the wafers;  eventually, they become too thin and are
discarded. Traditional processes have very low reclaim yields because they cannot remove
unwanted films completely.
   RegenSi'" is a novel, all-wet, single-step process that strips away most films from test wafers
and limits  damage to the underlying silicon. This eliminates or reduces the need tor wafer
surface planarization, which is  energy-intensive, requires a large volume of consumables, and is
expensive. RegenSi™ chemicals also have a much longer bath life, which reduces both chemical
waste and worker exposure. The RegenSi™1 process eliminates sulfuric, nitric, and hydrochloric
acids. It reduces hydrofluoric acid 24-fold. The process has a carbon footprint 28-fold lower
than the traditional three-step process and consumes 85-percent less energy. One Taiwanese
manufacturer  using RegenSi™ increased reclaim yields to 85 percent and reduced silicon loss
by 75 percent, increasing the life of each  test wafer fourfold. Another RegenSi'" customer
saved 20 tons  of deionized rinse water per day in each facility.
   This combination of higher  yields, fewer resources,  greater  productivity, and increased
reuse leads to  significant overall cost savings, energy savings, and waste reduction. Both IBM
and Texas Instruments are using RegenSi'™; many others are using or testing it.

Bipolar Membrane Electrodialysis for Greener

Processing of Cb elates

   Chelates are chemical agents that interact or complex with metal ions, often increasing their
solubility. Liquid redox sulfur recovery (LRSR) uses chelates to remove poisonous hydrogen
sulfide (HbS) from gas streams. A chelate called /V-hyd roxyethyl ethylenediamine triacetic acid
(HEDTA) is conveniently used in LRSR to complex iron and to keep it in solution,  where it
reacts with
   Several years ago, AkzoNobel developed two novel products containing HEDTA for use in
this LRSR process. At that time, the manufacturing process for these novel products included
treating the sodium salt of HEDTA (HEDTA-Na3) with ion exchange (IE) technology where
Na~" ions are  exchanged with H* ions. Although IE  offers favorable exchange of Na+ for H4,
it does so at  the expense of generating a significant waste stream during regeneration  of the
IE resin. The Na1  ions present on the resin combine with the regeneration acid, forming a
Functional Chemicals,

AkzoNobel Surface
Chemistry, LLC
waste salt solution. In addition, IE is inherently a dilution step: energy is required to boil and
concentrate the HEDTA product streams after IE processing,
  AkzoNobel has now developed and implemented a greener manufacturing technology to
replace IE. Bipolar Membrane Elcctrodialysis (BMED) is a technology that uses ion-permeable
membranes and electricity to exchange Na" for H+. Unlike IE, the BMED technology does
not generate a waste stream of salt; rather, it generates a stream of useable sodium hydroxide
(NaOH) and requires no  regeneration acid. BMED  actually concentrates the processed
HEDTA chelate solution and eliminates  FE's energy-intensive  concentration step, saving
approximately 360 kilograms of steam per metric ton of HEDTA products.
  AkzoNobel believes the BMED technology, implemented at its plant in the United States,
is the first major, if not the only, commercial use of this technology to process chelates. Since
the  technology's  introduction, AkzoNobel has identified other opportunities for BMED,
allowing greener processing of chelates and  other electrolyte products.

Novel Greener,  Water-Soluble, Hybrid Polymer

Technology for Fabric and Cleaning, Industrial Water

Treatment, and Oil Recovery Applications

  Many consumer and industrial applications require  the control and prevention of scales
such as calcium carbonate. Among these applications are automatic dishwashing and laundry;
maintaining equipment for industrial water treatment; and facilitating oil production, drilling,
and stimulation.  Synthetic  polycarboxylates created from acrylic acid  and other monomers
derived  from petrochemicals have been used traditionally  to manage water hardness and
prevent deposition of scale and other solids in these applications.
  AkzoNobel Surface Chemistry (ANSC), a global supplier of synthetic polycarboxylates for
over three decades, has created a new class of polymers called hybrid polymers. These polymers
have traditional synthetic functionality, but use plant-based feedstocks for half or more of the
polymer backbone. The  resulting products reduce ANSC's dependence on petrochemicals
and increase its use of agricultural products, resulting in better environmental sustainability.
Prototypes of the hybrid products show excellent cost- and weight-performance in automatic
dishwashing, laundry, water treatment, and oil drilling and production, making it feasible to
switch to the new hybrid polymers.
  Life cycle analysis (LCA) shows that replacing traditional, petrochemical-based polymers
with the ANSC hybrid polymers reduces energy use by 44 percent, petrochemical depletion
by 43 percent,  carbon dioxide (CC>2) emissions by over 35 percent, acid rain by 10 percent,
and ground-level ozone by 40 percent. These benefits result from the sustainable, plant-based
materials in  the hybrid polymers. Incorporating polysaccharides into the hybrid  polymers
gives them substantial biodegradability; purely synthetic polymers are not biodegradable.
  Current hybrid  prototypes based  on  65-percent polysaccharide,  for example, can  be
manufactured in existing equipment with water as the solvent. The aquatic and human toxicity
profiles  of the  hybrids are equal to or better than  their synthetic counterparts. ANSC first
used this technology in cleaning and oilfield drilling applications. The  company is exploring
commercial extensions into petrochemical, personal care, and water treatment applications.
ANSC expects to begin commercialization in 2010.

An Environmentally Friendly Process for Upcycling

Plastic Waste into Advanced Carbon Nanotubes

Carbon  Spheres

   Left unchecked, the escalating volume of plastic waste that requires hundreds of years to
degrade will cause severely negative environmental and human health effects on life on earth.
Current recycling technology is only a partial solution; it often results in downcycling plastics
rather than making new, high-quality products. Thus, innovative approaches for upcycling or
remediating plastics are needed in addition to conventional recycling facilities,
   Argonne has developed an original, solvent!ess, solid-state, controlled pyrolysis process
that uses mixed plastic waste in a one-pot, closed system. This reproducible, environmentally
friendly process presents an opportunity to use plastic waste as a feedstock to produce carbon
spheres (CSs) and carbon nanotubes (CNTs), which are industrially significant, value-added
products. Argonne's approach for fabricating CNTs is inexpensive and innovative relative to
other current methods. This technology also eliminates the air and water pollution caused
by incinerating plastic waste or burying it in a landfill. It also uses less energy than do typical
recycling methods for plastic waste.
   Argonne has successfully tested as-prepared dry CSs and CNTs in lithium, Li-ion, and Li—air
batteries. The CSs and CNTs acted as superior anode materials, improving the electrochemical
performance  in   Li-ion  batteries. Cobalt-encapsulated  CNTs  also  showed   promising
performance as an air cathode in Li—oxygen batteries. The micrometer-sized, smooth, carbon
spheres are pure, conducting, and  paramagnetic. They have potential applications in toners,
printers, lubricants, and the tire industry.
   Argonne designed a prototype reactor with a 40 cubic centimeter (cc) capacity to upcycle
plastic waste; it optimized the reaction conditions (e.g., temperature, effect of single or mixed
plastic waste, selection and amounts of catalysts, autogenic pressure measurements). It  is
working to elucidate the mechanism of CS and CNT formation. Argonne is systematically
characterizing the atomic structure, composition, and morphology of the CSs and  CNTs with
advanced structural, spectroscopic, and imaging techniques. Argonne is seeking licensees for
this technology.

