v>EPA
United States
Environmental
Protection
Agency
Presidential
Green Chemistry Challenge
Awards Program:
Summary of 201 1 Award
Entries and Recipients
An electronic version of this document is available at:
http://www.epa.gov/greenchemistry
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of
Introduction [[[ 1
Awards [[[ 3
Academic Award ............................................ 3
Small Business Award ........................................ 4
Greener Synthetic Pathways Award ................................ 5
Greener Reaction Conditions Award .............................. 6
Designing Greener Chemicals Award .............................. 7
Entries from Academia ............................................ 9
Entries from Small Businesses ...................................... 17
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Introduction
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.
Throughout the 16 years of the awards program, EPA has received more than 1,400
nominations and presented awards to 82 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.
Each year together our 82 winning technologies are responsible for reducing the use or generation
of more than 199 million pounds of hazardous chemicals, saving 21 billion gallons of water, and
eliminating 57 million pounds of carbon dioxide releases to air. Adding the rest of the nominated
technologies makes the benefits far greater.
This booklet summarizes entries submitted for the 2011 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 2011 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 20, 2011, 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/greenchemistry.
Note: The summaries provided in this document were obtained from the entries received for the 2011 Presidential Green Chemistry
Challenge Awards. EPA edited the descriptions for space, stylistic consistency, and clarity, but they were not written or officially
endorsed by the Agency. The summaries are intended only to highlight a fraction of the information contained in the nominations.
These summaries were not used in the judging process; judging was based on all information contained in the entries received.
Claims made in these summaries have not been verified by EPA.
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Towards Ending Our Dependence on Organic Solvents
Innovation and Benefits
Most chemical manufacturing processes rely on organic solvents, which tend to be volatile,
toxic, and flammable. Chemical manufacturers use billions of pounds of organic solvents
each year, much of which becomes waste. Water itself cannot replace organic solvents as the
medium for chemical reactions because many chemicals do not dissolve and do not react in
water. Professor Lipshutz has designed a safe surfactant that forms tiny droplets in water.
Organic chemicals dissolve in these droplets and react efficiently, allowing water to replace
organic solvents.
Organic solvents are routinely used as the medium for organic reactions and constitute a large
percentage of the world's chemical production waste. Most organic solvents are derived from
petroleum and are volatile, flammable, and toxic. Typically, organic reactions cannot be done
in water because the reactants themselves are insoluble. Surfactants can be used to increase the
solubility of organic reactants in water, but they often disperse the reactants, slowing the reactions.
Professor Lipshutz has designed a novel, second-generation surfactant called TPGS-750-M. It is
a "designer" surfactant composed of safe, inexpensive ingredients: tocopherol (vitamin E), succinic
acid (an intermediate in cellular respiration), and methoxy poly(ethylene glycol) (a common,
degradable hydrophilic group also called MPEG-750). TPGS-750-M forms "nanomicelles"
in water that are lipophilic on the inside and hydrophilic on the outside. A small amount of
TPGS-750-M is all that is required to spontaneously form 50—100 nm diameter micelles in water
to serve as nanoreactors. TPGS-750-M is engineered to be the right size to facilitate broadly used
organic reactions, such as cross-couplings. Reactants and catalysts dissolve in the micelles, resulting
in high concentrations that lead to dramatically increased reaction rates at ambient temperature.
No additional energy is required.
Several very common organic reactions that are catalyzed by transition metals can take place
within TPGS-750-M micelles in water at room temperature and in high isolated yields. These
reactions include ruthenium-catalyzed olefin metatheses (Grubbs), palladium-catalyzed cross-
couplings (Suzuki, Heck, and Sonogashira), unsymmetrical aminations, allylic aminations and
silylations, and aryl borylations. Even palladium-catalyzed aromatic carbon—hydrogen bond
activation to make new carbon—carbon bonds can be done at room temperature, an extraordinary
achievement. Product isolation is straightforward; complications such as frothing and foaming
associated with other surfactants are not observed. Recycling the surfactant after use is also very
efficient: the insoluble product can be recovered by extraction, and the aqueous surfactant is
simply reused with negligible loss of activity. Future generations of surfactants may include a
catalyst tethered to a surfactant to provide both the "reaction vessel" (the inside of the micelle)
and the catalyst to enable the reaction. Tethering catalysts in this way may reduce one-time use of
rare-earth minerals as catalysts.
In all, this technology offers opportunities for industrial processes to replace large amounts
of organic solvents with very small amounts of a benign surfactant nanodispersed in water only.
High-quality water is not needed: these reactions can even be run in seawater. Sigma-Aldrich is
currently selling TPGS-750-M, making it broadly available to research laboratories.
Professor Bruce
H. Lipshutz,
Department of
Chemistry and
Biochemistry,
University of
California,
Santa Barbara
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BioAmber, inc.
Integrated Production and Downstream Applications
of Biobased Succinic Acid
Innovation and Benefits
Succinic acid is a true "platform molecule," that is, a starting material for other important
chemicals, but the high cost of producing succinic acid from fossil fuels has restricted its use.
Now, however, BioAmber is producing succinic acid that is both renewable and lower cost
by combining an E. coli biocatalyst licensed from the Department of Energy with a novel
purification process. BioAmber's process uses 60 percent less energy than succinic acid made
from fossil fuels, offers a smaller carbon footprint, and costs 40 percent less.
Succinic acid has traditionally been produced from petroleum-based feedstocks. In addition to
its current use in food, drug, and cosmetic applications, succinic acid is a platform molecule that
can be used to make a wide range of chemicals and polymers.
BioAmber has developed an integrated technology that produces large, commercial
quantities of succinic acid by fermentation rather than from petroleum feedstocks. Since early
2010, BioAmber has been producing succinic acid by bacterial fermentation of glucose in the
world's only large-scale, dedicated, biobased succinic acid plant. This $30 million plant includes
an integrated, continuous downstream process. BioAmber believes its renewable succinic acid is
the first direct substitution of a fermentation-derived chemical for a petroleum-derived chemical.
BioAmber has successfully scaled up an E. coli biocatalyst licensed from the Department of
Energy and integrated a novel, water-based downstream purification process. The fermentation
process, although pH neutral, produces no significant byproducts. BioAmber's technology
produces succinic acid at a cost that is 40 percent below that of petroleum-based succinic acid.
Even at oil prices below $40 per barrel, BioAmber's product boasts cost advantages over succinic
acid derived from fossil fuels.
BioAmber's economic advantage has given a number of chemical markets the confidence both
to use succinic acid as a substitute for existing petrochemicals and to develop new applications
for succinic acid. Succinic acid can replace some chemicals directly, including adipic acid for
polyurethane applications and highly corrosive acetate salts for deicing applications. BioAmber
has also made it economically feasible to (1) transform biobased succinic acid into renewable
1,4 butanediol and other four-carbon chemicals; (2) produce succinate esters for use as nontoxic
solvents and substitutes for phthalate-based plasticizers in PVC (poly(vinyl chloride)) and
other polymers; and (3) produce biodegradable, renewable performance plastics. BioAmber is
leading the development of modified polybutylene succinate (mPBS), a polyester that is over
50 percent biobased and offers good heat-resistance (above 100 °C) and biodegradability (ASTM
D6400 compliant). BioAmber's process reduces energy consumption by 60 percent compared to
its petrochemical equivalent and actually consumes carbon dioxide (CC>2), rather than generating
it.
In 2011, BioAmber plans to begin constructing a 20,000 metric ton facility in North America
that will sequester over 8,000 tons of CC>2 per year, an amount equal to the emissions of
8,000 cross-country airplane flights or 2,300 compact cars annually. BioAmber has also signed
partnership agreements with several major companies, including Cargill, DuPont, Mitsubishi
Chemical, and Mitsui & Co. The scale up of biobased succinic acid to commercial quantities
will expand markets, reducing pollution at the source and increasing health benefits at numerous
points in the lifecycles of a variety of chemicals made from succinic acid.
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Production of High-Volume Chemicals from Renewable
Feedstocks at Lower Cost
Innovation and Benefits
1,4-Butanediol (EDO) is a high-volume chemical building block used to make many
common polymers, such as spandex. Using sophisticated genetic engineering, Genomatica
has developed a microbe that makes EDO by fermenting sugars. When produced at
commercial scale, Genomatica's Bio-EDO will be less expensive, require about 60 percent
less energy, and produce 70 percent less carbon dioxide emissions than EDO made
from natural gas. Genomatica is partnering with major companies to bring Bio-EDO to
the market.
Most high-volume commodity chemicals, including monomers, are made from natural gas or
petroleum. Genomatica is developing and commercializing sustainable basic and intermediate
chemicals made from renewable feedstocks including readily available sugars, biomass, and syngas.
The company aims to transform the chemical industry through the cost-advantaged, smaller-
footprint production of biobased chemicals as direct replacements for major industrial chemicals
that are currently petroleum-based in a trillion-dollar global market. By greening basic and
intermediate chemicals at the source, Genomatica's technology enables others to make thousands
of downstream products more sustainably without changing their manufacturing processes. By
producing the building-block chemicals directly, Genomatica also reduces unwanted byproducts.
The first target molecule for Genomatica is 1,4-butanediol (EDO). EDO is used to make
spandex, automotive plastics, running shoes, and many other products. It has an approximately
2.8 billion pound, $3 billion worldwide market. Genomatica has been producing Bio-BDO at
pilot scale in 3,000 liter fermentations since the first half of 2010 and is moving to production
at demonstration scale in 2011. Multiple large chemical companies have successfully tested
Genomatica's Bio-BDO as a feedstock for polymers. The performance of Bio-BDO has met the
standards set for petroleum-based EDO. Initial lifecycle analyses show that Genomatica's Bio-
BDO will require about 60 percent less energy than acetylene-based EDO. Also, the biobased
EDO pathway consumes carbon dioxide (CC>2), resulting in a reduction of 70 percent in CO2
emissions. Fermentation requires no organic solvent, and the water used is recycled. Furthermore,
the Bio-BDO fermentation process operates near ambient pressure and temperature, thus
providing a safer working environment. These advantages lead to reduced costs: production
facilities should cost significantly less, and production expenses for Bio-BDO should be
15—30 percent less than petroleum-based EDO. Genomatica expects Bio-BDO to be competitive
at oil prices of $45 per barrel or at natural gas prices of $3.50 per million Btu.
Genomatica's unique, integrated bioprocess engineering and extensive intellectual property
allow it to develop organisms and processes rapidly for many other basic chemicals. Because
the chemical industry uses approximately 8 percent of the world's fossil fuels, Genomatica's
technology has the potential to reduce carbon emissions by hundreds of millions of tons annually.
Genomatica has entered into partnerships with several major companies including Tate & Lyle,
M&G (a major European chemicals producer), Waste Management, and Mitsubishi Chemical
to implement their technology at a commercial scale. Genomatica expects to begin commercial
production of Bio-BDO in 2012. They plan to roll out plants in the United States, Europe, and
Asia over time.
Genomatica
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Kraton Performance
Polymers, inc.
NEXAR™ Polymer Membrane Technology
Innovation and Benefits
Purification of salt water by reverse osmosis is one of the highest-volume uses of membrane
filtration. Kraton has developed a family of halogen-free, high-flow, polymer membranes
made using less solvent. The biggest benefits are during use: A reverse osmosis plant using
NEXAR™ membranes can purify hundreds of times more water than one using traditional
membranes, save 70 percent in membrane costs, and save 50 percent in energy costs.
Polymer membranes are used in a variety of purification processes. Membranes selectively allow
some molecules to pass while preventing others from crossing the barrier. Membrane purifications
include water desalination by reverse osmosis, water ultra-purification, salt recovery, and waste
acid recovery. Membrane efficiency is limited by the rate at which water (or another molecule)
crosses the membrane, a property called the flux. Increasing the pressure of the "dirty" side of the
membrane can increase the flux, but a higher pressure requires a stronger membrane.
Kraton Performance Polymers has developed NEXAR™ polymer membrane technology for
applications requiring high water or ion flux. Kraton's NEXAR™ polymers are block copolymers
with separate regions that provide strength (poly(Y-butyl styrene)), toughness and flexibility
(poly(ethylene—propylene)), and water or ion transport (styrene—sulfonated styrene). These
A-B-C-B-A pentablock copolymers exhibit strength and toughness in dry and wet conditions.
Kraton's production process for NEXAR™ polymers uses up to 50 percent less hydrocarbon solvent
and completely eliminates halogenated cosolvents.
The biggest benefits are during use. NEXAR™ polymers have an exceptionally high water
flux of up to 400 times higher than current reverse osmosis membranes. This could translate
into significant reductions in energy and materials use. Modeling shows that a medium-sized
reverse osmosis (RO) plant could save, conservatively, over 70 percent of its membrane costs and
approximately 50 percent of its energy costs. For applications in electrodialysis reversal (EDR), the
higher mechanical strength of NEXAR™ polymers makes it possible to use thinner membranes,
which reduces material use by up to 50 percent and reduces energy loss due to membrane resistance.
More important, NEXAR™ polymers eliminate the current use of PVC (poly(vinyl chloride)) in
electrodialysis membranes. The outstanding water transport rate of NEXAR™ membranes also
significantly improves energy recovery ventilation (ERV), by which exhausted indoor air conditions
incoming fresh air. For other humidity regulation applications, including high-performance
textiles and clothing, NEXAR™ polymers offer environmental benefits by completely eliminating
halogenated products such as Nafion® polymers and PTFE (poly(tetrafluoroethylene)) that may
require hazardous halogenated processing aids.
Kraton introduced NEXAR™ polymers in the United States, China, and Germany during
2010. In the third quarter of 2010, Kraton completed its first successful large-scale production of
NEXAR™ of about 10 metric tons.
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Water-basedAcrylic Alkyd Technology
The Sherwin-
Williams Company
Innovation and Benefits
Oil-based "alkyd" paints have high levels of volatile organic compounds (VOCs) that
become air pollutants as the paint dries. Previous acrylic paints contained lower VOCs,
but could not match the performance of alkyds. Sherwin-Williams developed water-based
acrylic alkyd paints with low VOCs that can be made from recycled soda bottle plastic
(PET), acrylics, and soybean oil. These paints combine the performance benefits of alkyds
and low VOC content of acrylics. In 2010, Sherwin-Williams manufactured enough of
these new paints to eliminate over 800,000 pounds of VOCs.
The high cost and uncertain availability of petroleum-based raw materials makes dependence
on these materials unsustainable. Furthermore, the tightening of volatile organic compound
(VOC) regulations by the Ozone Transport Commission (OTC) and the South Coast Air
Quality Management District (SCAQMD) necessitates VOC-compliant waterborne coatings in
place of solventborne coatings. Today, acrylic latex emulsions dominate the low-VOC waterborne
coatings and alkyds dominate the solventborne coatings, but latex-based coatings have difficulty
meeting all the performance and application properties of solventborne coatings.
To address this challenge, The Sherwin-Williams Company developed a novel, low-VOC,
water-based acrylic alkyd technology based on sustainability principles. At the heart of this
water-based acrylic alkyd technology is a low-VOC, alkyd—acrylic dispersion (LAAD). This
polymer dispersion has PET (poly(ethylene terephthalate)) segments for rigidity, hardness, and
hydrolytic resistance; it has acrylic functionality for improved dry times and durability; and it
has soya functionality (from soybean oil) to promote film formation, gloss, flexibility, and cure.
Sherwin-Williams designed this water-based acrylic alkyd technology to meet key performance
attributes of solvent-based alkyds for architectural and industrial maintenance coatings
applications, but with lower VOCs, without surfactants, and with excellent hydrolytic stability
similar to that of latex paints. Sherwin-Williams water-based acrylic alkyd coatings bring together
the best performance benefits of alkyd and acrylic paints, offering the application and finish of
alkyds, including high gloss and excellent adhesion and moisture resistance, with the low VOC
content, low odor, and non-yellowing properties of acrylics.
Since the launch of their LAAD products, ProClassic Waterbased Acrylic Alkyd, ProMar
200 Waterbased Acrylic Alkyd, and Prolndustrial Waterborne Enamel, in 2010, Sherwin-
Williams has eliminated the use of over 800,000 pounds of VOC solvents and other petroleum-
based feedstocks.
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Ethyl L-Lactate as a Tunable Solvent for
Greener Synthesis of DiarylAldimines
Imines are essential intermediates in many reactions of pharmaceutical interest. For example,
diaryl aldimines are used to synthesize blockbuster drugs such asTaxol® (used in chemotherapy) and
Zetia® (used in cholesterol reduction). Diaryl aldimines are also used as additives to polyethylene
to increase its rate of photodegradation in the environment. Unfortunately, traditional syntheses of
diaryl aldimines are typically inefficient and environmentally unfriendly. They often use hazardous
solvents such as benzene, toluene, and methylene chloride and require energy-intensive, multihour
reflux steps. Although some recent imine syntheses have successfully used more benign solvents or
conditions, these still require long reaction times and recrystallization or other purifications that
negate some of the benefits of the otherwise greener syntheses.
Recently, Professor Bennett found that ethyl L-lactate, an FDA-approved food additive, can
replace the hazardous solvents traditionally used to synthesize imines. Since then, she and her
undergraduate students have used this method to synthesize over 140 diaryl aldimines. The
method is extremely efficient under ambient conditions; it has a median yield of over 95 percent
and a median reaction time of less than 10 minutes. The method also requires less solvent than
published methods. The resulting imines are usually of such purity that recrystallization is
unnecessary, thus avoiding additional waste. The key to the process is "tuning" the polarity of the
ethyl lactate by adding water. The starting materials remain dissolved, but the imine crystallizes
out of solution as it forms. Traditional methods often remove water to drive the reaction forward.
In contrast, Professor Bennett's method drives the reaction forward by removing the product
by direct crystallization. In summary, her ethyl lactate method is faster, usually results in higher
purity and yield, uses less energy, uses less solvent, generates less waste, and uses a more benign
solvent than previous methods. During 2010, Professor Bennett filed a provisional patent for
this technology.
Metal Adhesive Polymers from Cd-Catalyzed
Azide—Alkyne Cy do addition:
A New Approach to Solder Replacements
Lead—tin solder is typically used to assemble printed circuit boards for personal microelectronic
devices such as cell phones. The global proliferation of these devices results in unacceptable
exposures of workers to lead, tin, and other toxic chemicals during device fabrication and,
eventually, disassembly for recycling. International and state laws are beginning to limit these toxic
substances in electronics, expanding the market for lead-free solder replacements.
In his research on finding lead-free solder, Professor Finn at The Scripps Research Institute
has pioneered the discovery and application of Cu'-catalyzed azide—alkyne cycloaddition
(CuAAC) reactions. The Sharpless and Finn labs were first to use this reaction to produce metal-
adhesive materials from multivalent azide and alkyne monomers. Metallic copper at surfaces of
metal substrates exposed to air provides enough Cu1 ions to catalyze the formation of triazole
cross-links, which bind the metal tightly. Triazole cross-links are also nontoxic and resistant to
oxidation, reduction, irradiation, and heat. The highly efficient CuAAC process provides high
conversions of azide and alkyne groups to triazoles. This process maximizes the cross-link density
of the adhesive and thereby its strength, but at the expense of increasing the brittleness of the
material. The incorporation of flexibility-inducing components and additional amine ligands in
the adhesive mixtures enhances strength as determined by measuring maximum load before failure
in a modified peel test on a custom-built, high-throughput instrument.
Professor
Jacqueline Bennett,
Department of
Chemistry &
Biochemistry,
State University of
New York Oneonta
Professor M.G.
Finn, The Scripps
Research institute
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Professor Mark
Mascal, Department
of Chemistry,
University of
California, Davis
Professor Satomi
Niwayama,
Department of
Chemistry and
Biochemistry,
Texas Tech
University
Current research is examining the conductivity, surface composition, and thickness of mixtures
of the adhesive with conjugated molecular wires, silver nanoparticles, and carbon black using
conductive probe atomic force microscopy (CP-AFM), X-ray photoelectron spectroscopy (XPS),
infrared (IR) spectroscopy, and ellipsometry. This work provides exciting prospects for replacing
resource-intensive solder composites with low-cost, nontoxic, conductive organic mixtures. In
2008, Professors Finn and Sharpless submitted a patent application for this technology and had a
second patent published.
High-Yield Conversion ofBiomass into a New Generation
ofBiofuels and Value-Added Products
The worldwide transition from petroleum-based technologies to alternatives creates
an extraordinary need for bioenergy research. Consequently, researchers are developing schemes
to exploit lignocellulose, the most abundant organic material on the planet. These schemes vary
considerably, but each aims to cleave the glycan into monosaccharides, then derive useful products
efficiently and inexpensively. The most successful schemes will be those that produce the highest
yields, minimize capital and operating expenses, and allow the greatest feedstock flexibility.
In 2008, Professor Mascal and his group described a method to convert cellulose into a mixture
of 5-(chloromethyl) furfural (CMF) and three minor furfural-derived products in a remarkable
85 percent overall yield. This method involves acidic digestion of cellulose in a biphasic aqueous-
organic solvent reactor. Once formed, the organic products separate from the acid before they
decompose. Subsequently, Professor Mascal discovered that his method works equally well on raw
biomass. The Mascal method produces not only CMF in high yield from the cellulose fraction of
biomass, but also furfural itself from the C5-sugar (hemicellulose) fraction. Thus, it exploits all of
the carbohydrate in the biomass.
More recently, Professor Mascal upgraded his process such that cellulose produces only
CMF (84 percent) and levulinic acid (LA, an important chemical building block; 5 percent)
in an overall 89 percent yield. The same method processes sucrose into CMF and LA in
a remarkable 95 percent yield. The method also works well on biodiesel feedstocks; from
safflower seeds, for example, the method leads to a 25 percent increase in biofuel production.
The product is a hybrid lipidic—cellulosic biodiesel. No other known process gives simple
organic products from cellulose in comparable yield. Professor Mascal has now expanded the
derivative manifold to include renewable polymers, agrochemicals, and pharmaceuticals.
He is forging development partnerships with Dow Chemical, Clorox, Aerojet, the U.S. Navy,
and Micromidas.
Highly Efficient, Practical Mono hydrolysis of
Symmetric Diesters
Water is among the most environmentally friendly solvents and is the least expensive of all
solvents. Among various synthetic conversions, the desymmetrization of symmetric compounds
is one of the most atom-economical, cost-effective reactions. The symmetric starting compounds
are typically available commercially at low cost or made easily on a large scale from inexpensive
precursors. Water-mediated desymmetrization of symmetric organic compounds is, therefore, of
tremendous synthetic value and can make a significant contribution to green chemistry.
Professor Niwayama pioneered water-mediated desymmetrization and has been developing
the monohydrolysis of symmetric diesters to half-esters with remarkable success. Half-esters have
considerable commercial value. They are highly versatile building blocks for organic synthesis
and are used frequently to synthesize polymers, dendrimers, and hyperbranched polymers with
applications to industrial products. Because the two ester groups in the symmetric diesters are
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equivalent, however, the statistically expected yield of half-esters is only 50 percent. Classical
saponification usually produces complex mixtures of dicarboxylic acids, half-esters, and the starting
diesters, which are difficult to separate and therefore, generate a large amount of undesirable
waste. In contrast, alternate ring-opening reactions of cyclic acid anhydrides to half-esters usually
require hazardous organic solvents.
Professor Niwayama 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 that may or may not contain a small amount of an aprotic
cosolvent such as tetrahydrofuran at 0 °C. Monohydrolysis occurs at the interface between the
aqueous phase and the organic phase containing the diester. This reaction produces pure half-esters
in high to near-quantitative yields without hazardous organic solvents or dirty waste products.
This reaction is anticipated to contribute significantly to green chemistry in both industry and
academia. Two companies have licensed the technology and 10 resulting half-esters are now
available commercially.
Ethylene: A Superior Reagent for Enantioselective
Functionalization ofAlkenes
New carbon—carbon bond-forming processes have been responsible for significant advances in
organic synthesis. Practical methods using feedstock carbon sources as starting materials to form
enantioselective carbon—carbon bonds are rare, however. To qualify as green, any new reaction
must: (1) use abundantly available, carbon-neutral sources; (2) produce a functional intermediate
for other common organic functional groups; (3) be highly catalytic, generating little or no waste
including toxic metals; (4) provide high, reagent-dependent selectivity to produce all isomers
including enantiomers; and (5) include easy product recovery. A broadly applicable reaction using
ethylene to install highly versatile vinyl groups enantiomerically could thus have significant impact
in organic synthesis.
Professor RajanBabu and his group have developed highly catalytic (substrate—catalyst ratio
up to 7,412:1) protocols for nearly quantitative (isolated yields up to over 99 percent) and
highly selective (approximately 100 percent regioselectivity; enantiomeric ratios of over 99:1)
co-dimerization of ethylene and various functionalized vinylarenes, 1,3-dienes, and strained
alkenes. These reactions proceed under mild conditions (-52 °C to 25 °C; 1 atmosphere of ethylene)
to produce intermediates such as 3-arylbutenes, which can be transformed to nonsteroidal anti-
inflammatory drugs (NSAIDs) in two steps. These reactions consume both starting materials,
leaving no side products. Successes include highly enantioselective syntheses of common NSAIDs,
such as ibuprofen, naproxen, flurbiprofen, and fenoprofen, from the corresponding styrenes
and ethylene.
Cyclic and acyclic 1,3-dienes also undergo efficient enantioselective addition of ethylene.
Syntheses of several 1-vinylcycloalkenes and l-substituted-l,3-butadienes achieve yields up
to 99 percent. Professor RajanBabu has found expeditious routes to biologically relevant
classes of compounds including bisabolanes, herbindoles, trikentrins, steroid D-ring 205- or
207?-derivatives, (-)-desoxyeseroline, pseudopterosin A—F, G—J, and K—L aglycones, and
helioporins. These syntheses require fewer steps than traditional methods and produce uncommon
configurational isomers. In 2010, Professor RajanBabu published three papers on this work.
Professor I.V.
RajanBabu,
Department of
Chemistry, The Ohio
State University
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Professor Phillip E.
Savage, Chemical
Engineering
Department,
University of
Michigan
Professor
David Schiraldi,
Department of
Macromolecular
Science and
Engineering, Case
Western Reserve
University and
Aeroclay, Inc.
Terephthalic Acid Synthesis at High Concentrations in
High- Temperature Liquid Water
Acetic acid is the traditional solvent used to synthesize terephthalic acid commercially, but
it has several drawbacks. First, acetic acid is flammable. Second, the commercial terephthalate
process requires an expensive, energy-intensive distillation to separate acetic acid from water,
which is a byproduct of terephthalic acid synthesis, and allow acetic acid recycling. Third, acetic
acid oxidizes during the reaction. At current terephthalate production levels, replacement of
oxidized acetic acid requires approximately 4 billion pounds of makeup acetic acid worldwide
every year. Manufacturing this makeup acetic acid not only requires substantial raw materials and
energy but also creates pollutant emissions. Finally, acetic acid reacts with the bromide catalyst to
produce high levels of methyl bromide emissions. According to EPA's Toxics Release Inventory, a
single terephthalic acid plant releases about 45,000 pounds of methyl bromide annually.
Professor Savage has discovered reaction conditions and a reactor strategy for the catalyzed
partial oxidation of/>-xylene at high concentrations in high-temperature liquid water to synthesize
terephthalic acid in high yields at nearly 100 percent selectivity. As a replacement solvent, water
eliminates the formation and emission of methyl bromide as well as oxidative solvent losses. As a
result, this process eliminates the raw materials, energy, and pollutant emissions associated with
producing 4 billion pounds of make-up acetic acid annually. Because the byproduct and solvent
are both water, the distillation is eliminated, along with its associated costs and energy use.
Professor Savage and his group have developed and analyzed conceptual chemical process
designs for this new reaction medium to show quantitatively that it is competitive in its economics,
energy consumption, and environmental impacts. They have also developed processing strategies
so that these greener reaction conditions can be used at the high concentrations required for
commercial processes. In 2008, University of Michigan filed a provisional patent application for
this technology.
AeroClay®: A Green Aerogel for Industry
Expanded polystyrene (EPS) is made from polystyrene (PS), a petroleum product. It is used
as a packaging material, thermal insulator, and acoustical insulator. PS is foamed into EPS beads
using pentane, a volatile organic compound (VOC), as the blowing agent. The EPS beads are
expanded and molded into blocks, which are then cut into specific shapes as required for various
applications. Of the 2.62 million tons of polystyrene generated in 2008, only 0.8 percent were
recycled and less than 1 percent were incinerated for energy.
AeroClay® is a sustainable, tough, lightweight material that has the potential to replace EPS.
AeroClay® is made by mixing clay and biodegradable polymers such as casein or poly(vinyl
alcohol) with water, pouring the mixture into molds, and then freezing and freeze-drying it. Water
is both the only byproduct and the only processing aid in AeroClay® manufacture, so byproduct
water can be incorporated back into the manufacturing process. AeroClay® can be formed into a
variety of molded shapes to meet many demanding applications, eliminating the need for cutting
or shaping to fit any one application. It is water-soluble and is expected to be biodegradable.
AeroClay® eliminates worker exposure to styrene, a suspected carcinogen, and does not require
any blowing agents. Instead, AeroClay® uses poly(vinyl alcohol) and clay, which are essentially
nontoxic, nonhazardous materials that would not harm workers who are currently exposed to
chemicals during EPS manufacture. AeroClay® would also reduce the amount of waste in landfills.
Because it is biodegradable, AeroClay® does not take up space in landfills or cause pollution
during production or incineration. AeroClay® is also less flammable than EPS, while providing
similar mechanical properties in packaging and insulating applications. During 2010, Aeroclay,
Inc. established a pilot facility in Cleveland, Ohio, to produce and test prototypes and to produce
small batches.
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An Efficient, Biocatalytic Process for the Semisynthesis
of Simvastatin
Statins are important drugs for treating cardiovascular diseases. Lovastatin, a secondary
metabolite produced by the fungus, Aspergillus terreus, was the first FDA-approved statin.
Simvastatin, a semisynthetic derivative of lovastatin, has two methyl groups instead of one at the
C2' position of the side chain. Simvastatin has become the second-highest-selling generic drug in
the world since 2007 when it went off-patent as Merck's Zocor®.
Converting lovastatin into simvastatin by adding a methyl group currently requires protecting
and then deprotecting other functionalities in the lovastatin molecule in a multistep synthesis.