BioBased Tile9 with BioStride9: A  Revolutionary New

Flooring Made  with Rapidly  Renewable Resources

   Today, more than three-quarters of a billion feet of vinyl composition tile (VCT) is installed
annually. Historically, resilient VCT flooring has been manufactured with binders derived
from fossil fuel. Typical binders tor VCT include polyfyinyl chloride) (PVC), polyolefins,
ethylene acrylic resins, and synthetic rubbers. These binders combine plasticizers, processing
aids, stabilizers, limestone, and pigments,
   In 2008, Armstrong commercialized Migrations* BioBased Tile* flooring, a revolutionary
plasticizcr-frcc, biobascd flooring product. Armstrong is  the first  manufacturer in over
100 years  to  develop a  biobased polymer as a binder for a  hard-surface flooring product.
Linoleum is the only other such flooring available. The new binder, BioStride*, created a new
category of composition tile. Branded by Armstrong as BioBased Tile*, it couples indoor air
quality and environmental benefits with improved performance.
   The BioStride* polymer binder contains ingredients from rapidly renewable, domestic crops,
resulting in reduced reliance on fossil fuels and a  lower carbon footprint. The development
of the BioStride* binder and BioBased Tile* flooring  followed important principles of green
chemistry, life cycle assessment, and  Design for the Environment  (Dffi). The consumer
product made from the  BioStride*  binder contains 10-percent  preconsumer recycled
Argonne National
Armstrong World

limestone. Replacing VCT with BioBased Tile'"' flooring could save 108 million pounds of
virgin materials,  eliminate 259,000 pounds of volatile organic  compounds (VOCs) from
manufacturing, capture 34 million pounds of carbon dioxide (CC>2) from  the atmosphere
in biobased  components, reduce  energy consumption by 365  billion Btu (equivalent to
43 million pounds of CO-j), and improve indoor air quality, BioBased Tile* flooring is certified
by Floor Score with no detectable  levels of total VOCs; it contains no materials listed in the
table of Chronic  Reference Exposure Levels (CRELs) established  by the California Office of
Environmental Health Hazard Assessment (OEHHA). BioBased Tile* is helping customers
qualify for LEED certification and other green building initiatives.

Highly Water-Dispersed Oilfield Corrosion  Inhibitors

Eliminate over One Million  Pounds  of Nonrenewable

Solvents Annually

   Corrosion-induced leaks in hydrocarbon-producing equipment threaten safety, health, and
the environment. Only recently, however, has anyone focused on safer corrosion inhibitors
with reduced environmental impacts. Extensive product development by Baker Hughes has
led to an  innovative line of corrosion management  chemicals that is free  of hydrocarbon
solvents, but contains active inhibitors that historically could only be formulated with these
flammable solvents. The new, highly water-dispersed products exhibit better dispersibility and
water partitioning in use than traditional products and, therefore,  deliver the active inhibitors
to metal surfaces  more efficiently. The net result is  significantly reduced field-level chemical
use rates that do not compromise corrosion inhibitor performance.
   This  innovative technology entails much  more than simply making water-soluble
formulations. What  truly distinguishes  the new  technology is its use  of the inhibitors
themselves as dispersing agents, both eliminating  the need  tor  hydrocarbon solvents and
limiting or eliminating the need  for additional additives or surfactants. The chemistry  is
based on formulated fatty acid amide—imidazoline technology. Careful adjustments of pH,
hydrophilic-lipophilic balance, and levels of active ingredients  produce  stable  dispersions
of the inhibitors  with no or only  minimal added  surfactants. As a result, oilfield operators
can reap the benefits of the  powerful chemicals commonly found in hydrocarbon-based,
corrosion-inhibiting products in safer, water-based formulas that have less impact on the
environment. The water-based products contain  no naphthalene; they have higher flash-
points than traditional, solvent-based products, so they are safer to store and handle.
   Since 2006, Baker Hughes has commercialized five of these products.  Based on 2009
sales, the net direct environmental impact of this  technology is  the elimination of at least
1 million pounds of hydrocarbon solvents annually.  With continuing development and as
oilfield deployment of this technology grows, the direct and indirect positive impacts of the
technology are expected to increase several-fold in the very near term.

ReFlex™ 100 Bioderived Green Bioplasticizers for

Poly (vinyl chloride)

   Global production of plasticizers is over 13 billion pounds annually. Ninety percent of all
plasticizers are used with poly(vinyl chloride) (PVC) to make it  softer or more flexible for
applications including vinyl flooring, films, blood bags, wallpaper, inks, plastisols, and shoes.
Eighty percent of all plasticizers are phthalates,  but  some phthalates have come under severe
regulatory scrutiny as suspect endocrine disrupters. For example,  President George W Bush
signed the Consumer Product Safety Improvement  Act (CPSIA) in August 2008, which led
to banning three  phthalate ester plasticizers in toys.

   Consequently, the PVC industry has an immediate need to replace phthalates with cost-
effective, safe, green plasticizers. Replacing 25 percent of the U.S. plasticizer production with
biobased products derived from renewable resources  offers energy savings of approximately
5 trillion Btu per year. In addition, each pound of bioplasticizer consumed reduces carbon
dioxide (CC>2) emissions by about one pound.
   Battelle's technology addresses the need for a safe,  cost-effective alternative to phthalates.
Battelle has developed several novel plastici/ers based on extensive modeling studies to identify
those chemical structures derived from renewable feedstocks that exhibit optimal compatibility
with PVC resin  and enhance both thermal stability and plasticization efficiency. One such
plasticizer is epoxidized propylene glycol disoyate.
   In 2008, Battelle licensed its patented  technology to  PolyOne,  based  in Ohio, and
Nexoleum, based in Brazil. In 2009, PolyOne and Archer Daniels Midland successfully scaled
up and commercialized reFlex™ 100, a first-generation, bioderived, green plasticizer for PVC.
ReFlex™ has superior solvation, higher thermal stability, and increased plasticization efficiency.
It can replace butyl benzyl phthalate across a range of applications, particularly plasdsols and
inks. Nexoleum has sold several hundred tons of its bioderived Nexo El™ plasticizer in Brazil.
These  new bioplastidzers are proving to  be drop-in replacements for phthalates in many
applications; they require minimal, if any, changes to current practices in the PVC industry.

IMPACT  Technology: A  Greener Polyether Polyol


   The Bayer MaterialScience (BMS) IMPACT  technology  for polyether polyol (PET)
production couples a breakthrough catalyst invention with an equally  innovative  process
design. The IMPACT process includes modifying the double metal cyanide (DMC)  catalyst
to increase its reactivity more than  10-fold and exploiting an unusual kinetic property: the
modified DMC  selectively adds alkylene oxides to  the lower-molecular-weight  molecules in
a mixture of molecular weights. Combining these two inventions gives a continuous process
that requires less equipment.  The new process generates less waste,  eliminates process steps,
and is inherently safer.
   A gate-to-gate life cycle assessment (LCA) of the continuous process in comparison with
conventional  technology shows reductions of 76—80 percent in energy consumption, carbon
dioxide (CC>2) generation, acidification, eutrophication potential, and smog. Moreover, the
BMS Channelview, TX plant eliminates over 34 kilotons of wrastewater  annually at typical
run  rates and  reduces over 32  kilotons of CO2 equivalents at full capacity. Recently, total
production in the United States using the  continuous process reached  a billion pounds,
and  BMS completed licensing  its technology to major competitors. These milestones have
established IMPACT as the  industry standard  in  environmental savings and  productivity.
Worldwide, plants will be converted or constructed for IMPACT technology, increasing the
positive effects on the environment. Polyethers for use in polyurethanes have a multi-billion-
pound worldwide market with applications spanning  nearly every market segment including
insulation, coatings, elastomers, and flexible foams such as bedding, furniture, and automotive
seating. BMS has a 23-percent market share with a global capacity of over 1,100 kilotons.
Around 50 percent of BMSs PET production can  be manufactured using the IMPACT
technology. BMS has converted about half of this volume to  the new processes. BMS has
used this technology to double PET production at the Channelview plant within four years to
200 kilotons and has lowered  its variable production costs by 40 percent.
MaterialScience, LLC

Berry Plastics; Flame
Chk Inc.; Chemische
Fabrik Budenheim
Nonhalogenated Flame Retardantfor Use in High-

Performance Adhesives and Coatings

   Deaths due to fire claim thousands of lives every year all over the world. The challenge is to
make products that will burn more slowly or not at all when exposed to fire, allowing occupants
to escape and giving firefighters a chance to save lives and property. For decades, fire-retardant
systems were made up of halogcnatcd materials including bromine, chlorine, and antimony.
These  materials have recently come under scrutiny, however.  They have been found  to
accumulate in the environment and in humans. This has led many domestic and international
organizations to regulate and phase out these materials, as is the case with decabromodiphenyl
ether (decaBDE). Many customers are requiring their suppliers to provide products that are
halogen-free. The challenge is finding effective, nonhalogenated replacements.
   Berry Plastics has shown that melamine borate (i.e., Budit 313 made by Chemische Fabrik
Budenheim and distributed by Flame Chk) is an effective replacement in the pressure-sensitive
adhesives it  manufactures.  Melamine borate  is  not expected to harm  humans or aquatic
environments. In contact with heat, it decomposes, acts as a heat sink, and releases inert
nitrogen gases, which dilute the oxygen and flammable gases. It inhibits burning, prevents fire
from spreading, and  reduces the emission of toxic fumes by building a char barrier. The char
barrier greatly diminishes the fuel available to fire.
   The current challenge with nonhalogenated flame retard ants is that more of the material
is  required to produce the same effect  as the halogenated flame retardants. Thus,  each
application being made flame retardant requires a unique formula to balance flame retardancy
with product functionality. The technology is  not a one-to-one replacement and will require
more research, but the cost is expected to be  competitive with the halogenated systems.  In
November, 2009,  Flame Chk  submitted a Premanufacture Notification and Low Volume
Exemption for melamine borate to EPA.
 The Development and Commercialization of a

Low-pH,  Lactic Acid Process for Renewable Plastics

   Lactic acid is a commodity-scale fermentation product, ranking among the highest-volume
chemicals produced by fermentation. Greater than 95 percent of the world's 370,000 metric
tons of lactic acid  is produced by  submerged  fermentation of sugar. This fermentation has
traditionally been carried out  by lactic acid bacteria maintained near neutral pH (pH 5—7).
At this pH, however, the fermentation product is a lactic acid salt that requires neutralization.
One of the primary limitations of the bacterial lactic acid process is the cost and environmental
footprint of the recovery and subsequent disposal of the waste salt caused by the neutralizing
agent used during purification.
   Cargill, in an effort cofunded by the Department of Energy (DOE), has developed and
commercialized a  metabolically engineered yeast biocatalyst that efficiently produces free
lactic acid  at low pH (significantly below the pKa of lactic acid). The lactic add production
attributes (rate, titer, and yield) of this yeast biocatalyst are near those of a bacterial lactic acid
producer, but the low pH of the fermentation produces free lactic add as the product, not a
lactate salt. This technology improves product quality and reduces production costs by roughly
50 percent. It also  reduces the use of sulfuric add and calcium hydroxide and formation of
the calcium sulfatc byproduct by approximately 85 percent. Finally, it leads to a 35-percent
reduction in greenhouse gas emissions (GHG)  over the bacterial process.
   Cargill uses lactic acid as the monomer to produce Nature Works LLC Ingeo™ poly(lactic
acid) (PLA). Ingeo'™  biopolymer  is the  world's  first and only performance plastic made

from 100-percent annually renewable resources. Ingeo™ biopolymer is clear and strong like
petroleum-based plastic, yet can be commercially composted. Plant-based Ingco™ biopolymer
offers the cost and performance necessary to  compete with traditional petroleum-based
materials in the packaging and serviceware markets. Cargill commercialized its new yeast-
based process in 2008.

Rapid Enablement of Green Processes for Chiral

Alcohols by the  Codex ™ Panel of Robust,  Divergent

Evolvants of One Ancestral Ketoreductase

   Chiral secondary alcohols are intermediates  in the syntheses of numerous chiral active
pharmaceutical ingredients (APIs). They are  commonly produced from the corresponding
ketones using hazardous, boron-based reducing agents or, more recently, asymmetric catalytic
reduction. Because these reduction methods  typically  produce inadequate stcrcosclcctivity,
additional processing is required to upgrade stereopurity, and product yields are low. Greener,
more economical alternatives to such hazardous reagents and their energy- and mass-intensive
processes are required to produce  the increasing volumes of chiral alcohols needed for current
and future drugs.
   Biocatalytic reduction of ketoncs has long been recognized as an attractive, green alternative
tor making chiral  alcohols. This promise went largely unfulfilled, however,  because the
available ketoreductase (KRED) biocatalysts were hampered by narrow substrate-specificity,
low activity, poor in-process stability, inadequate stereoselectivity, and productivity-limiting
product inhibition.
   Codcxis's widely applicable platform of diverse KREDs prc-cvolved from a common wild-
type ancestor successfully addresses these long-unmet needs for practical, greener processes to
manufacture chiral alcohols. The Codex'" KRED Panel comprises diverse variants of one KRED
that  are pre-evolved for in-process stability and  efficient manufacture. The variants contain
combinatorial mutations that, as  a population, confer activity on a wide structural variety of
ke tones and selectivity to either alcohol stereoisomer. The variants are arrayed on microtiter
plates for  rapid screening to find the desired activity  on any new ketone substrate and to
obtain Protein Sequence Activity Relationship  (ProSAR) data for rapid enzyme optimization if
needed. Codexis developed processes for chiral alcohol intermediates of four generic APIs with
variants identified from KRED panel screens and transferred them to contract manufacturers.
Codexis has used panel variants to synthesize material  for more than 15  drug candidates in
development. Building on its success, Codexis has since developed Codex™ panels for other
generally useful biocatalytic conversions including panels of transaminase, nitrilase, acylase,
halohydrin dehalogenase, and ene reductase biocatalysts.

Saturated Polyester-Phenolic Resin  Systems Eliminate

BisphenolA  and Epoxy from  Interior Can Coatings for

Food Packaging

   Recent studies ofbisphenol A (BPA) in animals have revealed potential endocrine-disrupting
effects. BPA, however, is a key raw material for the binders used in interior coatings for food
cans. Because these coatings are an important source for consumer exposure to BPA, the food
industry is demanding coatings that are free of BPA. Although U.S. regulatory agencies have
not yet made a final regulator}' decision about BPA, the use of this monomcric substance in
interior can coating systems has become a matter of public interest and scientific discussion.
   Cytec has developed a new generation of saturated polyester resins for use as the main
binder in conjunction with phenolic resins. Together, these two resins can be used in interior
    Codexis, Inc.
    Cytec Industries Inc.

Cytec              Inc.
Cytec              Inc.
can coatings for the metal packaging goods industry. Coating systems based on these resins
exhibit comparable performance to conventional high-molecular-weight epoxy systems, with
the additional advantage of being completely free of residual epoxy resin monomers and their
byproducts (e.g., BPA; bisphenol A diglycidyl ether and its derivatives).
   Cytec's saturated polyester resin,  DUROFTAL PE 6607/60BGMP, has a predominantly
linear structure and a molecular weight of approximately 10,000. All monomers used in its
synthesis comply with food contact laws. It does not contain any significant  levels of free
solvent if properly cured; in this and other features, it complies with FDA 21 CFR §175.300.
It is more flexible than conventional systems based on high-molecular-weight  epoxy resins.
Although  DUROFTAL PE 6607/60BGMP is  compatible with most existing cross-linkers
(predominantly phenolic resins and amino resins), Cytec designed a new, tailor-made phenolic
resin for this special application so that the system can be completely free of BPA and have
comparable performance to existing systems. DUROFTAL PE6607/60GMP does not have
the estrogenic properties of BPA. It has been on sale in the United States since 2008.

MAX' HT™ Bayer Sodalite Scale Inhibitor

   The Bayer process converts bauxite ore  to alumina, the primary raw material for aluminum.
The heat exchangers  and interstage  piping in the process  build up  sodalite scale (i.e.,
aluminosilicatc crystals), which reduces the efficiency of the heat exchangers. The equipment
must be taken offline periodically and cleaned with sulfuric acid.
   Cytec developed its MAX HT™ Bayer Sodalite Scale Inhibitor products for the Bayer process.
There are no other scale inhibitors on the market for this application. The active polymeric
ingredient contains silanc functional groups that inhibit crystal growth by incorporation into
the crystal or adsorption onto its surface.  Dosages range from 20 to 40 ppm. Assessments of
these polymers under EPA's Sustainable Futures Program indicated low overall concern for
human  health and the aquatic environment.
   Eliminating sodalite scale from heater surfaces produces many benefits. Heat recovery from
the steam produced in various unit operations is more efficient. Increased  evaporation makes
the countercurrent washing circuit  more efficient and reduces caustic. Reducing the use of
steam reduces emissions from burning carbon-based fuels. Lastly, reducing the sulfuric acid
used to  clean heaters reduces both worker exposure and waste.
   There are about 45 operating Bayer process plants worldwide with annual capacities of
0.5—6 million tons of alumina; most plants are  in the 1.5—3 million ton  range. Since Cytec
introduced MAX HT™ in  2004, 11  Bayer process plants worldwide have adopted it;  14
more plants are testing it.  Each plant using MAX HT™ saves $2—20 million annually. Per
ton of alumina produced, each plant  saves 0.25—1-25 million Btu,  the equivalent of about
29—202 pounds of carbon  dioxide (CO2) not released to the atmosphere depending on the
energy savings and fuel used. Fewer cleaning cycles and less  acid per cycle allow a typical
1.5-million-ton alumina plant  to reduce its waste by 1,500-4,500 tons of 5-percent acid