There are two main commercial routes. In the first route, lovastatin is hydrolyzed to the triol,
monacolin J, followed by protection with selective silylation, esterification with dimethyl butyryl
chloride, and deprotection. The second route involves protecting the carboxylic acid and alcohol
functionalities, methylating the C2' carbon with methyl iodide, and deprotecting the product.
These routes are inefficient at less than 70 percent overall yield and are mass-intensive due to
protection and deprotection.
Professor Tang and his group have developed an efficient route that circumvents protection
and deprotection and results in greater atom economy, reduced waste, and overall less hazardous
reaction conditions. First, they cloned LovD, a natural acyltransferase produced by Aspergillus
terreus that is involved in synthesizing 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
creating a new biocatalytic process. They then evolved this enzyme toward commercial utility.
Codexis licensed Professor Tang's technology, engineered the enzyme further, and optimized
the process for pilot-scale simvastatin manufacture. During 2010, Codexis scaled up enzyme
manufacture to the 150 kilogram batch scale and manufactured simvastatin ammonium salt in
400 kilogram batches for sampling with customers. Approvals of regulatory agencies in the United
States and European Union are expected in 2011.
Pre-Pulping Extraction of Hardwood Chips to Recover
Hemicelluloses as a High-Value Renewable Chemical
Feedstock that Reduces Waste and Saves Fossil Fuel
Commercial pulp mills do not generally recover hemicelluloses because traditional hot-water
extraction also extracts lignin, which can stick to and clog the mill piping and digesters. As a result,
hemicelluloses are usually degraded and burned.
A novel pre-pulping extraction technology discovered by researchers at the University of Maine
uses green liquor, an existing wood extract stream at Kraft pulp mills, to recover hemicelluloses
from hardwood chips prior to conventional pulping. The near-neutral green liquor (NNGL) is
rich in oligomeric hemicelluloses that can be a valuable, renewable feedstock for biorefineries.
Acetic acid is a major coproduct.
The NNGL extraction prevents pollution by recovering hemicelluloses that would otherwise be
wasted, improving energy efficiency by reducing fossil fuel used by lime kilns, and using existing
pulp mill facilities to create a new feedstock. Using forest products instead of corn, the current
dominant renewable feedstock, could further reduce greenhouse gases and toxic chemicals.
This new technology does not change the yield or physical properties of the pulp. In a
demonstration of the NNGL extraction process for over 800 hours at full commercial scale,
the Old Town mill in Maine produced several million gallons of extract while maintaining
quality pulp output. University of Maine researchers have successfully demonstrated both the
fermentation of NNGL wood extracts into ethanol and lactic acid and the separation of acetic
Professor Yi Tang,
Department of
Chemical and
Biomolecular
Engineering,
University of
California, Los
Angeles
Professors Adriaan
van Heiningen,
Joseph Genco, Peter
van Walsum, and
Hemant Pendse,
Forest Bioproducts
Research Institute,
University of Maine
13
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Professor Kent J.
Voorhees,
Department of
Chemistry, Colorado
School of Mines and
MicroPhage, Inc.
Professor Robert M.
Waymouth,
Department of
Chemistry, Stanford
University and
Dr. James L. Hedrick,
IBM Almaden
Research Center
acid from the extract. The Old Town mill is currently designing a commercial satellite biorefinery
to convert pre-pulping wood extract into biobutanol and acetic acid. Peer-reviewed analysis
shows that a 1,000 ton-per-day pulp mill could produce ethanol from NNGL wood extracts at
$1.63-$2.07 per gallon and acetic acid at $1.98-$2.75 per gallon. With this technology, the
bleached hardwood Kraft pulp mills in the United States could recover over 1 million tons of
hemicelluloses per year for biofuel and bioplastics.
Bacteriophage-based Test for MRSA/MSSA Infections
Acquired in Hospitals
Staphylococcus aureus causes most staphylococcal infections. The overuse of antibiotics may
have caused the emergence of methicillin-resistant Staphylococcus aureus (MRSA), which is now a
major, worldwide nosocomial pathogen. Over the past 15 years, hospitals have seen double-digit
growth in the number of observed MRSA cases. By 2005, there were nearly 95,000 reported
MRSA infections in the United States, resulting in 18,650 deaths.
Professor Voorhees has developed a greener, more efficient method for detecting S. aureus at the
point of care. His method uses phage (bacteriophage) amplification to identify S. aureus rapidly
and distinguish between MRSA and methicillin-susceptible S. aureus (MSSA) infections without
time-consuming bacterial cultures.
Phages are highly species-specific viruses that infect bacteria. The rapid infection process can
amplify phage numbers up to 105-fold. This reduces incubation times for phage amplification
assays, resulting in complete phage-based assays in 1—5 hours instead of 24—48 hours for
traditional bacterial culture assays. Professor Voorhees and MicroPhage have miniaturized the
process and incorporated modern approaches, such as lateral flow immunochromatography,
to detect the species-specific progeny phage. The test looks and functions much like a typical
immunoassay, but requires neither expensive instruments nor highly trained personnel. This
phage amplification platform is the first and only rapid, direct, in vitro diagnostic tool to identify
bacteria and determine their antibiotic resistance or susceptibility.
The phage-based MRSA/MSSA hospital acquired infection test specifically incorporates green
chemistry into its design, resulting in benefits to humanhealth and the environment relative to existing
methods. The test eliminates culturing, reduces the generation of waste, eliminates a hazardous
synthesis, minimizes the use of auxiliaries and energy, uses renewable feedstocks, and is safer to use.
The U.S. Food and Drug Administration is currently reviewing a 2010 application for this test.
In 2009, MicroPhage received approval and began marketing the test in Europe.
Organic Catalysis: A Broadly Useful Strategy for Green
Polymer Chemistry
Catalysis is a foundation for sustainable chemical processes, but conventional routes
for synthesizing polyester plastics require metal oxide or metal alkoxide catalysts that have
negative environmental impacts. In addition, although plastics are ubiquitous, useful materials,
their lack of biodegradability and indiscriminate disposal have left an adverse, enduring
environmental legacy.
Motivated by their desire to generate new classes of metal-free polymeric materials for
microelectronic applications, the team of Professor Waymouth and Dr. Hedrick has pioneered the
design and application of organic catalysts for polymer chemistry. Together, they have developed
highly active, environmentally benign, metal-free catalytic processes for polyesters that contribute
to meeting a central goal of green chemistry. Several new families of organic catalysts that
14
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they discovered rival or exceed metal-based alternatives for polyester synthesis, both in activity
and selectivity. Their work includes developing a broad class of organic catalysts to synthesize
biodegradable and biocompatible plastics.
These new synthetic strategies provide an environmentally attractive, atom-economical,
low-energy alternative to traditional, metal-catalyzed processes. This technology includes
organocatalytic approaches to ring-opening, as well as anionic, zwitterionic, group transfer, and
condensation polymerization techniques. Their monomer feedstocks are primarily renewable
compounds such as lactides from biomass, but also include some petrochemicals.
The team has designed and implemented organic catalysts to depolymerize such petrochemically
derived polymers as poly(ethylene terephthalate) (PET) quantitatively. This allows a bottle-to-
bottle recycling strategy to reduce the millions of pounds of PET that are disposed of in landfills.
These catalysts also tolerate a wide variety of functional groups, enabling the synthesis of well-
defined biocompatible polymers for biomedical applications. As these catalysts do not remain
bound to the polymer chain, they are effective at low concentrations. These results, coupled with
cytotoxicity measurements in biomedical applications, have highlighted the environmental and
human health benefits of this approach. The team holds eight patents on this work.
15
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AeroClay®: A Green Aerogel for Industry
NOTE: This project is the result of a partnership between Professor David Schiraldi of Case
Western University and Aeroclay, Inc. The project was judged in both the academic and small
business categories. The abstract appears in the Academic section on page 12.
Source Reduction through Software Technology
Source reduction is the core of Chemical Safety's EMS (Environmental Management Systems)
software. The most recent version, EMS 2010, introduced Chemical Safety's greener chemical
alternatives search tool in its material safety data sheet (MSDS) and chemical inventory modules.
EMS software is the only technology that incorporates greener chemical alternatives as a key
feature for inventory search, procurement, and use. EMS software offers the ability to search
for and select greener chemical alternatives in a database of chemical alternatives identified by
EPA as well as leading universities and institutions. Users range from chemists and researchers to
manufacturing and facilities managers. With EMS software, users reduce their acquisition, use,
and release of toxic and hazardous chemicals and materials used for research, manufacturing,
maintenance, repair, and operations; they also maximize their acquisition and use of environmentally
preferable products.
EMS software provides steps essential to efficient chemical procurement, storage, distribution,
reuse, recycling, and disposal. These steps reduce unnecessary chemical purchasing, reduce the
footprints of hazardous chemicals at facilities, and decrease the generation and disposal of chemical
waste. Chemical Safety has incorporated EPA's Design for the Environment (DfE) program into
its EMS software. The DfE program evaluates the human health and environmental effects,
performance, and cost of traditional and alternative technologies, materials, and processes. It
helps reduce the use and disposal of chemicals of concern.
EMS software supports easy tracking of chemical containers and important data from the point
materials are purchased or received through delivery, use, and storage to disposal and ultimate
destruction. When users request a chemical from their company's inventory that is maintained
in EMS 2010, the system prompts them to substitute a safer chemical. Clients as diverse as the
Department of Energy's Stanford Linear Accelerator, Novartis Vaccines and Diagnostics, E&J
Gallo, the L'Oreal Group, Baxter Healthcare, and EPA Region 9 laboratories are currently using
this EMS software.
Suga®Nate: A Safer, Milder, Greener Surfactant
Currently, the two most common anionic surfactants used in shampoo, body wash, and other
personal care products are based on lauryl sulfate and lauryl ether sulfate. A large percentage of
these surfactants are made from ethylene, a petroleum feedstock. Products with these ingredients
are highly irritating to eyes and skin. Products containing ethoxylated lauryl ether sulfate also
contain various levels of 1,4-dioxin, a known carcinogen. Some manufacturers and retailers no
longer make or carry products with these ingredients.
Colonial Chemical developed sulfonated alkyl polyglucosides to replace lauryl alcohol as the
hydrophobic component of surfactants. These unique, patented products represent a breakthrough
in mild surfactant technology. They are produced from renewable resources, using naturally
Aeroclay, inc.
and Professor
David Schiraldi,
Department of
Macromolecular
Science and
Engineering,
Case Western
Reserve University
Chemical Safety
Software
Colonial
Chemical, inc.
17
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Commercial Fluid
Power LLC
derived, biodegradable raw materials. They do not irritate eyes or skin, giving formulators of
personal care products an opportunity to start with totally irritation-free ingredients. They are
also completely free of dioxin.
These products are synthesized using raw materials that are nearly 90 percent renewable and
could reach 100 percent renewable as development progresses. The synthetic pathway is very
atom-economical and the only byproduct is sodium chloride. Water is the only solvent used to
make these products. The relatively mild reaction conditions are closer to ambient than those of
competing technologies, and there is no need for separation or purification.
The toxicity of these products is quite low compared to the toxicity of competing technologies;
surprisingly, these products are even less toxic than their raw starting materials. The products are
also readily biodegradable and are not irritating to humans in tests of both eye and skin irritation.
These products have been used in commercial shampoo in the United States since 2007. In
2010, Colonial Chemical submitted data for approval by the REACH program (Registration,
Evaluation, Authorization, and Restriction of Chemicals) in the European Union.
Elimination of Hexavalent Chromium Used in Hydraulic
and Pneumatic Tubing
Chrome-plated rods and tubes are the backbones of the hydraulic and pneumatic cylinders used
in the fluid power market. These cylinders are used in applications from oil and gas production
to food processing. Chrome plating is used widely because it has an excellent wear surface, great
lubricity, and good corrosion resistance; it is also economical, time-tested, and readily available.
The plating process is problematic, however, because plating produces a mist containing hexavalent
chromium ions (i.e., Cr(VI), Cr6+) that are carcinogenic. Most large chrome-plating facilities
currently meet or exceed EPA, OSHA, and other government standards for air quality, disposal,
and containment of waste. There is a trend toward tighter regulatory controls, however, and more
stringent regulations will increase 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 nonmetallic epsilon iron nitride (s-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 losing quality or strength. These
efforts are reducing the use of hexavalent chromium.
Recent research, development, and testing have overcome earlier challenges and opened new
markets for Nitro-tuff tubes and bars. In conjunction with NitroSteel and Nitrex, Commercial
Fluid Power continues to strive to bring an eco-friendly, cost-effective solution to the fluid
power market.
Desilube Technology
and United Soybean
Board
High-Performance, Soy-Based Metalworking Fluids
Metalworking fluids used in operations requiring high lubricity are typically formulated with
petroleum oil and chlorinated paraffins, which are neither environmentally friendly nor readily
biodegradable. In fact, EPA has placed chlorinated paraffins under regulatory scrutiny because
they exhibit aquatic toxicity and certain chain lengths are considered to be carcinogens. Current
annual sales of chlorinated paraffins for metalworking fluids are approximately 75 million pounds.
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Desilube Technology has developed an environmentally friendly metalworking fluid that
contains the methyl ester of soybean oil plus the organic amine salt of a phosphoric acid and a fatty
acid. This fluid does not contain any chlorinated or sulfurized compounds and is not prepared
with petroleum oil. It has been used successfully in commercial applications that require high
lubricity. Desilube's soybean oil based metalworking fluid outperforms conventional petroleum
oil formulated with 35 percent chlorinated paraffin in two heavy-duty machining operations:
deep drawing and fine blanking. The performance of Desilube's metalworking fluid is due to
synergism between the methyl ester of soybean oil and the amine salt of phosphoric acid with a
fatty acid. This synergism also applies to water-dilutable metalworking fluid designed for metal
removal applications.
Most, if not all, metalworking fluids currently used in these and other heavy-duty applications
contain chlorinated paraffins. Desilube's soy-based metalworking fluid has the potential to
help replace chlorinated paraffins. In addition, the soybean oil base stock also has the potential
to replace petroleum oil, reduce the dependency of the United States on crude oil, and take
advantage of the large domestic supply of soybean oil provided in good part by farmers supporting
the United Soybean Board.
The most recent patents for these soy-based technologies were published in 2010 and assigned
to the United Soybean Board. Commercial sales of the environmentally friendly metalworking
fluid over the past two years have averaged $45,000 per year.
A Safer, Less Toxic, Reliable, and Green Water Treatment
by Smart Release® Technology
Smart Release® Technology is a controlled-release technology designed to prevent scale,
corrosion, and microbial proliferation in water systems through the revolutionary delivery and
application of existing chemical treatments. Initially, the technology focused on controlling
corrosion and scale in cooling towers using tablets coated with a patented polymer that releases
the treatment chemicals over a specified time period. In 2010, Dober expanded its Smart Release®
product line to include biocides in solid granular form by creating a patent-pending canister
membrane that also releases the chemicals over a specified time period, often 30 or 60 days.
Treating cooling towers with Smart Release® technology has many advantages over traditional
liquid water treatments. Unlike traditional treatments, Smart Release® technology does not
require toxic additives. Smart Release® treatments contain 95 percent active ingredients compared
to 10—20 percent active ingredients in liquid treatments. The technology uses no pumps and so
requires no electricity. Reduced packaging and shipping weight lowers its carbon footprint by
74 percent compared to that of conventional liquids. This technology may also help facilities gain
up to eight LEED (Leadership in Energy and Environmental Design) credit points.