UV-Curable Pressure Sensitive Adhesive

   UV-curable Pressure Sensitive Adhcsivcs (PSAs) have attracted the attention of the PSA
market  due to their major advantages over the  traditional waterborne and  solventborne
products. These advantages include  (1) lower conversion costs because less energy is required,
(2) smaller space requirements due to the compact  equipment necessary  for processing,
(3) lower shipping costs and inventory needed because UV-curable PSAs are  100-percent
active, (4) more efficient processing because a thick film can be made in a single pass, and
(5) environmental friendliness because these products have low volatile organic compounds
(VOCs). UV-cured products are attractive to PSA coaters seeking lower  capital investment
and operational costs as well as  those facing footprint constraints. Although UV-curable PSA

formulations have been studied since the 1970s, problems with their performance and cost
have hindered their acceptance by the market.
   Through numerous experiments with synthesis and formulation, Cytec has created new
UV-curable PSA polymers with reasonable raw material costs, specially designed blocks of
microstructure domains, optimized molecular weights,  and efficient UV-curing properties.
Cytec's UV-curable PSA technology involves the formation of a unique, acrylated urethane
hybrid that combines soft segments to provide flexibility and adhesion with hard segments
to give  the film cohesive strength, high temperature resistance, and  chemical resistance.
Cytec's technology solves the five performance challenges faced  by other UV-curable PSA
technologies. This acrylated urethane hybrid provides good adhesion to substrates of both
low and high surface energy coupled with excellent high-temperature shear performance. In
addition, Cytec's technology achieves consistent performance over a broad UV curing range
and good through-cure for thick PSA films at a reasonable cost to the general PSA market. It is
a 100-percent-active PSA with no solvent or water, requiring much less energy for curing than
traditional watcrbornc or solvcntbornc PSA formulations. Currently, nine locations globally
are evaluating this technology.

Accelerated Solvent Extraction with  Solvent Saver

Mode™: Reducing Organic Solvent Consumption and

 Waste in Laboratories

   Accelerated  Solvent Extraction (ASE!~) is a sample preparation system that uses organic
solvents at elevated temperatures and pressures to extract analytes of interest from solid or
semisolid matrices prior to analysis. Higher temperatures increase the capacity of solvents to
solubilize analytes; they also enable analytes to move faster from the boundary layer near the
surface of the matrix from which they are extracted into the bulk solvent. Elevated pressures
speed up the extractions overall. They also make it possible to keep solvents in a liquid state
at temperatures above their boiling points, which is critical for efficient extraction. Dionex
developed ASE* to replace traditional extraction techniques such as Soxhlet that require large
volumes of solvent. The company's intent was to develop a technique that was faster, safer, and
more cost-efficient. Early results for the ASE® technology allowed extraction of a 10 g sample
in 15 minutes  with only 15—25 mL of solvent; a typical Soxhlet extraction requires 500 mL
of solvent.
   The end result, ASE* 350, is an automated system  that greatly reduces the  amount of
organic solvent required to extract analytes. ASE* technology significantly reduces solvent
waste, solvent vapors,  and solvent exposure to laboratory personnel. With the introduction of
the ASE* 350 system, users can reduce the amounts of solvent even further by activating the
Solvent Saver Mode™. This mode can save up  to an additional 33 percent of solvent during
each extraction. As one example, the amount of solvent  required to analyze a year's worth of
10 g samples is 49 L for the ASE'"' 350 system in the Solvent Saver Mode™ and 3,120  L for
the traditional Soxhlet method. This is a significant decrease in the amount of organic solvent
waste generated and the amount of solvent vapors released into the environment. Dionex
introduced its ASE* 350 system in 2008.

Energy Savings from a New Manufacturing Route for

Vinyl Methyl Ether

   Glutaraldehyde is  a  broad-spectrum antimicrobial agent. Glutaraldehyde formulations
address the antimicrobial needs of a variety of applications including agriculture, metalworking
fluids, heat-transfer systems, oil and gas operations, water treatment, paper manufacturing,
Dionex Corporation
The Dow Chemical

The Dow Chemical
and medical and dental facilities. A key raw material in the production of glutaraldehyde is
vinyl methyl ether (VME), Historically, VME has been produced using a two-step chemical
process. The energy associated with the steam  needed for  this process is approximately
15,000 Btu per pound  of VME or approximately 300 billion Btu per year.
   Seeking more sustainable process  conditions, Dow Process  Research  and Development
identified the  synthesis of VME as a prime candidate for reactive distillation technology.
Reactive distillation combines chemical reaction  and distillation in a single  step.  This
technology is part of the separations road map supporting Vision 2020 for the U.S. chemical
industry because it can significantly reduce the energy consumption of separation processes.
   Applying reactive distillation to the VME process meant replacing one reactor and tour
distillation columns with a single reactive distillation column. The new process requires less
steam, leading to energy savings equivalent to 54,000,000 kWh each year. This is enough
energy to provide electricity for approximately 4,800 homes per year based on average 2007
household consumption reported by the Department of Energy. The primary aqueous waste
stream from the VME process using reactive distillation contains much less byproduct and
is efficiently cleaned by a wastewater treatment plant, eliminating chemical pretreatment. In
addition, careful selection of plant location reduced the transit distance between the VME
plant and its sister derivatization plant from  1,200 to 500  miles,  which lowered fuel use
per transported railcar  by  60 percent as an added benefit. A VME plant based on reactive
distillation was built at a contract manufacturing facility in early 2009; the conventional VME
plant closed later that year.

An  Innovative Approach to Texturizers without

Hydrofluoric Acid or Nitric Acid for Multicrystalline

Silicon Photovoltaics

   Solar cell fabrication includes a  texturizing step. A flat surface reflects energy away from
the cell, but raised structures on the surface reflect energy into the cell, increasing its energy
output. The texturizing step for multicrystalline photovoltaic cells reduces reflectance and
improves the efficiency of the cell; it is critical to the cell's ultimate performance.
   Current texturizing technologies for multicrystalline silicon wafers require several hazardous
chemicals. The photovoltaic industry currently dilutes concentrated 49-percent hydrofluoric
acid (HF) and 69-percent nitric acid in an exothermic reaction to a make a bath that contains
10-percent HF and 35-percent nitric acid. The nitric  acid oxidizes the silicon and the HF
does the bulk etching. The handling, storage, use, and  disposal  of these hazardous solutions
require extreme care and can contribute significant expense depending on local and regional
treatment requirements.
   Dow's new technology uses  an alkaline hydroxide solution with an  added oxidant, which
behaves isotropically like the HF—nitric acid bath and delivers equivalent or better performance
while significantly reducing the health, safety, and environmental negatives of the  current
technology. This alkaline texturizer is compatible with existing equipment configurations.
The process also reduces  the  cost of ownership by  reducing  operational costs including
process energy and waste treatment.  The makeup chemistry for  the new solution requires
about 8-pcrccnt active ingredients compared to 45-percent for the HF—nitric acid bath. The
HF system requires replenishment with three times more reagents than does the new system.
The new technology consumes substantially fewer materials, which results in significant cost
savings and less chemical waste. Dow will be alpha-testing its new, multicrystalline texturizer in
January 2010 and expects to make it available commercially later in 2010. There are no other
suitable replacements tor HF—nitric acid on the market today or described in the literature.