Benefits to humans include safe handling because the coating prevents contact with active
ingredients. Because the concentration of active ingredients is so high, 100 pounds of Smart
Release® chemicals equate to 600 pounds of standard liquid chemicals. The simplicity and
reliability of Smart Release® technology means that less service time is required.
Smart Release® technology has been endorsed by two of the leading water treatment companies
in the United States and a leading global supplier of cooling towers, fluid coolers, and evaporative
condensers. During 2010, Dober created an enhanced corrosion and scale-inhibitor tablet that
contains no phosphate. Due to increased regulations limiting phosphate products, Dober expects
this product to have large sales in the future.
Dober Chemical
Corporation
19
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Earth Friendly
Products
FRX Polymers Inc.
Earth Conscious Chemistry: Eliminating 1,4Dioxane in
Cleaning Products
1,4-Dioxane is an unwanted contaminant in many common personal care products sold in the
United States. It occurs as a byproduct of common ethoxylated surfactants (e.g., sodium lauryl
ether sulfate). 1,4-Dioxane is a cyclic ether that is highly miscible in water and migrates rapidly in
soil. EPA has listed the compound as a probable human carcinogen based on the results of animal
studies. 1,4-Dioxane is also listed with a group of pollutants in state and federal guidance for air
pollution control.
Earth Friendly Products has worked diligently to remove 1,4-dioxane from all of its products.
Testing for 1,4-dioxane by gas chromatography/mass spectrometry conducted by the Organic
Consumers Association (OCA) included new results from 20 laundry detergents: 13 conventional,
mainstream brands and 7 brands self-identified as "natural." The conventional brands had
significantly higher levels of 1,4-dioxane. The highest were Tide® with 55 ppm, Ivory Snow® with
31 ppm, and Tide® Free with 29 ppm. OCA has confirmed in their latest report for 2010 that
EGOS® Laundry detergent by Earth Friendly Products was free of 1,4-dioxane.
Since June 2008, Earth Friendly Products has successfully scaled up its formulas to produce
natural products that do not contain any harmful chemicals, including 1,4-dioxane. The company
uses a blend of coconut oil with anionic fatty acid chains that make excellent surfactants due to
their dual hydrophilic and lipophilic properties. There is no sodium chloride salt added or used
in any step of manufacturing or production of the company's laundry products. Each product is
made with sustainable, plant-based ingredients that are studied to ensure minimal environmental
impact before and after production. This ensures that all of the company's products are not
only biodegradable, but also free of phosphate, caustic, formaldehyde, petrochemicals, chlorine,
synthetic perfume, and ammonia.
Polymeric, Non-Halogenated Flame Retardants with
Broad Applicability in Multiple Industries
Traditional, halogenated, small-molecule flame retardant (FR) additives readily migrate
out of their applications, exposing humans to these often toxic chemicals and diminishing the
application's flame retardant function. Electronic device manufacturers have instituted voluntary
bans on plastic formulations with halogen-containing FR additives. Consequently, the plastics
industry is searching for cost-effective, non-migrating, halogen-free alternatives.
FRX Polymers is the first company to develop polymeric forms of phosphorus for use as
non-migrating FR additives that are also cost-effective and halogen-free. FRX makes diphenyl
methylphosphonate (DPMP) into polymers with over 10 percent phosphorus. These unique
polymers have the highest limited oxygen index (LOI) measured for thermoplastic materials,
highlighting their FR functionality. The polymers can be used as standalone, inherently FR
materials; they can also deliver FR performance and often additional beneficial properties to
polycarbonate blends, polyesters, thermoplastic polyurethane (TPU), unsaturated polyethylene
terephthalate (UPET), epoxies, and polyureas. Being polymeric, the FRX materials will hardly
deteriorate the physical properties of these plastics. Replacing bromine with phosphorus in FR
additives should allow greater recycling of plastics after use.
The DPMP monomer synthesis has essentially quantitative yields. The polymer synthesis is a
solvent-free, melt-based process whose only major byproduct, phenol, can be recycled into the
starting monomers. Less than 5 percent waste is expected from FRX polymer and copolymer
production. Because they can be processed by melting, FRX polymers can be used in applications
such as fibers and blow-molded articles that were impossible with other FR additives.
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FRX is scaling up its additives for applications including electronic housings, industrial
carpeting, textiles, electrical connectors and switches, wire and cable, printed circuit boards,
and transparent laminates. The FRX materials have completed Premanufacture Review under
the Toxic Substances Control Act (TSCA) and are proceeding toward global registration. FRX
plans to expand its current pilot plant from 50 to 100 metric tons per year during 2011.
Surachi Fuel Technology
Surachi fuel technology oxygenates petroleum fuels and other alternative hydrocarbon fuels.
The technology modifies the fuel with a reaction in water in the presence of a recyclable,
organic, semisolid catalyst. The reaction adds a hydroxy group and hydrogen atom at the
former alkene bond in the fuel. The catalyst does not stay in the fuel, but is removed after the
chemical reaction for reuse. This technology works for all internal combustion fuels including
diesel, gasoline, jet fuel, Bunker C, and other heavy fuel oils.
Fuel Energy Service Corporation developed the Surachi technology in collaboration with the
inventor. The technology allows internal combustion engines to run cleaner, quieter, and with
more power, but with lower levels of soot, unburned hydrocarbons, and other harmful exhaust
emissions. It expands the actual volume of the fuel and increases the Btu. The process removes
most of the sulfur from fuel: the sulfur precipitates and is deposited on the semisolid catalyst,
from which it can be removed. The Surachi technology does not adversely affect critical fuel
characteristics, such as viscosity, low corrosivity, or other parameters that are common problems
for fuel additives such as ethanol and other oxygenated species. The modified fuels are essentially
identical to the original fuel in storage, holding, and handling capabilities.
The Surachi process has not yet been scaled up to production volume, either as a batch or a
continuous process. In 2009, a patent was issued for this technology.
Polyelectrolytes: Reduce Your Carbon Footprint Using an
Eco-Friendly Technology to Disperse Wax in Water
without Heat
Emulsions containing waxes are common ingredients in wood or tile polishes, personal care
products, coatings, and sealants. The traditional process of making oil—wax—water emulsions
generally requires heating two mixing vessels: one for the aqueous phase and another for the
oil phase. The temperature of each vessel needs to be higher than the melting point of the wax
in the oil phase. Typically, steam, hot water, or cold water pumped through jackets around the
vessels control the temperature. Once formed, emulsions must be cooled very carefully because
the rate of cooling affects the aesthetics of traditional emulsions.
Previous cold process technologies solved the problems of multiple mixing vessels and the
necessity of heating and cooling. Because existing cold process emulsions do not contain wax,
however, they tend to feel more like gels than like conventional emulsions.
JEEN's Jeesperse Cold Process Wax (CPW) revolutionizes the science of making emulsions
with wax. The combination of waxes and polyelectrolytes in Jeesperse products allows
formation of complete emulsions without either heating or cooling. It uses only one mixing
vessel and reduces manufacturing time by 50—75 percent over conventional processes. Sodium
polyacrylate is the first polyelectrolyte used in Jeesperse CPW products, but many other
polyelectrolytes can be used. In the future, natural gums in combination with natural waxes
will lead to natural CPW products. Natural gums that can be used to create CPW products
include sodium polyaspartate, sodium alginate, carrageenan, guar, and xanthan.
Fuel Energy Service
Corporation
JEEN international
Corporation
21
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IVlicroPhage, Sue.
and Professor
Kent J. Voorhees,
Department of
Chemistry, Colorado
School of Mines
Nanotech
Industries, Inc.
Natural
Research, Inc.
Jeesperse CPWs do contain wax and will make emulsions that feel like conventional, heat
process ones. The ability to use waxes in cold process emulsions will expand the use of cold process
manufacturing. During 2010, JEEN applied for U.S. patents. The nominated technology is
available commercially as Jeesperse
Bacteriophage-based Test for MRSA/MSSA Infections
Acquired in Hospitals
NOTE: This project is the result of a partnership between Professor Kent Voorhees of Colorado
School of Mines and Micro Phage, Inc. The project was judged in both the academic and small
business categories. The abstract appears in the Academic section on page 14.
Green Polyurethane™
The manufacture and use of isocyanate-based polyurethanes (PU) require very strict safety
measures. Isocyanate monomers are hazardous and are considered potential human carcinogens.
Acute exposures to isocyanates can cause irritation of skin and mucous membranes, chest
tightness, and difficult breathing. Prolonged exposure can to cause severe asthma and even death.
Isocyanates are also very sensitive to moisture. These problems lead to a highly regulated, costly
environment for PU manufacturing.
Green Polyurethane™ from Nanotech Industries (NTI) is the first modified hybrid PU to
be manufactured without isocyanates. The main raw materials for Green Polyurethane™ are
polyoxypropylene triols and epoxidized vegetable oils. NTI also uses primary aliphatic diamines
prepared by biomimetic synthesis in its production of Green Polyurethane™.
Green Polyurethane™ is a potential replacement for current, isocyanate-based polyurethanes,
especially those polyurethanes in foams and coatings that contain free isocyanates in aerosol form
after polymerization. Green Polyurethane's™ unique formulation combines the best mechanical
properties of polyurethane with the chemical resistance properties of epoxy binders. Green
Polyurethane™ coatings contain no volatile organic compounds (VOCs). They are solventless,
100 percent solids-based, 30—50 percent more resistant to chemical degradation, 10—30 percent
more adhesive with some substrates, and 20 percent more wear-resistant. These coatings can also
be applied on wet surfaces and will cure in cold conditions.
Insulating foam made from Green Polyurethane™ provides energy savings of more than
30 percent, has one of the highest Rvalues per inch of all insulation materials, does not require a
primer, and has greater adhesiveness.
In 2010 EPA added Cycloate A, a key binder ingredient in Green Polyurethane™, to the
Toxic Substances Control Act (TSCA) Inventory following Premanufacture Review. NTI
submitted a Premanufacture Notice under TSCA for its proprietary hydroxyalkyl urethane
modifier (HUM). Also in 2010, Nanotech Industries began commercializing its hybrid
non-isocyanate polyurethane UV-resistant coating technology.
Conversion of Waste Plastics into Fuel
EPA estimates that the United States recycles less than 6 percent of the 30 million tons of
waste plastic it produces each year. In landfills, waste plastics produce methane gas, a greenhouse
gas that is 23-times more harmful than carbon dioxide (CC>2). The worldwide fishing industry
dumps an estimated 150,000 tons of plastic into the ocean each year, which constitutes almost
90 percent of all rubbish floating in the oceans.
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Natural State Research, Inc. (NSR) has developed a patent-pending, award-winning technology
that converts municipal solid waste plastics (PETE-1, HDPE-2, PVC-3, LDPE-4, PP-5, and
PS-6) into liquid fuels. The typical NSR process involves heating small pieces of waste plastic to
280—420 °C to form a liquid slurry. After it cools, the slurry is distilled in the presence of
cracking without catalyst to recover light gas and liquid hydrocarbons. Fractionation of the liquid
hydrocarbons produces fuels similar to gasoline, naphtha, diesel, jet fuel, fuel oil, and home
heating fuel that can be used in the majority of combustion engines.
NSR's technology is a new alternative to fossil fuels: it creates fuel sustainably without depleting
natural resources. The raw material required to make NSR fuel, waste plastic, is abundant; until
now, its disposal has posed significant environmental problems. Unlike other technologies, the
NSR thermal technology does not use any pyrolysis, catalyst, vacuum, or chemicals during its
process, and the overall yield is higher than for other methods.
When developed to commercial scale, the NSR technology can convert one ton of waste plastics
into about 335 gallons of liquid fuel at a cost of about $0.50—$0.75 per gallon. NSR will license
its technology to others, creating locally owned franchises employing up to 50 workers each. NSR
has produced about 200 gallons of fuels to date.
Catalytic Transformation of Waste Carbon Dioxide into
Valuable Materials
Novomer has developed a technology based on an innovative, proprietary catalyst system
that transforms waste carbon dioxide (CC>2) into valuable plastics and resins. The resulting
polypropylene carbonate (PPC) and polyethylene carbonate (PEC) contain up to half CC>2 by
weight and thus, not only sequester CC>2 but also displace one-half the petroleum feedstock
required for competing materials. Novomer technology has the potential to sequester and avoid
approximately! 80 million metric tons of annual CC>2 emissions. Novomer products have three
other advantages relative to competing materials: (1) inexpensive CC>2 enables competitive pricing,
(2) the highly selective catalyst enables unique performance characteristics, and (3) Novomer
products are free of bisphenol A (BPA). This combination of environmental responsibility, high
performance, and low cost make Novomer polymers commercially attractive in a broad range of
applications, including interior can coatings, packaging films, foams, and composite resins.
Novomer technology uses a greener synthetic pathway based on a novel catalyst system
developed at Cornell University. The catalyst is a highly selective, cobalt-based complex that is
over 25-times more active than current, zinc-based catalysts. It enables the creation of polymers
with a precise CC>2-epoxide molecular structure. It does what earlier catalysts could not: it enables
a waste greenhouse gas to replace petroleum-based raw materials in commercially viable polymers.
The process is also solvent-free. Novomer's energy-efficient manufacturing process makes its
reaction conditions greener than those of existing products.
Novomer materials are well-positioned to have a broad, significant impact on the polymer
industries and transform the broader polymer landscape. During 2009—2010, Novomer
successfully produced pilot-scale quantities of products for a wide range of applications. Now it is
partnering with major polymer producers and brand owners to refine, qualify, and commercialize
these products. The company expects to introduce its initial commercial products to the specialty
coatings industry in 2011.
inc.
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NSR
Technologies, inc.
Orono Spectral
Solutions
A Novel Energy-Efficient, Emission-Free Route to Produce
Potassium Hydroxide
Potassium hydroxide (KOH) is a strong alkali with many industrial applications. The current
U.S. consumption of KOH is approximately 1.3 billion pounds annually. During KOH production
alone, the traditional, electrolytic chlor-alkali process makes about 800 million pounds of chlorine
gas (C\2) annually in the United States and an estimated 1.8 billion pounds worldwide. C\2 is a
hazardous air pollutant (HAP); chlorine acts as free-radical catalyst that contributes to destroying
the ozone layer. Although chlor-alkali producers recover and sell C\2, the demand for C\2 is
decreasing as ozone-depleting, chlorinated chemicals are phased out.
NSR has developed and commercialized an electrodialysis process that manufactures
45—50 percent KOH and 7 percent hydrochloric acid (HC1). The process hinges on NSR's lonSel™
technology, which uses layers of ion- and bipolar-selective membranes to separate and rearrange
potassium and chlorine ions from the potassium chloride (KC1) feedstock. NSR's technology
is the first environmentally friendly, cost-effective alternative to the chlor-alkali process in
decades. It yields high-purity products free of mercury and oxidizing species such as chlorate and
hypochlorite. NSR's process operates under safer conditions and does not produce C\2-
NSR's manufacturing process uses about 40 percent less energy per unit of product and has
a compact design that allows smaller plants to produce equivalent amounts of acid and alkali
profitably. Lower capital investments and smaller plants make manufacturing safer by enabling
NSR to build plants close to end users, reducing shipping costs and hazards.
Both the chlor-alkali process and NSR's process can also produce sodium hydroxide (NaOH).