Cerenol9 Polyol  Technology Platform for a Sustainable,

Biobased Economy

   With its vision for a sustainable, biobased economy, DuPont has developed an innovative
technology platform based on renewably sourced polyols. This platform integrates biology,
chemistry, materials science, and engineering to develop renewably sourced products with
performance equal to or better than the petrochemical products they replace,
   DuPont Cerenol® is a family of high-performance poly(ether diols) made in a sustainable,
unconventional,  self-condensation polymerization process that primarily uses  a renewably
sourced ingredient, 1,3-propanediol (Bio-PDO™). The process uses a soluble acid catalyst at
less than one percent by weight that is subsequently removed during purification.  The benefits
of the Cerenol® platform include (1) a large number of polymers and products from renewably
sourced polyols, (2) high-value  uses for agricultural feedstocks,  and (3)  manufacturing
processes that not only eliminate hazardous chemicals and process conditions  but are also
more energy-efficient and  generate  reduced  levels of greenhouse gas  emissions versus
competing petroleum-based products. Although it has no in-kind competitors, Cerenol® has a
significantly lower environmental footprint than does the related petroleum-based compound,
poly(tetramethylene ether glycol), as determined by an ISO 14000-compliant life cycle analysis
(LCA). From cradlc-to-gatc, CcrcnoP provides  30-percent savings in nonrenewablc energy
and a 40-percent reduction in greenhouse gas (GHG) emissions.
   The exceptional properties of Cerenol® make it attractive for a variety of end-use applications,
including  performance coatings, inks, lubricants, functional fluids, plasticizers, and personal
care products. Cerenol* polymers are also  ideal  building blocks for  several  value-added
thermoplastic elastomers such as polyurcthanes, spandcx, copolycthcr esters, and copolycther
ester amides. DuPont's Cerenol'"' products include two high-performance industrial Iiiiron19
polyurethane coating products and Hytrel"  RS thermoplastic elastomers for the automotive
and sporting goods markets. Over the last two years, more than 20 customers have adopted
Cerenol* polyols in their product development with guidance and technology licensed from
DuPont; six customer products are in the marketplace today.

Cblorantraniliprole: Designing Green Chemistry for

Insect Control

   Historically, developers of pesticide active ingredients focused primarily on the effectiveness
of their pesticides against target pests. Now, however, new pesticide active ingredients must
also work by new modes of action to minimize the development of resistance and meet societal
demands for safety to humans and the environment. Consumers expect affordable, high-
quality food that is produced with minimal  impact on the environment. These expectations
arc reflected in higher regulatory hurdles.
   To meet these demands and expectations, DuPont redesigned its discovery process to include
early  optimization of  key  health and  environmental  characteristics  along with biological
efficacy. For its new insecticide, DuPont evaluated over 2,000 candidate analogs to find one
with the right balance in the complex dynamic of pesticidal efficacy, low toxicity to mammals
and other  nontargct species, and environmental  attributes. The result, chlorantraniliprolc, is
one of the most active and least toxic chemical insecticides ever discovered. It is a  replacement
for organophosphate insecticides such as azinphos-methyl, pyrethroids,  and neonicotinoids.
Chlorantraniliprole is effective at lower application rates and requires fewer applications per
growing season than other pesticides. It is effective against several pests  that have developed
resistance to other pesticides.
   Known by the trade names Rynaxypyr"" and Calteryx1"',  for crop and turf applications
respectively, chlorantraniliprole controls insect pests through a  new mode of action: activation
E. I. dy Pont de

E. I. du Pont de
Nemours and

Foam Sypplies, Inc.
Henkel Technologies
of insect ryanodine receptors (RyRs). Chlorantraniliprole is remarkably selective for insect
over mammalian RyRs; this selectivity is a key attribute of its low toxicity and high margins
of exposure. In 2008, EPA registered Rynaxypyr* as a reduced-risk pesticide for several major
uses. It was the first anthranilic diamide insecticide registered for use in the United States.
After less than 20 months of sales, products containing chlorantraniliprole have achieved
significant adoption by growers, approaching 10 percent of the total insecticide market on
key target crops.

Ecomate9'Environmentally Benign  Blowing Agent for

Polyurethane Foams

   For  many years, chlorofluorocarbons (CFCs)  were the  preferred  blowing agents used
to manufacture polyurethane foams. CFCs gave good insulating and structural properties
to foam used 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) are lower in ozone depletion potential
(ODP), but are scheduled for phaseout in the United  States in 2010. A related problem is
that some foam blowing agents, including CFCs, HCFCs, and hydrofluorocarbons (HFCs),
have very  high global  warming potentials (GWPs).  HCFCs and HFCs  have GWPs of
725—1810, compared to 1.00 for carbon dioxide (CCb).
   Foam Supplies developed ecomate*  (its trade name for methyl  formate) blowing agent
to replace CFCs, HCFCs, and HFCs as blowing agents for polyurethane foams. Ecomate*
blowing agent has zero ODP and zero GWP. Because it does not contribute to smog formation,
ecomate* blowing agent is also volatile  organic compound (VOC)-exempt. Each pound of
ecomate* blowing agent replaces about two pounds of alternatives, so one million pounds of
ecomate* blowing agent could eliminate 1.4—3.4 billion pounds of carbon dioxide equivalents
(CC*2c) or 0.6—1.5 million metric tons of CO2C. Ecomatc* blowing agent costs substantially
less than HFCs, and there are usually no significant expenses associated with implementing
the ecomate* technology. Using ecomate* foaming systems allows manufacturers to help the
environment without increasing costs.
   Ecomate* technology has outstanding properties and low environmental impact. It has
been demonstrated in pour-in-place, boardstock, and spray insulation systems as well as boat
flotation foam. Ecomate* foaming systems have been  introduced widely into refrigeration
applications. Using ecomate* blowing agent in polyurethane foams has saved close to 1 million
metric tons per year of high-GWP compounds such as  HFC-134a and HFC-245fa.

A Safer,  Environmentally Superior,  High-Performance

Acid Inhibitor  Designed to Protect Metallic

Infrastructure during Industrial Cleaning

   Since the early 1900's, additives have been used to prevent base-metal attack by adds during
industrial cleaning.  These additives have made cleaning highly efficient  through reductions
in acid use, base-metal  attack, and hydrogen generation, but early add inhibitors were  very
toxic. Typical current products include heterocyclic amines and sulfur compounds,  benzyl
sulfonium salts, formaldehyde, naphthalene  and  pyridine  derivatives, thioureas, propargyl
alcohol, and alkylphcnol ethoxylate surfactants (APEs), combined with solvents isopropanol
or methanol and water.
   Henkel has recently developed safer  inhibitors  including a new hydrochloric acid (HC1)
inhibitor for steel mills that is  free of propargyl alcohol and flammable solvents and is an

inhibitor for a variety of acids used in food processing equipment cleaning. This invention
involves high-performance inhibition that matches the high performance of the best current
product. Henkel's best inhibitor, Rodine* 213, is based on a sustainable raw material derived
from pine tree waste. Rodine* 213-SF uses dchydroabictylaminc solubilizcd with glycolic acid.
For safety, paraformaldehyde replaces uninhibited 37-percent  formaldehyde. The inhibitor
reaction takes place in one step with zero waste. The use of poly(alkoxylated propargyl alcohol)
and elimination of coproducts including vinyl methyl ketone and several chlorinated organics
eliminates flammability and toxicity. Residual formaldehyde is reduced by 90 percent. Finally,
alkoxylated natural fatty alcohols replace APE surfactants, which are estrogen mimics.
   Replacing all of Henkel's current sales of acid inhibitors with its newproduct would eliminate
27,300 pounds of propargyl alcohol, 94,680 pounds of alkylphenol alkoxylated surfactants,
68,750  pounds of isopropanol, 30,000 pounds of hydrochloric acid,  74,430 pounds of
acetone, 13,480 pounds of vinyl methyl ketone, 28,640 pounds of 37-percent formaldehyde,
2,130 pounds of residual formaldehyde, and 630 pounds of chlorinated organics.
   Henkel has completed final formulation improvements, testing, and reviews for full-
scale manufacturing. Rodine*'' 213-SF is currently being advertised and sampled to potential

 Tru-Core ® Protection System for  Wood

   Wood is the most widely used building material in the United States. Its environmentally
positive characteristics include low embodied energy and sustainability, but its susceptibility
to decay and insect attack can limit its durability.  For over  100  years, people have used
chemical treatments to improve wood's resistance to destructive organisms and  extend its
service life. Many traditional preservative chemicals had relatively poor health, safety, and
environmental profiles, however.  A newer generation of wood preservatives has addressed
some of the drawbacks of the older chemicals, but delivering these preservatives into the wood
is still largely based on 19th-century technologies.
   TheTru-Core* Protection System rapidly delivers globally accepted wood preservatives and
insecticides deep into the core of wood substrates without high pressure,  vacuum treatment,
or volatile organic solvents such as mineral spirits. The Tru-Core* system  embodies a unique
chemical infusion process that uses  nonvolatile, polar,  bonding carriers (amine oxides) in
a minimal amount of water to penetrate the cellular structure of wood and to deposit and
bind wood-protecting preservatives and insecticides deep within the substrate. Buffers (e.g.,
borates) bring the pH to 7 or 8 to control the penetration and binding. Unlike conventional
treatments, the Tru-Core* process uses very little water to carry the preservatives;  thus, it
eliminates the  costly, energy-consuming redrying  of wood after  treatment.  The Tru-Core"
treatment is applied to the wood surface by dipping or inline spraying. The preservatives
typically require a 12—24 hour activation period for full penetration. Afterwards, the wood
can be used or subjected to further processing or painting without drying.
   The Tru-Core* technology has recently been granted a U.S.  patent. This process is in
commercial use in three plants in the United States and eleven plants in New Zealand, where
it has largely replaced a  vacuum-treatment process requiring large amounts of petroleum-
based solvents that emitted volatile organic compounds (VOCs).