As of July 2008, more than 500 companies worldwide used chor-alkali processes and recovered
140 billion pounds of C\2 as a byproduct of NaOH production. Global implementation of NSR's
technology could eliminate billions of pounds of C\2 production. NSR has been operating a
commercial plant and selling products to customers since 2009.
Device and Method for Analyzing Oil and Grease in
Wastewater without Solvent
The 1974 Clean Water Act lists oil and grease together as one of five conventional pollutants. 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 annually in the United States.
Following the Montreal Protocol in 1989, EPA replaced a Freon extraction method for oil and
grease testing with an w-hexane extraction method (EPA 1664; EPA 1664a). This created several
problems: (1) w-hexane is a hazardous, flammable liquid; (2) w-hexane is a known neurotoxin; and
(3) testing generates millions of liters per year of w-hexane waste that require disposal. Thus, the
current methodology is inconsistent with the intent of the Clean Air Act and Clean Water Act,
both of which identify w-hexane as a hazardous pollutant.
Orono Spectral Solutions (OSS) developed a solid-phase, infrared-amenable extractor
technology that both eliminates solvents from oil and grease analysis and provides more
economical, accurate analyses. OSS's extractor unit is small, robust, and disposable (or partially
recyclable), and it contains no toxic substances. The extractor unit includes a Teflon™-based
polymeric membrane to capture and concentrate oil and grease from water, a metal-membrane
support, and a polypropylene housing designed for pressurized water samples. The 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.
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This patent-pending technology has successfully completed ASTM (American Society for
Testing and Materials International) multi-laboratory validation and received ASTM method
number D7575. EPA is currently considering replacing method 1664 with this one. This
replacement would save one million liters of hexane annually and produce estimated benefits to the
U.S. economy of $50—$60 million. OSS is actively commercializing this technology worldwide.
Enzymatic Catalysis for Biodiesel Production
Biodiesel is comprised of monoalkyl esters of long-chain fatty acids derived by
transesterification or acid esterification of vegetable oils or animal fats. High-quality feedstocks
for biodiesel are primarily triglycerides (e.g., vegetable oils), which are easy to process by alkaline
transesterification. Low-quality feedstocks (e.g., yellow and brown greases) have higher levels of
free fatty acids (FFAs). They are difficult to process and thus largely underused. The decomposition
of fats and oils also creates FFAs. Alkaline transesterification catalysts (e.g., potassium and sodium
hydroxide) react with FFAs to produce soaps that complicate downstream processing and reduce
the yield of biodiesel. Using a strong acid to catalyze esterification reduces soap formation and
improves yields but generates an acidic methanol waste.
Enzymes can easily convert both triglycerides and free fatty acids into fuel-grade esters.
In collaboration with Novozymes A/S, Piedmont developed three techniques for enzymatic
biodiesel production: (1) lipase transesterification to replace alkaline transesterification for
high-quality feedstocks; (2) bulk lipase esterification to replace acid esterification for feedstocks
with high levels of FFAs; and (3) an acid-value reduction process for low amounts of FFAs.
Piedmont's enzymatic process accommodates low-quality and high-quality feedstocks without
loss of biodiesel yield. Enzymatic catalysis operates near room temperature and does not form
soaps, require vacuum or pressure, or produce unintended side-reactions. The process eliminates
water use, requires little excess methanol feedstock, and significantly improves glycerin quality to
low-ash, technical grade with over 97 percent purity. The soap-free, enzymatic biodiesel process
improves separation between biodiesel and glycerin phases because the emulsifier (soap) is not
present. The new process also uses less energy than the current process or other second-generation
processes (e.g., metal oxides). Piedmont's biodiesel meets ASTM (American Society for Testing
and Materials International) standards and is economically viable for existing biodiesel processors.
During 2011, Piedmont Biofuels and Novozymes A/S will commercialize this process.
Zero- VOC, BioBased HiOmega * Linseed Oil Epoxies,
Adhesives, and Alkyd Resins as Replacements for
Epichlorohydrin-Epoxy Resins and Other
VOC-Containing Coatings, Paints, Adhesives,
and Epoxies
Of the 2 billion pounds of epichlorohydrin manufactured worldwide each year, 76 percent is
used in epoxy resins. Epichlorohydrin is both a probable human carcinogen and a deadly poison
at high levels.
Polar Industries is commercializing products from HiOmega® linseed, a flax plant developed
by conventional breeding that is an annual, renewable crop grown in the United States and
Canada. HiOmega® linseed oil is highly suitable for epoxidation because it has 20—40 percent
more a-linolenic acid than does conventional linseed oil. Environmentally friendly epoxidation
methods at moderate temperatures yield epoxidized HiOmega® linseed oil with high oxirane
values (11.0—13.0) that exceed the highest values of epoxidized conventional linseed oil (9.0—10.0).
Epoxy and alkyd resins made from HiOmega® linseed oil contain no volatile organic compounds
Piedmont Biofuels
Industrial, LLC
Polar Industries, Inc.
25
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SIGNa
Chemistry, Inc.
Solvair LLC
(VOCs). They are biodegradable and require no special handling or disposal. The entire lifecycle
of HiOmega® linseed oil epoxy resins, from crop growth and harvest to oil extraction, epoxidation,
industrial use, and final disposal, is nonhazardous and follows environmentally sound practices.
In initial testing, the performance of HiOmega® epoxy resins and alkyd resins met or exceeded
the performance of other linseed oil epoxy resins in bonding strength, moisture resistance, and
resistance to fatigue. HiOmega® linseed oil epoxy resins are suitable replacements for epoxy
resins made from epichlorohydrin. HiOmega® epoxy resins can be used in conventional two-part
epoxy systems (i.e., resin and amine hardener) or one-part, UV-photoinitiated systems. Biobased,
environmentally friendly, nontoxic epoxy resins and adhesives synthesized with epoxidized
HiOmega® linseed oil could potentially reduce epichlorohydrin production by approximately
1.5 billion pounds per year.
Polar Industries has successfully commercialized nontoxic epoxy coatings, epoxy adhesives, and
alkyd resins made from HiOmega® components. The California Department ofTransportation is
currently using Green Graffiti Coat, an antigraffiti clear coating based on HiOmega® epoxidized
linseed oil, to protect road signs.
Sodium Silicide: On-Demand Hydrogen Generation for
Back-Up Power and Portable Fuel Cells
Sodium silicide (NaSi) is a stabilized alkali metal silicide powder developed by SiGNa that
reacts with water to generate hydrogen. In a fuel cell, NaSi produces pure hydrogen gas in real
time, as needed, and at pressures less than those found in a soda can. NaSi eliminates the most
significant challenges that have prevented low-temperature proton exchange membrane (PEM)
fuel cells from becoming commercial products: storing high-pressure hydrogen and building
costly infrastructure for hydrogen refilling.
By generating hydrogen on demand, NaSi will enable high-performance, portable, commercially
viable fuel cell systems. This clean, sustainable material is inexpensive, easily transportable, and
safe for indoor and outdoor use. Fuel cells powered by NaSi produce only hydrogen and water
vapor; they create no greenhouse gases, toxic byproducts, or harmful emissions. Recyclable fuel
canisters can easily deliver NaSi to any PEM fuel cell. Once the NaSi in a canister is spent, the
nontoxic residue, sodium silicate, can be recycled as an industrial feedstock for many products.
SiGNa's NaSi technology offers significant environmental benefits throughout its lifecycle.
SiGNa manufactures NaSi using renewable, sustainable materials that are independent of oil
prices. The manufacturing process requires little energy and has a very small carbon footprint.
Replacing lithium batteries and internal combustion (1C) engines with NaSi fuel cells will
significantly reduce both greenhouse gases released into the atmosphere and toxic materials
entering the waste stream.
In the marketplace, SiGNa's new technology is proving that hydrogen fuel cells are not only
commercially viable, but are even more cost-effective than batteries or low-power 1C engines
(under 3 kilowatts). For example, an electric bicycle powered by a NaSi fuel system can go
3—4-times farther than a bicycle powered by traditional lithium-powered batteries. SiGNa's
hydrogen-generation approach can enable cost-effective back-up and portable fuel cells for the
medical, military, transportation, disaster relief, and consumer electronics industries.
Solvair Cleaning System
Eighty percent of the 30,000 commercial drycleaning facilities in the United States use
perchloroethylene. Unfortunately, perchloroethylene is a hazardous air pollutant under the Clean
Air Act (CAA) and waste streams generated by perchloroethylene drycleaning are hazardous under
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the Resource Conservation and Recovery Act (RCRA). In California, health and environmental
concerns are leading to the phase-out of perchloroethylene drycleaning; other states are proposing
similar actions. Alternative solvents are available for use in conventional drycleaning systems,
but all rely on evaporative hot-air-convection drying to remove the solvent from the textiles after
cleaning. As a result, these alternatives have similar problems with environmental release, operator
exposure, and hazardous waste streams.
Solvair initially developed its technology to replace traditional drycleaning with a safer,
more environmentally friendly, more-effective cleaning technology. The Solvair system replaces
evaporative hot-air-convection drying with a counter-current process including multiple liquid
carbon dioxide (CC>2) rinses that remove the solvent from textiles after cleaning. It allows the
practical use of safer, more effective drycleaning solvents including dipropylene glycol w-butyl
ether (DPnB). DPnB is miscible in liquid CC>2 and is readily rinsed from textiles. It is commonly
used in household cleaners, has extremely low volatility, and is biodegradable. Compared to
conventional perchloroethylene systems, the Solvair system with DPnB eliminates hazardous
waste streams, reduces the amount of waste by approximately 60 percent (including eliminating
contact waste water), and maximizes the recovery and reuse of fluids in the system. The
CC>2 in the Solvair process is a byproduct of other industrial processes and not a new source of
CC>2 release.
Because the Solvair cleaning technology can use a wide range of solvents, it has potential
applications in many industrial and commercial cleaning applications beyond drycleaning. In
December 2010, commercial facilities using the Solvair cleaning technology processed over
3 million pounds of garments.
Development and Commercial Application of SAMMS®:
A Novel Compound that Adsorbs and Removes Mercury
and Other Toxic Heavy Metals
Mercury contamination poses a serious threat to the environment and human health,
but many common adsorbents are themselves problematic. Self-assembled monolayers on
mesoporous supports (SAMMS®) successfully adsorb and remove toxic metals (e.g., mercury,
cadmium, lead) and replace less-effective adsorbents (e.g., activated carbon, ion exchange resins).
SAMMS® is a mesoporous ceramic substrate with a single layer of functional sorbent molecules
bonded to the surface. The functional molecules have high affinity for specific ions. SAMMS®
has superior adsorption capacity for targeted heavy metals, is cost-effective, and significantly
reduces the volume of hazardous waste. The original SAMMS® synthesis required toluene
and other flammable organic solvents. The resulting waste stream contained water, methanol,
toluene, and traces of mercaptan. It required disposal as hazardous waste.
Steward Advanced Materials dramatically improved the SAMMS® syn thesis withnonflammable,
nontoxic supercritical carbon dioxide (SC CC>2). With this patented, commercially viable, green
chemical process, SAMMS® manufacturing is faster and more efficient; it also yields a higher-
quality product. The only byproducts are carbon dioxide (CC>2) and the alcohol resulting from
the hydrolysis of the alkoxysilane. The CC>2 and alcohol are readily separated, allowing the
CC>2 to be captured and recycled. The pure alcohol can be recycled as a feedstock, rather than
becoming waste as in the original synthesis. The SAMMS® materials emerge from the reactor
clean, dry, and ready for use. The benefits of the green manufacturing process for SAMMS®
materials coupled with the superior adsorption characteristics of SAMMS® materials currently
deployed in the chemical industry result in substantially reduced releases of toxic metals to
the environment.
Steward Advanced
Materials
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Terrabon, inc.
limber Treatment
Technologies, LLC
Commercial uses of thiol-SAMMS® include removal of: (1) multiple toxic heavy metals from
contaminated mining impoundments, (2) heavy metal catalysts from pharmaceutical reaction
mixtures, and (3) mercury from contaminated ground water and industrial process water with a
discharge limit of 1.3 parts per trillion.
Conversion of Municipal Solid Wastes to Drop-In Fuels
and Chemicals
Terrabon's MixAlco® process converts any anaerobically biodegradable material (e.g., proteins,
cellulose, hemicellulose, fats, and pectin) into a variety of chemicals (e.g., ketones and secondary
alcohols) and fuels (e.g., 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 conventional chemistry to convert the mixed
acids and salts into desired chemicals or fuels.
Feedstocks for the MixAlco® process include a number of wastes that typically end up in
landfills: municipal solid waste (MSW), sewage sludge, forest product residues (e.g., wood chips
and wood molasses), and non-edible energy crops (e.g., sweet sorghum). The process can also
use liquid wastes such as leachate from landfills and raw sewage. Terrabon's process will increase
landfill life and replace nonrenewable petroleum. A life cycle analysis (LCA) using the GREET
model (Greenhouse gases, Regulated Emissions, and Energy use in Transportation) shows that
the MixAlco® process will reduce greenhouse gas emissions by over 174 percent compared to
conventional gasoline. With high-water effluents as the water source along with MSW, this
process does not compete with local water resources.
Terrabon currently operates a demonstration plant in Bryan, Texas to confirm the commercial
scalability of this process. This plant can potentially ferment the equivalent of about 5 dry tons
of biomass per day to produce 100,000 gallons of biogasoline per year. The on-site conversion
to biogasoline includes dewatering the fermentation salt product by evaporation and drying,
thermally converting it into ketones, and catalytically converting the ketones into alcohols and
hydrocarbons. Terrabon has successfully produced good-quality gasoline at this plant. In 2011,
the company will begin constructing a 220 dry ton-per-day biorefinery at the Waste Management
landfill in Alvin, Texas. This plant will convert MSW into 5 million gallons of gasoline per year.
TimberSIL®
Toxic, waterborne chemical infusion processes are typically used to pressure-treat lumber and
industrial wood products. The new TimberSIL® glass wood chemistry uses environmentally
friendly, nontoxic, sustainable chemicals and processes to protect wood.
To produce TimberSIL® glass wood, Timber Treatment Technologies converts sodium silicate,
a common industrial chemical, into amorphous glass in situ with a suitable substrate such
as wood or another natural fiber. Amorphous glass forms as millions of microscopic ribbons
become intimately attached to the wood fiber to make TimberSIL® lumber. Production of the
proprietary TimberSIL® formulation uses no petroleum products. Most of the wood used comes
from renewable, sustainable, southern yellow pine trees. In addition, the processing of recycled
rice hulls to make sodium silicate, a primary component of the glass wood chemistry, requires
no energy, has no greenhouse gas emissions, and produces two times more energy than the
combustion of coal.
TimberSIL® glass wood can take any shape that can be milled by existing wood mills. It is
stronger, more stable, and more resistant to fire, rot, and decay than pressure-treated wood. It
can readily be used wherever long-lasting wood materials are the proper design and economic
choice. The strength ofTimberSIL® lumber means that less lumber is needed to achieve the same
building integrity.
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TimberSIL® technology can eliminate many toxic materials that are widely used in wood
treatments. For example, every mile of TimberSIL® rail ties that replaces creosote rail ties
eliminates 108,000 pounds of crude oil. Over its lifetime, one mile of TimberSIL® railroad ties
displaces over 9,300,000 pounds of carbon dioxide (CC>2). With no toxic mode of action and
increased strength, TimberSIL® glass wood is an environmentally superior choice for residential,
commercial, and industrial applications. Since 2005, installations ofTimberSIL® glass wood have
totaled approximately 2.7 million board-feet in the United States.