NEXAR™ Polymer Membrane Technology for Water

Purification  and Moisture Management

   The global production of  desalinated water is currently 11 billion gallons per day and is
growing each year. Sixty percent of desalination  capacity is based on membrane technology.
Current  membranes  are  limited,  however, by  their poor resistance to chlorine.  Typical
desalini/ation plants chlorinate water to prevent biofouling. They then dechlorinate it before
Kop-Coat, Inc.
Kraton Polymers LLC

passing it through the desalination membrane, and, finally, rechlorinate it prior to its entry into
the drinking water system. With current technology, capital equipment and energy account
for 70—80 percent of the cost of producing desalinated water and, typically, energy costs alone
account for up to 40 percent of operational costs.
   Kraton Polymers addressed  these problems by developing NEXAR"" polymer membrane
technology  for  applications  requiring high  water and ion  flux.  Reverse  osmosis and
electrodialysis are two of the key market segments in which NEXAR"" technology will increase
water flux and save energy. High water-transport materials like NEXAR™ polymers offer a
solution to reduce energy consumption. The system increases flux at a given pressure, thus
allowing greater  efficiency ot the overall process. NEXAR™ polymers exhibit good  chlorine
resistance that could allow processes that do not require a pretreatment to remove chlorine.
   Kraton's NEXAR™  polymers  are  sulfonated. pentablock copolymers, a new family  of
ionomeric  polymers. The unique  pentablock structure  allows  regiospecific sulfonation of
the  midblock,  which  is poly(styrene-co-styrene sulfonate); nonionic  endblocks  provide
strength and toughness in dry  and  wet conditions. Kraton Polymers improved  the synthesis
of sulfonated block copolymers by eliminating halogenated hydrocarbons; this has significant
environmental and human health benefits.  In addition, the synthesis ot this unique structure
uses as little as half the amount of aliphatic hydrocarbon.
   NEXAR'™ technology brings  performance  enhancements  to  numerous   commercial
applications including liquid  separation,  humidification control, breathable  textiles, and
advanced batteries.  During 2009,  Kraton completed initial field efficacy trials and  began
commercial sales.

A  Green,  Energy-Efficient,  Biocatalytic Process to

Manufacture Pregabalin

   Pregabalin, the active ingredient in the drug Lyrica™, is  a compound for the successful
treatment of several indications associated with neuropathic pain. The drug is approved in
154 countries including the United States. Pfizer's new route to Pregabalin is an innovative
biocatalytic process  that is more sustainable than the chemical process it replaced. Pfizer has
implemented exceptional innovation in green chemistry by using a biocatalytic reaction,
conducting reactions in water  rather than  organic solvents, selectively synthesizing  chirality
earlier in the  process  sequence, recycling the undesired enantiomer  using a continuous
process, telescoping reactions tor higher efficiency,  and implementing catalytic as  opposed
to stoichiomctric reactions.  Key innovations were overcoming product inhibition in the
biocatalytic step  to allow exceptionally high substrate concentrations and designing, building,
and validating a  new continuous plant to allow recycling of the undesirable enantiomer. The
revised route dramatically improves environmental performance, worker safety, and process
efficiency. Now, Pregabalin is one of the very few small-molecule pharmaceutical  agents where
every chemical step in the manufacturing process is performed in water.
   Pfizer has successfully implemented its new biocatalytic process in a production facility at
a 10 metric ton batch size. Between 2007 and 2020,  Pfizer estimates that the new process will
eliminate 185,000 metric tons  of solvent, 4,800 metric tons of mandelic acid, 11,000 metric
tons of the starting cyanodiester, and 2,000 metric tons  ofRaney* nickel. The biocatalytic
process also uses 83 percent less energy than the classical resolution process and reduces the
E factor of the process from 86 to 9- In the current chemoenzymatic route, the enzyme is
less expensive than the resolving agent, (5)-mandelic acid, used in the first-generation route.
Pfizer believes it  has brought an important pain-relieving medicine to the patient in the most
environmentally responsible manner.

Waterborne, Low-VOC, AlkydAcrylic Dispersion


   The high cost and uncertain availability of petroleum- and oil-based raw materials makes
dependence on these materials  questionable.  Further,  the tightening of volatile organic
compound (VOC) regulations by the Ozone Transport Commission (OTC) and the South
Coast Air  Quality Management District (SCAQMD) are  necessitating VOC-compliant
waterborne technologies that perform like solventborne coatings.
   Responding to  this challenge, Sherwin Williams developed a novel, waterborne,  low-
VOC, alkyd acrylic dispersion (LAAD) that incorporates sustainable and naturally occurring
materials. Poly(ethylene terephthalate) (PET)  is commonly used in beverage bottles. Sherwin
Williams depolymerizes post-industrial,  recycled, or virgin PET with soy tatty acids and
then rcpolymcrizcs it with trimcthylol ethane. This soy—PET liquid polyester is grafted with
hydrophobic and hydrophilic acrylic monomers in soybean oil (a reactive diluent) instead of
solvent. The anionic prepolymer is dispersed in water using triethylamine under high-shear
conditions; the resulting dispersion is formulated into coatings. The polymer dispersion has
hard PET segments of 1—2 microns for hardness; acrylic functionality for improving dry times
and barrier properties; and soya functionality to help in film formation, gloss, flexibility, and
   Coatings formulated from LAAD technology perform like the conventional, solvent-based
alkyd paints with high gloss and excellent adhesion, moisture resistance, and hydrolytic (shelf)
stability. This surfactant-free technology enables alkyd-like properties with water cleanup
and less odor than currently available conventional and high-solids alkyd and latex coatings.
Replacing all solventborne coatings (500 million gallons  in 2007) with LAAD technology
would  use about 250  million pounds of recycled PET and about 320 million pounds of
soybean oil, replace over a million barrels of crude oil, and eliminate 800 million pounds of
VOCs. The LAAD technology could also provide a secondary binder for conventional latex
paints.  Sherwin Williams  commercialized its LAAD technology  in industrial maintenance
coatings in 2009 and will  launch waterborne products for interior and exterior architectural
products in 2010.

Green  Chemistry Process for the Large-Scale Manufacture

ofPolyamino Acids

   Polyamino acids have properties that mimic proteins, making them ideal for targeted
drug delivery. They are water-soluble, selective, biodegradable, low-toxicity molecules. Their
production involves both unstable intermediate amino acid A/-carboxyanhydrides (NCAs) and
polymer processing. These two steps involve large quantities of hazardous chemicals including
phosgene, hydrogen bromide—acetic acid, acetone, and dioxane.
   Sigma-Aldrich developed novel manufacturing processes for polyamino acids that minimize
hazardous chemicals while improving quality and  efficiency.  For NCA production, they
removed uncertainty in quality and yield, which is critical for  targeted drug delivery. They
also eliminated repeated NCA recrystallizations and minimized manufacturing runs by over
30 percent, consequently  reducing phosgene and tetrahydrofuran by 30 percent and ethyl
acetate and hexane by 50 percent.
   Sigma-Aldrich also applied green practices to manufacturing poly-L-glutamic acid, a major
drug-delivery polymer, which requires hazardous operations with  highly flammable solvents
and hydrogen bromide—acetic acid or hydrogenation. By replacing a benzyl protecting group
with an ethyl group, they were able to replace hazardous chemicals with water-based chemicals,
decrease cycle time by more than half, and improve the scaleup potential 10-fold.
The Sherwin Williams

USA Corp.
   The production of polylysine polymers and polyamino acid copolymers achieved similar
savings with manufacturing processes that reduce hazardous chemicals and improve product
yield  and quality.  For polylysine polymers,  the yield increased from 10—30  percent  to
43—53 percent with half the hazardous chemicals (dioxanc,  hydrogen bromide-acetic acid,
and acetone). Production runs were halved, saving hundreds of gallons of hazardous chemicals,
generating less waste, and saving energy. Polyamino acid copolymer production was switched
to water-based  systems, eliminating generation  of the hazardous lachrymator  byproduct,
benzyl bromide, and saving hydrogen bromide—acetic acid and acetone.
   Sigma-Aldrich believes that its scientific contributions will lead to efficient chcmotherapeutic
treatments for serious human diseases such as cancer and diabetes and pave the way for greener
chemical industry practices.