Saf-T-Vanish®: A Zero-VOC, Green Replacement for
Petroleum Solvent Vanish Oils
Tens of thousands of U.S. manufacturers who make metal parts by stamping or drawing use
evaporative lubricants known as vanish oils. These oils typically contain over 90 percent highly
evaporative, combustible, or flammable petroleum hydrocarbon solvents plus small amounts of
lubricants. The human health and environmental impact of the solvents is of major significance. In
the United States alone, vanish oils release over 120 million pounds of volatile organic compounds
(VOCs) each year and expose tens of thousands of metalworking plant employees to noxious
and potentially hazardous fumes. On January 1, 2010, South Coast Air Quality Management
District (SCAQMD) Rule 1144 went into effect in Southern California, banning the use of high-
VOC vanish oils from the local marketplace. Until recently, however, U.S. manufacturing had no
proven, successful, environmentally friendly alternative to high-VOC vanish oils.
In July 2009, Tower Oil & Technology introduced Saf-T-Vanish®, the first truly green
technology to prove itself as a successful replacement for high-VOC vanish oils. It is derived from
renewable feedstock and is both fully recyclable and biodegradable. Saf-T-Vanish® is VOC-free
and nonhazardous to manufacturing workers and the environment. Saf-T-Vanish® contains no
mineral oils or hazardous air pollutant (HAP) ingredients; it is totally nonflammable and emits
no noxious fumes.
To date, Saf-T-Vanish® has enabled the total elimination of vanish oil VOCs in hundreds
of manufacturing applications throughout the United States. It has vastly improved plant and
worker safety while making huge contributions to corporate environmental goals. In addition,
Saf-T-Vanish® is the only commercially available, truly green technology that enables Southern
California manufacturers to comply totally with SCAQMD Rule 1144. As the manufacturing
industry continues to replace conventional vanish oils, Saf-T-Vanish® could eliminate over
120 million pounds of VOCs per year from the environment.
Tower Oil &
Technology Co.
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GLDA: The Greener Chelate; Sustainable, Safe,
and Strong
Because chelating agents solubilize metal ions, they have many applications, including cleaners,
water treatment, and agriculture. Many traditional chelates such as ethylenediamine tetraacetic
acid (EDTA) and nitrilotriacetic acid (NTA) are based on aminocarboxylic acids; others such
as sodium tripolyphosphate (STPP) are based on phosphorous in the form of phosphates or
phosphonates. However, these chelates and several similar structures are not environmentally
friendly and safe. The degradation of phosphorous-containing materials in the environment can
lead to the eutrophication of waterways, and common phosphorous-free alternatives have their
own problems with biodegradation and safety.
To address concerns surrounding traditional chelates, AkzoNobel has developed a strong,
nontoxic, nonpolluting, readily biodegradable chelate, GLDA (tetrasodium L-glutamic acid, N,N-
diacetic acid). The principle raw material for GLDA is the monosodium salt of glutamic acid
(MSG), which is both a natural amino acid and a fermentation product of readily available corn or
beet sugars. MSG is renewable, making GLDA the only chelating agent manufactured from such
a renewable feedstock. The GLDA manufacturing process is also waste-free.
As a chelate for calcium, GLDA is more than twice as effective as Baypure® (i.e., sodium
iminodisuccinate, IDS), a previous Presidential Green Chemistry Challenge-winning technology.
GLDA is also stronger than many other common, readily biodegradable counterparts. GLDA
offers an impressive human and ecological safety profile that is comparable to IDS, but IDS
and other green chelates are made almost exclusively from petroleum feedstocks. GLDA has a
smaller environmental impact than EDTA, NTA, and STPP because it uses a renewable feedstock,
biodegrades rapidly, and lacks phosphorous.
These attributes make GLDA ideal for applications including household and industrial
cleaners and detergents, gas sweetening, metal and oil industries, personal care products, polymer
production, printing ink, textile processing, and pulp and paper processing. Since late 2009,
AkzoNobel has expanded its Lima, Ohio, plant and commercialized GLDA as Dissolvine® GL.
Concrete-Friendly™ Powdered Active Carbon (C-PAC™)
for Safely Removing Mercury from Air
Coal-fired power plants emit 45 tons of gaseous mercury to air and produce 65.5 million
tons of fly ash annually in the United States. This fly ash has a composition similar to volcanic
ash and is an excellent replacement for cement in concrete. Currently, it is used in about half
of the concrete produced in the United States. Of the 65.5 million tons of fly ash generated in
the United States in 2008, more than 11.5 million tons were used in concrete, and 16.0 million
tons were used in structure fills, soil modification, and other applications. According to EPA's
2008 report to Congress, federal concrete projects alone used 5.3 million tons of fly ash in 2004 and
2005, saving about 25 billion megajoules of energy as well as 2.1 billion liters of water and reducing
carbon dioxide (CO2) emissions by about 3.8 million tons.
Activated Carbon Injection (ACI) technology injects mercury sorbents into flue gas in power
plants and captures the mercury-laden sorbents in fly ash. Although this technology reduces
mercury emissions, conventional mercury sorbents render fly ash unsuitable for concrete and thus,
generate huge amounts of landfill waste. Disposal of 11.5 million tons of sorbent-contaminated fly
ash would require more than 322 million cubic feet of landfill space and cost about $196 million.
AkzoNobel
Functional
Chemicals, LLC
Albemarle
Corporation
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Argonne National
Laboratory
Ashland
Performance
Materials
Albemarle, with partial funding from the National Science Foundation (NSF), designed,
synthesized, developed, and commercialized the novel mercury sorbent, Concrete-Friendly™
Powdered Active Carbon (C-PAC™). C-PAC™ is activated carbon with tailored pore structures
and surface properties. Albemarle manufactures C-PAC™ from renewable carbon sources using
a greener synthesis that includes gas-phase catalytic bromination. C-PAC™ removes large amounts
of mercury from air, preserves the quality of fly ash for concrete use, and eliminates the need
for large amounts of landfill space. Several power plants across the United States currently
use C-PAC™.
Upcycling Plastic Bags into More Valuable Products
Carbon spheres (CSs) and carbon nanotubes (CNTs) find uses in water purification, as
additives for lubrication, in energy storage devices such as common lithium-ion batteries, and in
other applications. At Argonne National Laboratory, Dr. Vilas Pol has researched, demonstrated,
implemented, and patented an environmentally friendly process to remediate or upcycle waste
plastic bags (WPB) into CSs and CNTs. Argonne's original, solvent-free, solid-state-controlled,
pyrolytic process upcycles WPB of single or mixed types by heating them to 700 °C to produce
pure CSs and CNTs. Systematic characterization of the atomic structure, composition, and
morphology of the CSs and CNTs with advanced structural, spectroscopic, and imaging
techniques has elucidated the mechanism of CS and CNT formation.
With no catalysis, the process yields smooth, micrometer-sized carbon spheres that are
conductive and paramagnetic. They can be used in toners and printers, as additives for
lubricants, and in the tire industry. An industrial collaborator, Superior Graphite, has heat-
treated CSs at higher temperature; this improves their performance significantly as anodes for
lithium-ion batteries.
With a cobalt acetate catalyst, the process yields CNTs that have been successfully tested at
Argonne as anodes for energy storage devices and additives for lubrication. This process is the
cheapest, most straightforward way to fabricate CNTs in mass quantities. It also avoids the air and
water pollution caused by landfilling or incinerating WPB.
The process uses less energy to manufacture these materials than do existing methods; it also
replaces a petrochemical feedstock with WPB. It reduces air and water pollution, ultimately
reducing the hazards to public health and the environment by diverting plastic from landfills or
toxic incineration.
Argonne designed a prototype reactor with an 80 cubic centimeter capacity and optimized
the reaction conditions. Argonne is working with G2 NanoTechnologies, LLC to scale up and
develop high-volume reactors to commercialize this technology.
Envirez™ Technology: Incorporating Renewable and
Recycled Feedstocks into Unsaturated Polyester Resins
Envirez™ resins are a versatile family of unsaturated polyester resins synthesized with both
renewable and recycled raw materials. The renewable raw materials are obtained from corn,
soybeans, and other biomass. The biobased building blocks include soybean oil, ethanol,
1,3-propanediol, and proprietary monomers derived from biomass. Other building blocks are
monomers and polymers recycled from postconsumer poly(ethylene terephthalate) (PET) and
airplane deicer. Envirez™ resins meet the same performance and processing requirements of
100 percent petroleum-based unsaturated polyester resin products. They are used to fabricate
an ever-expanding portfolio of thermoset composite products for the building, construction,
infrastructure, transportation, and marine industries.
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The first Envirez™ resin was targeted at compression-molded parts for agricultural equipment.
With its growing interest in sustainable materials, Ashland recently strengthened and expanded
the Envirez™ family of resins in several significant ways: First, Envirez™ resins now exist for a
wide variety of composite fabrication methods. Ashland has developed formulations for infusion,
pultrusion, casting, and gelcoats, expanding the reach of Envirez™ into a much wider assortment
of products and markets including green buildings and wind energy. Second, Envirez™ resins
now contain a higher percentage and wider assortment of renewable raw materials. Ashland
accomplished this by intensive, on-going research and development to identify and use new
biobased building blocks. Third, Ashland synthesized and developed the first Envirez™ resins
that incorporate recycled raw materials and combine both recycled and renewable raw materials.
Fourth, Envirez™ resins have become an enabling technology for composite fabricators interested
in using sustainable components. This product line has experienced double-digit growth in the
past several years.
A significant, recent milestone that illustrates the growing, widespread acceptance of Envirez™
was the launch ofCompositeBuild.com at the 2010 GreenBuild Expo. This showcase and its
accompanying website featured a portfolio of interior and exterior building products based on
Envirez™ resin technology commercialized since 2008.
Green Sens^M Concrete
Concrete is the most widely used, versatile building material in the world. It uses raw materials
such as Portland cement and water (cement paste) as glue to hold fine and coarse aggregates
together, creating a solid material for constructing buildings, houses, and roadways. Portland
cement manufacturing requires so much energy that it produces a reported 5 percent of the
world's carbon dioxide (CC>2) emissions according to the Portland Cement Association. Although
the CO2-equivalent emissions, or carbon footprint, of products like concrete are often used as
the only measure of environmental impacts, this information alone may produce misleading
conclusions because the mining of aggregates also depletes natural resources. Considering several
environmental impacts and rigorously measuring the comprehensive environmental impact
and lifecycle costs of products allow more informed and science-based decisions on the most
sustainable solutions.
BASF has developed a series of Glenium® chemical admixtures for use in concrete for multiple
applications. The Glenium® chemical admixtures are engineered and carefully formulated
products containing an aqueous solution of dispersants based on polycarboxylate ether chemistry.
The aqueous Glenium® admixtures are nontoxic, nonhazardous, and nonflammable. These
admixtures, when combined with alternative raw materials in concrete mixes, make up Green
SenseSM Concrete. Glenium® admixtures allow BASF to replace CO2-intensive Portland cement
with traditional waste materials such as fly ash, slag, and cement kiln dust.
BASF also developed its Eco-Efficiency Analysis (EEA) tool for concrete. EEA is a third-party-
validated, award-winning holistic and strategic environmental lifecycle assessment methodology
that focuses on multiple environmental parameters, not only CC>2 emissions. With this tool,
BASF can analyze each concrete mix to achieve new levels of economy and sustainability.
In 2009, BASF introduced Glenium® admixtures, Green SenseSM concrete, and its EEA
tool. In 2010, BASF Construction Chemicals worked with hundreds of concrete producers in
the United States to optimize their concrete mixes with Glenium® admixtures and Green
SenseSM concrete.
BASF Corporation
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Champion
Technologies, inc.
Cooper Power
Systems
Lysine-Based Phosphonate Scale Inhibitor with Improved
Biodegradation and Maintained Performance
Offshore oil production is increasing the demand for scale inhibitors as reservoirs age and
production more frequently requires secondary recovery techniques, such as saltwater injection.
Offshore oil wells are susceptible to accumulating scale when ions in injected seawater mix with
ions in oil-bearing formations. The precipitation of calcium carbonate, barium sulfate, and other
scales from the water that comes up with the oil can reduce production rates, increase maintenance
costs, or block pipelines completely. The annual worldwide market for oilfield scale inhibitors is
$200 million.
Organic phosphonates inhibit scale formation as low-dose additives (sometimes at levels below
parts-per-million, far below the dosage required for comparable carboxylate chelants). They
have high efficacy, low toxicity, and a low tendency to bioaccumulate. They typically exhibit low
rates of biodegradation, however, and legislation in the United States and North Sea countries
has driven research into biodegradable scale inhibitors. Although polymeric scale inhibitors can
substitute for phosphonates because they have greater biodegradation rates and a low tendency to
bioaccumulate, they cost more and require higher dosages to be effective.
Champion Technologies has developed new phosphonate scale inhibitors that biodegrade more
readily and offer a competitive price yet preserve the inherently high performance, low toxicity,
and low bioaccumulation of phosphonates. Champion replaced diethylenetriamine (DETA) and
other synthetic polyamine starting materials for traditional phosphonates with lysine, a naturally
occurring amino acid that is also a renewable polyamine. Champion optimized the extent of
phosphonomethylation to maximize both performance and biodegradation. Lysine phosphonate
exhibits the desired scale inhibition and is inherently biodegradable, demonstrating 20—60-percent
biodegradation in 28 days by OECD 306 (the seawater biodegradation test of the Organisation
for Economic Co-operation and Development). By comparison, traditional phosphonates are
nonbiodegradable, with less than 20 percent biodegradation in 28 days by OECD 306. In 2009,
Champion submitted a patent application for this technology.
Green Chemistry for High-Voltage Equipment:
The Research, Development, and Application of
Soy-Based Dielectric Coolant
Polychlorinated biphenyls (PCBs) formed the basis for traditional dielectric coolant fluids, but
they presented environmental problems and liabilities for the electric power industry. Cooper
Power Systems has developed a replacement insulating fluid, Envirotemp™ FR3™ fluid, to
provide the electric power industry with a sustainable dielectric coolant that has the best possible
environmental and health profile.
Envirotemp™ FR3™ fluid contains approximately 97 percent soy oil blended with nontoxic
cold-flow modifiers and food-grade oxidation stabilizers. The inherent properties of soy oil
result in improved fire safety, hydrolytic interaction, biodegradability, high gas absorption,
and compatibility with common transformer materials. Envirotemp™ FR3™ fluid was
99.9 percent biodegradable in EPA's Office of Chemical Safety and Pollution Prevention (OCSPP)
Biodegradation Test. In EPA's Acute Aquatic Toxicity Test, Envirotemp™ FR3™ fluid was nontoxic
with zero mortality. Envirotemp™ FR3™ fluid has the most favorable Biobased for Environmental
and Economic Sustainability (BEES) score among dielectric coolants, including an outstanding
score for being essentially carbon-neutral from planting the soy seeds through filling a transformer.
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The degradation of the insulating paper in power transformers is a major factor in their
operating life expectancy. Cooper researchers discovered that their fluid decreases the aging rate of
transformer insulating paper compared to other common fluids; the soy oil hydrolyzes with water
to dehydrate both the fluid and the paper. Transformers filled with soy-based fluid have a lower
lifecycle cost than do transformers filled with mineral oil.
Envirotemp™ FR3™ fluid has the highest flash and fire points of all common dielectric fluids.
Its fire point is twice that of mineral oil, which leads to increased safety. Currently, transformers
filled with soy-based fluid have operated over one million unit-years in the field without any
reported fire incidents.
Cooper holds nine U.S. patents for this technology. Envirotemp™ FR3™ fluid is listed in the
Federal BioPreferred™ product catalog.
iSUSTAIN® Green Chemistry Index Tool for
Sustainable Development
Cytec Industries Inc., in collaboration with Dr. John Warner, has developed the iSUSTAIN®
Green Chemistry Index scoring tool. This is the first such tool to be based on the 12 Principles of
Green Chemistry. The tool includes a metric for each of the twelve principles, which range from
atom economy to reduced energy use and process hazard. The tool makes assessments using a novel
algorithm and a database of safety, health, environmental impact, and regulatory status scores for
the raw materials used to prepare the products being assessed. Information for assessments comes
from several sources including EPA's Sustainable Futures™ modeling, qualitative structure-activity
analysis (QSAR), literature searches, and testing.
iSUSTAIN® measures the sustainability of Cytec's products and processes, allowing the
company to develop both initial sustainability baselines and improvements. The index allows
Cytec's technical community to identify those factors within their control that can affect the
overall sustainability of their processes. Cytec has been using the tool internally since 2009 to
score both new product ideas and existing commercial products. Cytec has also incorporated the
tool as part of its Stage-Gate New Product Introduction (NPI) system.
Starting in March 2010, Cytec, in partnership with Sopheon Corporation and Beyond Benign
Foundation, made the iSUSTAIN® Green Chemistry Index available to the public without
charge. An enhanced version is available for a fee, but Cytec provides it free to academic users.
iSUSTAIN® will foster learning and change the mindset of university scientists so future researchers
will have the principles of sustainability ingrained in their thinking. By the end of 2010, over
771 users including industry, government, and academia had logged onto the tool. Users signed
up from 114 unique domains and 30 different domain types, creating over 1,000 scenarios using
442 substances from the materials database of 5,494 substances.
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., aluminosilicate
crystals), which reduces the efficiency of the heat exchangers. Periodically, the equipment must be
taken offline and cleaned with sulfuric acid.
Cytec developed its MAX HT® Bayer sodalite scale inhibitor products for the Bayer process.
No other scale inhibitors are on the market for this application. The active polymeric ingredient
contains silane functional groups that inhibit crystal growth by incorporation into crystals or
adsorption onto their surfaces. Dosages range from 20 to 40 ppm. Assessments of these polymers
under EPA's Sustainable Futures™ program indicated an overall low concern for human health and
the aquatic environment.
Cytec
industries inc.
Cytec
industries inc.
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Cyfec industries inc.
Cyfec industries inc.
Eliminating sodalite scale from heater surfaces has many benefits. Heat recovery from the
steam produced in various unit operations becomes more efficient. Increased evaporation makes
the countercurrent washing circuit more efficient and reduces caustic losses. Using less steam
reduces emissions from burning carbon-based fuels. Finally, reducing the sulfuric acid used to
clean heaters reduces both worker exposure and waste.
There are about 70 operating Bayer process plants worldwide with annual capacities of
0.2 million—6 million tons of alumina; most plants are in the 1.5 million—3 million ton range.
Thirteen Bayer process plants worldwide have adopted MAX HT® technology, and 13 more
plants are testing it. Each plant using MAX HT® saves $2 million—$20 million annually. Fewer
cleaning cycles and less acid per cycle result in a realized annual hazardous waste reduction of
50 million—150 million pounds. The annual realized reduction of 50 percent caustic is
50,000 tons—125,000 tons. The realized annual energy savings are 6 trillion—31 trillion Btu, which
equals about 0.7 billion—5 billion pounds of carbon dioxide (CC>2) that are not released into
the atmosphere.
Saturated Polyester—Phenolic Resin Systems for Bisphenol A-
Free Interior Can Coatings for Food Packaging
Bisphenol A (BPA) is a key raw material for the binders used in interior coatings of food cans,
but recent animal studies have found that BPA exhibits potential endocrine-disrupting effects.
Because these coatings are a significant source of consumer exposure to BPA, the food industry
is demanding coatings without BPA. Although U.S. regulatory agencies have not made final
regulatory decisions, the elimination of BPA from interior can coating systems has become a
matter of public and scientific interest.
Cytec has developed a new generation of BPA-free, saturated polyester resins for the main
binder. Together with phenolic resins, the polyester resins can be used in interior can coatings for
the metal packaging goods industry. Coating systems based on these resins exhibit performance
comparable 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 daltons. All monomers used in its
synthesis comply with food contact laws. It does not contain any significant levels of free solvent
if properly cured, and it complies fully with 21 CFR §175.300. DUROFTAL PE 6607/60BGMP
does not have the estrogenic properties of BPA. 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 interior can coatings so the system can be completely free of BPA and have performance
comparable to existing systems. Commercial sales began in 2008. In 2010, Cytec began its first
full-scale production of the phenolic part of the system. Currently, Cytec is negotiating the U.S.
production of the polyester part.
Waterborne, Ambient-Cure, Stain-Blocking Primer
When red cedar and other tannin-rich woods are painted, their tannins can bleed into topcoat
paints, producing undesirable discolorations. Solventborne, universal-stain-blocking primers
reduce tannin bleed and discoloration. Typical solventborne primers are based on alkyd resins and
contain volatile organic compounds (VOCs) at 350—450 grams per liter. During painting, these
solvents are released directly into the air. Eco-friendly systems, such as waterborne systems, are
needed to reduce VOCs, but existing commercially available waterborne primers, many of which
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are based on anionic alkyd resins, are generally less effective in blocking tannin bleed than are their
solventborne counterparts.
Cytec Industries has developed a family of cationic, waterborne, epoxy ester resins. The new
cationic polymer emulsions are synthesized by reactions of epoxy resins, fatty acids, and amines.
The polymers are neutralized with organic acids such as acetic or lactic acid and then dispersed in
water. To achieve the best film-forming properties, the emulsion is reacted with additional epoxy
resin to increase its molecular weight. These low-VOC esters show excellent tannin-blocking
performance. Their manufacturing uses a solvent-free process in which exothermic reactions heat
the reaction mixture to processing temperature. They also provide better drying performance
because they do not require oxidative cross-linking reactions, but only solvent evaporation for
complete drying. The primers cure at ambient or even low temperatures.
Cytec's new waterborne primers require very little cosolvent. Conventional stain-
blocking primers can contain up to 40 percent solvent, whereas the new products need only
1—2 percent cosolvent. The VOC content of Cytec's cationic, waterborne, stain-blocking primers is
20—45 grams per liter.
In 2010, Cytec produced its first technical-scale batch of primer and made its first commercial
sales to U.S. paint manufacturers. These small, initial sales reduced VOC emissions by
approximately 20 tons. Potential VOC reductions from low-VOC waterborne primers of equal
performance are 35,000—49,000 tons annually.
ReNew Air Scrubber Technology
Rendering facilities process the inedible parts of food stock into value-added materials
such as tallow, high-protein components for animal feed, and materials for the cosmetics and
pharmaceutical industries. The rendering process uses high-temperature cookers to convert
livestock waste into these finished products, but it also generates significant levels of malodorous
volatile organic compounds (VOCs). Rendering plants trap VOCs with several devices including
air scrubbers. Conventional air scrubbers rely on oxidizers, such as sodium hypochlorite, chlorine
dioxide, chlorine gas, and ozone, to convert insoluble VOCs in exhaust air into water-soluble
organic salts. Sodium chlorite, sodium bromide, sodium hydroxide, and mineral acids are often
used during scrubber operation or cleaning.
ReNew Air Scrubber technology is a pollution control program that reduces emissions of
unwanted VOCs from rendering plants. The program includes novel chemistry, a dosing system
indexed to the intensity of the incoming VOC-containing gases, several air-handling system
modifications, and air scrubber performance monitoring. ReNew Air Scrubber technology
uses enzymes, surfactants, and 50 percent citric acid (a relatively mild organic acid) to replace
conventional harsh chemicals. This technology removes odorous VOCs with efficiency that is
quantifiably equal to or better than the VOC-removal efficiency of conventional technology.
The ReNew Air Scrubber technology reduces total operating costs, uses chemicals that are
safer for workers and the environment, requires less water and energy to operate, and delivers air
quality results equal or superior to conventional systems. It does not produce any EPA-regulated
pollutants in the effluent water.
Since 2007, when Diversey started tests at customer sites, several dozen customer sites have fully
installed the ReNew Air Scrubber technology. Since its initial commercialization, this technology
has saved over 54.5 million gallons of water at U.S. rendering facilities and prevented the use of
over 5 million pounds of oxidizers and mineral acids.
Diversey inc.
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The Dow Chemical
Company
Ecolab inc.
INFUSE™ Olefin Block Copolymers
INFUSE™ Olefin Block Copolymers (OBCs) are produced with a patent-pending shuttling
process that represents an innovation in catalyst technology and delivers breakthrough performance
through new combinations of properties. These block copolymers have alternating blocks of
"hard" (highly rigid) and "soft" (highly elastomeric) segments as the result of reversible chain
transfers between two different catalysts. Dow's catalytic shuttling technology generates a variable,
yet controllable, distribution of block lengths that can generate tailor-made olefins for specific
uses. OBCs have highly differentiated material properties that break the traditional relationship
between flexibility and heat resistance. They also provide significantly improved compression set
and elastic recovery properties compared to other polyolefin plastomers and elastomers. OBCs
possess the ease of formulation and processing that are typical of polyolefms.
The unique block architecture of OBCs enables Dow's customers to expand into a wide range
of innovative market applications currently served by high-performance thermoplastic elastomers,
thereby adding value to fabricators and end-users alike. The sustainable chemistry benefits of OBCs
include (1) atom efficiency due to improved selectivity; (2) reduced toxicity and risk compared
to other polymers; (3) minimized auxiliary substances because the complex chain-shuttling, dual-
catalyst system is highly efficient; (4) reduced energy requirements for both polymer synthesis and
fabrication; and (5) better recycling and end-of-life management because OBCs are compatible
with disparate plastic waste streams and can even enhance the quality of waste streams. OBCs
are suitable for a very large number of applications; their economic benefits are great, thereby
enhancing market selection.
Dow created INFUSE™ OBCs using its INSITE™ Technology. From 2008 to 2010, Dow
OBCs replaced a number of existing polymers including styrene—ethylene—butylene—styrene
(SEES), thermoplastic vulcanizates (TPV), and flexible poly(vinyl chlorine) (f-PVC) for
85 customers worldwide.
DryExx Conveyor Lubricant Program
In commercial food and beverage container filling operations, conveying systems typically
move at very high speeds. Copious amounts of dilute, aqueous lubricant solutions are applied to
the conveyors or containers with spraying or pumping equipment. Traditionally, these solutions
lubricate the conveyor chain, run off the conveyor, and eventually enter the facility's effluent
stream. Concentrated lubricant solutions often consist of fatty acid or fatty amine surfactants.
Traditional lubricant solutions and their associated technology have several disadvantages.
First, dilute aqueous lubricants typically require large amounts of water on the conveyor line.
The area near the conveyor line becomes very wet and the excess water must then be disposed
of or recycled. Second, some aqueous lubricants can promote microbial growth. Third, diluting
the concentrated lubricant before use can produce variable concentrations of dilute solution and
thus, variable performance. Finally, variations in water quality can alter the performance of the
dilute lubrication solution. For example, alkaline water can lead to environmental stress cracks in
poly(ethylene terephthalate) (PET) bottles.
The DryExx Conveyor Lubricant Program lubricates conveyor chains without added
water. The DryExx Program consists of the DryExx chemical formulation and a dispensing
concept. The DryExx formulation contains a mixture of water-miscible silicone material
and a water-miscible lubricant. It contains no hazardous ingredients in quantities
requiring reporting. The product is targeted for food and beverage bottlers who package
products in PET containers using conveyors with plastic or polyacetyl chains. Currently,
Ecolab estimates this program is saving U.S. bottling facilities 240 million gallons of water
annually and is preventing an additional 1 million gallons of conventional lubricant concentrate
from entering the effluent stream.
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Low-Temperature Cleaning In Place
Most industrial processes for cleaning in place (CIP) combine chemistry, temperature, time,
and mechanical energy. Traditional CIP systems require high-strength chlorinated caustic soda
and temperatures of 150 °F. In an average fluid milk plant, these CIP processes account for
approximately half of the plant's total fossil fuel use and carbon dioxide (CC>2) emissions.
Ecolab has developed the Advantis LT two-product program for CIP in the dairy and
food industries. The first product is an alkaline detergent including water conditioners and a
transition metal catalyst (MnSC>4 or Fe2(SC>4)3). The second product is a detergent containing
hydrogen peroxide (H2O2). Injecting the two products sequentially into the CIP balance or
supply tank during circulation generates microbubbles of oxygen on soiled structures, enabling
fluid in the system to flush away the loosened soil. The Advantis LT program results in
successful cleaning at lower temperatures: steam heat exchangers bring the temperature up to
HOT instead of 150 T, saving 50 percent in energy. Atypical cheese plant could save steam equal
to 5,000 decatherms of natural gas annually; the 350 large dairy plants in North America could
save a total of 2.0 million decatherms.
Lower-temperature cleaning cycles reduce the length of heat-up steps by as much as
10—15 minutes per object being cleaned. In many plants, this can translate to increased output.
Reduced cleaning temperatures also extend equipment life by avoiding temperature stress on
stainless steel structures and elastomeric gaskets and seals. Finally, Ecolab's technology reduces
caustic soda consumption by 35 percent without using any chlorine bleach, resulting in
less wastewater.
Calculations for the International Dairy Foods Association estimate that the Advantis LT
program can reduce the overall carbon footprint of a fluid milk plant by up to 10 percent. Following
further refinements, Ecolab plans to commercialize this technology during the latter half of 2011.
Chlorantraniliprole: Greener Chemistry for
Sustainable Agriculture
DuPont redesigned its discovery process for new active ingredients by integrating chemistry
and biology with lexicological, environmental, and site-of-action studies to optimize safety and
product performance simultaneously. This approach focused on those candidates combining high
levels of crop protection with the greatest safety. The resulting product, chlorantraniliprole, has
excellent safety and environmental profiles yet is one of the most potent, efficacious chemical
insecticides ever discovered.
Chlorantraniliprole selectively interferes with muscle contraction in insects by activating a site in
ryanodine receptor channels that is highly divergent between insects and mammals. On key safety
measures, it may be the safest of all lepidopteran insecticides, including those derived from natural
sources. Its unique mode of action selectively targets insects, making it inherently safer to people
and other nontarget organisms. Chlorantraniliprole is classified by EPA as a reduced risk pesticide.
Chlorantraniliprole is usually one to two orders of magnitude more potent against target pests than
commercial standards such as pyrethroids, carbamates, and organophosphates. Its resulting lower
use rates translate into less pesticide going into the environment and a corresponding reduction
in the exposure of workers and the public. Chlorantraniliprole's proven safety to bees and other
beneficial arthropods allows its use in Integrated Pest Management (IPM) programs. In addition,
its mode of action provides an important new tool for managing insecticide resistance.