An Environmentally Friendly Alternative for Cleaning

Surgical Instruments in Healthcare Facilities

   Cleaning is the single most important step in processing a surgical instrument for reuse.
Instrument cleaning, as defined by the Association for Advancement of Medical Instrumentation
(AAMI), is "the removal, usually with detergent and water,  of adherent visible soil, blood,
protein substances, and other debris from the surfaces, crevices, serrations, joints, and lumens
of instruments, devices, and equipment by a manual or mechanical process that prepares items
for safe handling and/or further decontamination." Inorganic and organic soils that are not
removed from surgical  instruments during cleaning can negatively compromise subsequent
disinfection and sterilization of surgical instruments, leading to patient  infection. If surgical
instruments are repeatedly exposed to harsh chemicals, their useful life may be shortened,
leading to increases in  both cost and waste for the healthcare facility.  Current, traditional
chemistries  have several disadvantages:  poor  substrate compatibility,  ineffective  cleaning
performance, packaging that is not ergonomic, and ingredients that are  not environmentally
   STERIS developed Prolystica'8' Ultra Concentrate cleaning chemistries and introduced them
in 2006 as an innovative, green alternative. The product line includes a neutral pH enzymatic
presoak and cleaner, a neutral pH detergent, and an alkaline detergent with lower alkalinity. All
three formulations are phosphate-free. They contain surfactants that are biodegradable, as well
as biodegradable corrosion inhibitors (biodegradable polycarboxylic acid), chelating agents (an
iminodisuccinate and a methyl glycine diacetate), and sequestering agents (including inulin
derived from chicory). These 10-fold-concentrated cleaning products provide industry-leading
cleaning and protection for surgical instruments and arc environmentally friendly. The smaller
product containers of the Prolystica'8' Ultra Concentrate products reduce the amount of waste
generated for disposal and increase staff safety. Overall, Prolystica"" Ultra Concentrate products
with biodegradable formulas reduce shipment fuel  costs, plastic packaging consumption,
and chemicals used per wash cycle. Prolystica* Ultra Concentrate products are now in use at
1,442 healthcare facilities in the United States and Canada.

Dequest®' PB: Carb oxy methyl Inulin, A  Versatile Scale

Inhibitor from  the Roots of Chicory

   Fouling of surfaces by mineral salt scale is a major problem in water-bearing systems. Scaling
reduces  heat-transfer efficiency and interferes with industrial process operations. Similarly,
hardness  ions hinder the efficiency of detergents and cleaning processes. Scale inhibitors are
used to prevent the deposition of inorganic scales onto surfaces. Previous scale inhibitors were
either biodegradable with limited applicability or poorly biodegradable with moderate toxicity
but good performance. Previous inhibitors did not use renewable resources.

   Carboxymethyl inulin (CMI), developed by Solutia in collaboration  with  Royal  Cosun,
provides an environmentally friendly, cost-effective, sate, and versatile alternative to traditional
scale  inhibitors  in  a wide variety  of industrial applications.  Moreover, CMI  is  a  good
chelator and an  excellent dispersant, which makes  it an attractive ingredient for household
detergents. Recent research has shown that CMI can be formulated in lower amounts than can
polyacrylates and polyaspartates. Unlike polyaspartate, CMI  is stable  in the presence of low
levels of oxidizing agents like hydrogen peroxide. Thermphos has discovered synergistic effects
between CMI and other chelants and has filed patents.
   Phosphorous in detergents is a growing environmental concern. Many commercial detergents
include CMI because it can be used in phosphorus-free formulas at much lower concentrations
than other co-builders. CMI is based on inulin, an oligosaccharide harvested from the  roots of
chicory. It does not compete with food production.  Current commercial applications  include
household, industrial, and institutional detergents and cleaners, secondary oil recovery, and
pulp and paper processing. CMI can also replace poorly biodegradable scale inhibitors in water
and process water treatment, sugar refining, and other industrial applications. It performs well
on sulfate  scales, especially under high total dissolved solids and high iron conditions.  CMI is
not a strong chelator of transition metals and, therefore, does not contribute to the unintended
mobilization of heavy metals.  CMI is the first inulin derivative to reach the market.

Diesel and Jet Fuels from Renewable Resources  That Are

Fungible  with  Petroleum Fuels

   Two roadblocks preventing the widespread use of renewable sources in transportation fuel
are compatibility with the existing fuel distribution infrastructure and blending compatibility
with  current  petroleum-based  fuels.  The primary  components of  current  renewable
transportation fuel are ethanol and fatty acid methyl ester (FAME; biodicscl). Because neither
of these components is compatible with the  existing infrastructure, they must  be  splash-
blended at fuel distribution terminals. Also, they are limited  to about 10 percent  by  volume
because they are incompatible with current gasoline, jet, and diesel engines. This presents a
huge hurdle for their commercial acceptance.
   Scientists and engineers at LJOP have developed the innovative approach of hydroprocessing
biofeedstocks into transportation fuels. Using new catalysts and process-flow schemes, UOP
can produce both diesel and jet fuels from a broad range of biofeedstocks  including jatropha,
camelina,  algal oil, animal  fats, and used cooking  oil. Their products are compatible with
the existing refiner)' infrastructure, technology, and  distribution network.  More importantly,
the bioproducts  resulting from the UOP processes can be blended directly into current fuels
without modifying the jet or diesel engines or the delivery infrastructure.
   UOP took these inventions through full process design leading to the UOP/Eni Ecofining™
process for green diesel, which it licensed to four refiners. UOP has extended its technology to
jet fuel and produced commercial quantities of  green jet fuel. Five commercial demonstration
flights by major  international  airlines have used the  fuel successfully. Although  the diesel and
jet processes are  similar, the detailed flow schemes and catalysts are different because of the
differing specifications for the two fuels. A life  cycle analysis (LCA) estimates greenhouse gas
(GHG) savings to be 84 percent for green jet fuel and 89 percent for  green diesel. UOP has
filed  a total of 28 U.S. patent  applications for the Ecofining™ diesel and jet fuel technologies.


                                   with *.

            Technology             Inc.
RegenSi™: A Wafer Reclaim Solution with a Low Carbon Footprint that Extends the
Life Cycle of Silicon  Test Wafers	29
                          Chemicals, LLC
Bipolar Membrane Electrodialysis for Greener Processing ofChelates ........... 29
Novel,  Greener, Water-Soluble, Hybrid Polymer Technology for Fabric and Cleaning,
Industrial Water Treatment, and Oil Recovery Applications	30
APTech          Inc.
Safer, Sustainable, Biodegradable, Solid-State Chemistry for Treating Cooling Water
Systems	15

An Environmentally Friendly Process for Upcycling Plastic Waste into Advanced
Carbon Nanotubes and Carbon Spheres. ............................... 31
BioBased Tile9 with BioStridf': A Revolutionary New Flooring Made with Rapidly
Renewable Resources.............................................. 31
A.S.       &             Inc.
HCR-188C1: An All-New, High-Efficiency Hydrocarbon Refrigerant with No Impact
on  Global Warming or the Ozone Layer	15

Highly Water-Dispersed Oilfield Corrosion Inhibitors Eliminate over One Million
Pounds of Nonrenewctble Solvents Annually ............................. 32
*BASF; The       Chemical Company
Innovative, Environmentally Benign Production ofPropylene Oxide via
Hydrogen Peroxide ................................................ 5

ReFlex™ 100 Bioderived Green Bioplasticizers for Poly (vinyl chloride)	32
IMPACT Technology: A Greener Poly ether Polyol Process	33

Recovering and Using a Formerly Incinerated Sodium Nitrite Waste Stream to
Disinfect and Stabilize Municipal Biosolids	16
Spray-Dried Dispersions Based on Hydroxypropyl Methylcellulose Acetate Succinate
for Delivery of Low-Solubility Drugs .................................. 16
                         Chk Inc.;
Nonhalogenated Flame Retardantfor Use in High-Performance Adhesives

    Supercritical—Solid Catalyst Reaction Process for Converting Waste Fats, Oils, and
    Greases into Premium Biodiesel	17

    The Development and Commercialization of a Low-pH, Lactic Acid Process for
    Renewable Plastics  ................................................  34

    Elimination ofPerftuorinated Alky I Surfactants from Fire-Fighting Foams	18

            Chk Inc.
    Nonhalogenated Flame Retardantfor Use in High-Performance Adhesives
    and Coatings [[[  34

    Nattdaf" Larvicide: Adapting Spinosadfor Next-Generation Mosquito Control. .... 7
    Rapid Enabiement of Green Processes for Chirai Alcohols by the Codex"" Panel of
    Robust, Divergent Evolvants of One Ancestral Ketoreductase ..................  35
    *Codexis, Inc.;        & Co., Inc.
    Greener Manufacturing of Sitagliptin Enabled by an Evolved Transaminase	6

    Elimination of Hexavalent Chromium from Hydraulic and Pneumatic Tubing . ...  18

    Corrosion Control with a Greener Pathway ..............................  19

    Saturated Polyester—Phenolic Resin Systems Eliminate BisphenolA and Epoxy from
    Interior Can  Coatings for Food Packaging	35
    MAXHT" Bayer Sodalite Scale Inhibitor	36
    UV-Curable Pressure Sensitive Adhesive	36

    Accelerated Solvent Extraction with Solvent Saver Mode™: Reducing Organic Solvent
    Consumption and Waste in Laboratories. ................................  37

    Safer, Less Toxic, Sustained Release Chemistry: Green Water Treatment with Smart
    Release® Technology................................................  19
    Energy/ Savings from a New Manufacturing Route for Vinyl Methyl Ether ........  37
    An Innovative Approach to Texturizers without Hydrofluoric Acid or Nitric Acid for

Innovative, Environmentally Benign Production ofPropylene Oxide via
Hydrogen Peroxide ................................................. 5
                            LLC;         C. Liao,              of
California, Los
Recycling Carbon Dioxide to Biosynthesize Higher Alcohols	3
E. I. du       de
Ce renof Polyol Technology Platform for a Sustainable, Bio based Economy.  ...... 39
Chlorantraniliprole: Designing Green Chemistry for Insect Control	39

        Chk Inc.;
Nonhalogenated Flame Retardantfor Use in High-Performance Adhesives
and Coatings	34
Ecomate® Environmentally Benign Blowing Agent for Polyurethane Foams	40
FIX            Inc.
Green Chemistry to Replace Bromine-Based Flame Retardants.  ...............  20
Sustainable Chemicals from Renewable Resources: A. Breakthrough for
Biomanufacturing. ...............................................  20

                  L,                                              M.
Organic Catalysis: A Broadly Useful and Environmentally Benign Strategy
to Synthetic Polymer Materials	12

A Safer, Environmentally Superior, High-Performance Acid Inhibitor Designed to
Protect Metallic Infrastructure during Industrial Cleaning ..................  40

                                            L.                    M.
Organic Catalysis: A Broadly Useful and Environmentally Benign Strategy
to Synthetic Polymer Materials. ......................................  12

                Uniwersity,               of
Green Process of Unfolding Soy Protein Polymers for Green Adhesives	11
                     Co., Ltd.;
Uniwersity;                    USA, Inc.
Highly Efficient and Practical Monohydrolysis of Symmetric Diesters	10

Kop-Coat, Inc.
Tru-Core* Protection System for Wood.  ................................  41

    NEXARM Polymer Membrane Technology for Water Purification and Moisture
    Management	41

    *Liao,         C.,                           LLC                  of
    Recycling Carbon Dioxide to Biosynthesize Higher Alcohols. .................. 3
    Microbial Production of Renewable Petroleum ™ Fuels and Chemicals	4

                             1.,                of
    of        University of
    Template-Controlled Reactivity in the Organic Solid State .................... 9

    Zequanox", an Environmentally Safe. Solution for Controlling Invasive Zebra and
    Quagga Mussels .................................................. 21

                                   of                          of
    California,                            for
    High-Yield Conversion ofBiomass into a New Generation ofBiofnels and Value-Added
    Products	9
             &  Co., Inc.;           Inc.
    Greener Manufacturing of Sitagliptin Enabled by an Evolved Transaminase	6
    An Acyl Amino Acid Surfactant Produced by Sustainable Chemistry	22

                                  of                          of
    High-Yield Conversion ofBiomass into a New Generation ofBiofuels and Value-Added
    Products	9

                                                                 USA, Inc.;
    Highly Efficient and Practical Monohydrolysis of Symmetric Diesters	10

    Device and Method for Analyzing Oil and Grease in Wastewaters without Solvent. . 22
    2-Methyltetrahydrofuran: A Green Alternative to Oil-Derived Ethers and Chlorinated
    Solvents	23
    A Green, Energy-Efficient, Biocatalytic Process to Manufacture Pregabalin. ...... .42
50  PRE-TEC3000s: An Environmentally Friendly Wood Treatment.  ............. 23

Recovering and Using a Formerly Incinerated, Sodium Nitrite Waste Stream to
Disinfect and Stabilize Municipal Biosolids .............................. 16

          Phillip E.f
University of
Terephthalic Acid Synthesis in High-Temperature Liquid Water at
High Concentrations	10

Waterborne, Low-VOC, AlkydAcrylic Dispersion Technology	43
Green Chemistry Process for the Large-Scale Manufacture ofPolyamino Acids	43
Renewable Oil Production from Algae	24
            LLQ                Sun,                of

Green Process of Unfolding Soy Protein Polymers for Green Adhesives. .......... II
                                       of                       M.
Organic Catalysis: A Broadly Useful and Environmentally Benign Strategy
to Synthetic Polymer Materials	12

An Environmentally Friendly Alternative for Cleaning Surgical Instruments in
Healthcare Facilities	44

Development and Commercial Application ofSAMMS®: A Novel Adsorbent for the
Removal of Mercury and Other Toxic Heavy Metals	25
Bioil Technology: One-Pot,  Catalytic Hydrolysis ofLignocelluloses	25
Sun,                                of
Green Process of Unfolding Soy Protein Polymers for Green Adhesives	11

Tang, Yif                of Chemical
                             of California, Los
An Efficient, Biocatalytic Process for the Semisynthesis of Simvastatin. .......... 12
Terrabon, Inc.
Conversion of Municipal Solid Wastes to Drop-In Fuels and Chemicals	26
             Uniwersity,                of
                                                           USA, Inc.;
                     Co., Ltd.
Highly Efficient and Practical Monohydrolysis of Symmetric Diesters	10

    Deques"f PB: Carboxymethyl Inulin, A Versatile Scale Inhibitor from the Roots of
    Chicory	44
    Source Reduction and Sustainability through Use ofMergaf 753 Antimicrobial
    Preservative [[[ 26
                of California,                      of
    High-Yield Conversion ofBiomass into a New Generation of Bio fa-els and Value-Added
    Products	9
    *Uni¥ersitf of California, Los
                       LLC,        C.
    Recycling Carbon Dioxide to Biosynthesize Higher Alcohols. ................... 3
                of California,                              of
    An Efficient,  Biocatalytic Process for the Semisynthesis of Simvastatin	12
                of                       of Chemistry,           R.
    Template-Controlled Reactivity in the Organic Solid State	9
                of                                             of
                         of                       R.
    Template-Controlled Reactivity in the Organic Solid State ................... 9

    Phillip E.
    Terephthalic Acid Synthesis in High- Temperature Liquid Water at
    High Concentrations	10

    Diesel and Jet Fuels from Renewable Resources TfjatAre Fungible with
    Petroleum Fuels .................................................. 45

                       USA, Inc.;
                                    USA, Inc.;
    Co., Ltd.
    Highly Efficient and Practical Mono hydrolysis of Symmetric Diesters	10
    Wayrnouth,         M.f               of Chemistry,
    Organic Catalysis: A. Broadly Useful and Environmentally Benign Strategy



on 100% recycled/recyclable paper with a minimum 50% post-consumer waste using vegetable inks.
                               of Pollution                     744K10001
                         Toxics                                www.epa.gov
                         Prevent'orl and                        June 2010