DuPont manufactures chlorantraniliprole in a convergent commercial process that minimizes
organic solvents, recovers and recycles the solvents it does use, minimizes waste, eliminates
regulated waste products, and establishes inherently safer reaction conditions. Chlorantraniliprole
is rapidly displacing less desirable products from many key markets. It is sold under multiple trade
Ecolab Inc.
E.I. du Pont de
Nemours and
Company
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E. S. du Pont de
Nemours and
Company
E. S. du Pont de
Nemours and
Company
names including Coragen®, Altacor®, and Acelepryn®. In the United States during 2010, over
900,000 acres of vegetables were treated with Coragen® and over 600,000 acres of tree fruit, nuts,
and vines were treated with Altacor®.
Development of a Commercially Viable, Integrated
Cellulosic Ethanol Technology
DuPont and Genencor have developed and scaled up an improved biochemical technology
for producing ethanol from lignocellulosic biomass. This process integrates three components.
First, dilute ammonia pretreatment prepares the biomass for hydrolysis with minimal formation
of compounds that inhibit subsequent fermentation. This pretreatment runs at up to 70 percent
biomass with less than 10 percent ammonia by weight. Second, genetically engineered cellulase
and hemicellulase enzymes from Hypocrea jecorina (a filamentous fungus) produce high yields
of fermentable sugars at high liters. Third, optimized metabolic pathways of a recombinant
ethanologen (Zymomonas mobilis) produce ethanol efficiently by metabolizing both 6-carbon and
5-carbon sugars from the sugars produced by pretreatment and enzymatic hydrolysis. Integrating
and optimizing these three components enables a very efficient process and a green footprint
with lower cost and less capital investment than other known cellulosic ethanol processes. At the
200 liter semiworks scale, this technology achieves consistent ethanol yields of over 80 gallons per
U.S. ton of biomass and ethanol liters of over 80 grams per liter.
Removing the yield, titer, and cost barriers to commercializing cellulosic ethanol is a
significant step toward large-scale production of cleaner, more sustainable liquid transportation
fuels. Comprehensive well-to-wheel lifecycle assessments (WTW LCA) show that this combined
process could potentially reduce greenhouse gas (GHG) emissions by over 100 percent compared
to gasoline. The combined process could potentially have significantly lower GHG emissions
than current grain-based ethanol processes. If suitable feedstocks cost $50 per ton, the ethanol
from this process could cost $2 per gallon.
In 2010, a flexible-feedstock, 250,000 gallon-per-year facility began operating in Vonore,
Tennessee, to scale up this technology and develop basic data for commercial-scale facilities. The
first commercial plant, a facility to convert corn stover feedstock to over 25 million gallons per
year of ethanol, is expected to start up in 2013 in the U.S. Midwest.
Pioneering Industrial Biotechnology to Meet Global
Needs for a Cost-effective, Drop-in, Renewable Fuel
and Chemical
As an advanced biofuel, isobutanol can offer significant advantages over fossil fuels and
ethanol. Isobutanol has a high octane number, good distillation qualities, low vapor pressure,
high compliance value in fuels, materials compatibility, low toxicity, and the ability to reach
targeted production economics.
DuPont has developed an economical, green-chemistry-based process that uses
microorganisms to manufacture isobutanol from renewable biomass. DuPont's strategy for low-
cost commercialization includes retrofitting existing ethanol plants to produce biobutanol. One
key is using current ethanol-industry feedstocks (i.e., corn grain, wheat grain, and sugar cane),
low-cost lignocellulosic biomass, and macroalgae. A second key is developing a yeast-based
isobutanologen as a drop-in biocatalyst for the retrofitted ethanol plants.
Initially, DuPont focused on developing an efficient biocatalyst that functions on saccharified
feedstocks. DuPont engineered yeast strains with a novel pathway of several engineered enzymes
that convert pyruvate to isobutanol in the yeast cytosol. DuPont selected key enzymes based on
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their isobutanol specificity and cofactor requirements, then maintained flux through to isobutanol
by eliminating byproduct reactions that could compete with their chosen pathway. To establish a
redox-balanced pathway and achieve the desired yield, DuPont changed the nucleotide cofactor
preference of the ketol-acid reductoisomerase (KARI) enzyme from NADPH to NADH. Finally,
they integrated novel process technologies to reduce the aqueous concentration of isobutanol
in fermentations, thereby avoiding enzyme inhibition by its product and eliminating energy-
intensive purification. This second-generation biocatalyst has achieved the milestones of yield,
rate, and titer that demonstrate cost-effective production of isobutanol.
DuPont's accomplishment is a significant step towards commercializing a green process
to produce isobutanol. This biobutanol technology reduces greenhouse gases (GHG) by
40—70 percent compared to gasoline or traditional acetone—butanol—ethanol (ABE)
fermentations. During 2010, DuPont began operating a large-scale demonstration plant for
biobutanol in the United Kingdom in a joint venture with Butamax Advanced BioFuels, LLC.
Continuous Processing Enables a Convergent Route to a
New Drug Candidate: LY26248Q3*H3PQ4
The commercial production of LY2624803*H3PC>4, an investigational new drug candidate
currently in phase II clinical trials, illustrates the importance and impact of designing green
processes. Lilly acquired this drug with its purchase of Hypnion, Inc. The original synthesis
enabled early development, but was not amenable to large-scale manufacture. Lilly identified
several major environmental and safety issues with the original chemistry. Among them
were: (1) dimethylformamide/sodium hydride (DMF/NaH) in step 1, (2) methylene in
various steps, (3) a molten step with observed self-heating, (4) an aldehyde purification
that would be unsafe at increased scale, (5) phosphoryl chloride (POC^) in large excess,
(6) chromatographic purification.
After brief explorations, Lilly discovered a convergent variant of the original route. Flow
processing proved critical to this new route's success. First, an extremely efficient carbonylation
replaced an inefficient oxidation catalyzed by TEMPO (tetramethyl pentahydropyridine
oxide). Subsequently, hydrogen replaced sodium triacetoxyborohydride (STAB) in a reductive
amination. Although both operations require high pressure (1,000 psi) that is unsafe
in traditional batch tanks, both proved amenable to flow processing, resulting in safe,
efficient syntheses.
Lilly uses process mass intensity (PMI) in its process development. PMI is the total mass
of raw materials (including water) put into a process for every kilogram of drug produced. The
original route had a PMI of over 1,000 before chromatography. Lilly's new route has a net PMI
of 59, representing a 94 percent reduction (96 percent reduction including chromatography).
This PMI is extraordinary given the complexity of the drug and its nine-step synthesis. Lilly
implemented its new route for LY2624803*H3PO4 on a pilot-plant scale in Indianapolis, Indiana,
during 2009 and on a commercial scale in Kinsale, Ireland, during 2010. Lilly's application
of green chemistry, as well as its development and use of flow chemistry, led to an efficient,
convergent synthetic route and a significantly improved manufacturing process.
Eli Lilly and
Company
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Eli Lilly and
Company
FMC Corporation
Grignard Reactions Go Greener with
Continuous Processing
Since the start of the 20th century, the Grignard reaction has been applied to the synthesis of
numerous intermediates for food additives, industrial chemicals, and pharmaceuticals. Despite
these successes, the acute hazards of the Grignard reaction make it one of the more challenging
reactions to bring to commercial scale. These hazards include: (1) strongly exothermic activation
and reaction steps; (2) heterogeneous reactions with potential problems suspending and mixing
the reaction mixture; and (3) extreme operational hazards posed by ethereal solvents, such as
diethyl ether.
Eli Lilly and Company developed inherently safer Grignard chemistry using a novel,
continuous stirred tank reactor (CSTR) that allows continuous formation of Grignard reagents
with continuous coupling and quenching. This strategy minimizes hazards by operating at a
small reaction volume, performing metal activation only once during each campaign, and using
2-methyltetrahydrofuran (2-MeTHF) as a superior Grignard reagent and reaction solvent that
may be derived from renewable resources. Grignard reactions using 2-MeTHF also result in
products with chemo- and stereoselectivity superior to Grignard products using other ethereal
solvents. Relative to batch processes, the continuous approach allows rapid, steady-state control
and reductions of 43 percent in metal use, 10 percent in Grignard reagent stoichiometry, and
30 percent in process mass intensity (PMI). The continuous approach reduces reaction impurities
substantially. In addition, small-scale operation at end-of-reaction dilution allows all-ambient
processing conditions, something impossible with batch processing.
Lilly is using its CSTR Grignard approach to produce two key materials including the
penultimate intermediate of LY2216684'HC1, a norepinephrine reuptake inhibitor currently
under clinical investigation for treatment of depression and ADHD. Lilly uses a similar
approach to synthesize a key intermediate for an investigational new drug candidate under
clinical evaluation to treat benign prostatic hyperplasia. Lilly anticipates commercial production
on a 22 liter scale that will replace the 2,000 liter reactors used in batch processes.
VigorOx® Biocide: Advancing Environmentally
Responsible Energy Production
Recent advances in horizontal drilling and hydraulic fracturing have unlocked significant
reserves of natural gas in the United States, providing opportunities to increase the nation's
energy independence. Because microbes present in well treatment fluids can fowl wells, the oil
and gas industries must use biocides. Some of these biocides could contaminate ground water
and drinking water wells, however, so the industry has been seeking biocides with minimal
environmental impact. Glutaraldehyde, the most commonly used biocide in the oilfield
industry, is an effective biocide but is also toxic to aquatic organisms and requires high rates of
application. Historically, oxidizing biocides have not been practical because they may interact
negatively with other chemicals in well treatment fluids.
FMC Corporation has met this challenge with VigorOx® biocide. FMC's research team
took peracetic acid (PAA), a safe chemical that was already established in the healthcare and
food processing industries, and reformulated it for energy-production applications. VigorOx®
biocide is a mixture of high-purity hydrogen peroxide and acetic acid treated with a proprietary
purification process and a small amount of chemical stabilizer.
PAA is an oxidizing biocide that rapidly destroys aerobic and sulfate reducing bacteria (SRB)
while decomposing into environmentally benign oxygen, water, and acetic acid, thus minimizing
risk to the environment and human health. VigorOx® peracetic acid formulations contain lower
levels of hydrogen peroxide than standard PAA blends, so they do not inhibit the polyacrylamide
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friction reducers commonly used in "slick water" fracturing. Field trials confirm that PAA does
not persist in the environment or pose chronic toxicity risks. Moreover, the oxidizing power of
peracetic acid can be used to clarify produced water, allowing greater water reuse in hydraulic
fracturing operations. The low rates of use can also provide an economic advantage.
In 2010, FMC's patent-pending formulation received EPA pesticide registration
#65402-3 for oil and gas applications.
Ecomate®: Environmentally Benign Blowing Agent for
Polyurethane Foams
Traditionally, chlorofluorocarbons (CFCs) were the preferred blowing agents for polyurethane
foams. Foams blown with CFCs had good insulating and structural properties for use in
refrigerators, building construction, and spray foam. CFCs were removed from polyurethane foam
in the 1990s, however, due to their potential to destroy the ozone layer. Hydrochlorofluorocarbons
(HCFCs) have a lower Ozone Depletion Potential (ODP) and are currently replacing CFCs, but
were scheduled for phase out by 2010 in the United States.
Ecomate® (methyl formate) is a zero-ODP, zero Global Warming Potential (GWP) blowing
agent designed to replace CFCs, HCFCs, and hydrofluorocarbons (HFCs). Ecomate® is also
VOC-exempt, meaning it does not contribute to smog. With little or no modification of existing
manufacturing processes, ecomate® foaming systems provide foam with insulating and structural
characteristics equivalent to those of conventional polyurethane foams.
Foam Supplies, Inc. developed ecomate® as a green replacement for both HCFCs and the
high-GWP hydrofluorocarbons (HFCs), which have GWPs of 725 to 1,810. Each pound of
ecomate® replaces about two pounds of alternative blowing agents. Using ecomate® as a blowing
agent in polyurethane foams has eliminated almost one million metric tons per year (mt-CC^e)
of high-GWP compounds such as HFC-134a and HFC-245fa. Using one million pounds of
ecomate® would eliminate the equivalent of 1.4 billion—3.4 billion pounds of CC>2 emissions or
0.6 million—1.5 million mt-CC^e.
Ecomate® blowing agent costs substantially less than HFCs, and there are usually no
significant capital expenses associated with implementing the ecomate® technology. Ecomate®
foaming systems allow manufacturers to help the environment without increasing their costs.
Ecomate® has been demonstrated in pour-in-place, boardstock, and spray insulation systems
as well as in boat flotation foam. Ecomate® currently has a variety of applications in several
countries; its availability has allowed EPA to accelerate the phase out of HCFCs in the
United States.
Gentle Power Bleach™: A Revolutionary Enzymatic
Textile Bleaching System
Currently, the textile industry faces major challenges in managing its use of natural resources.
Traditional textile processing has a substantial impact on natural resources and requires potentially
hazardous materials. Textile wet processing (e.g., bleaching) is the most environmentally
hazardous stage in the textile supply chain. Regulatory and consumer pressure support reducing
the environmental impacts of textile production; the future of the textile industry depends on
reduced impacts.
Foam Supplies, inc.
Genencor
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General Motors
Huntsman Textile Effects and Genencor, a division of Danisco A/S, collaborated to introduce
Gentle Power Bleach™ (GPB), a first-to-market enzymatic textile pretreatment bleaching system.
GPB uses Genencor's PrimaGreen™ Eco White liquid enzyme formulation containing a bacterial
arylesterase. This unique, proprietary enzyme catalyzes the perhydrolysis of propylene glycol
diacetate (PGDA) to propylene glycol and peracetic acid at neutral pH over a wide range of
temperatures. Genencor engineered the enzyme to favor the perhydrolysis reaction to peracetic
acid over the hydrolysis reaction to propylene glycol. The generation of peracetic acid in situ sets
the GPB system apart from other enzyme systems and traditional chemical bleaching systems.
Using Genencor's enzyme formulation, Huntsman developed the GPB technology. Introduced
in March 2009, GPB perfectly prepares cotton and elastane blends for dying. GPB enables low-
temperature, neutral pH bleaching of fabrics and replaces harmful chemicals such as caustic soda.
Gentler processing yields softer, bulkier, higher-quality fabrics than traditional bleaching and also
reduces cotton loss during processing by 50 percent. An environmental lifecycle assessment (LCA)
shows that GPB has a marked advantage over traditional textile bleaching for cotton fabrics.
Lower treatment and rinsing temperatures and fewer rinse baths can result in water and energy
savings of up to 40 percent for GPB. The LCA results demonstrate at least a 20 percent benefit
in most categories, including climate change, human health, ecosystem quality, and water use,
relative to a traditional bleaching system.
Applying Green Chemistry Principles to Enable
Zero-Waste Manufacturing
General Motors (GM) has created an environmentally sustainable process that eliminates
GM's use of landfills for waste disposal. GM's process technology addresses environmental
footprint reductions, potential long-term landfill impacts, and natural resource depletion. This
process includes establishing goals; entering and analyzing data from all operations monthly;
adhering strictly to a zero-landfill best practice; monitoring, maintaining, and reporting progress;
and collaborating internally and externally. First, the process focuses on source reduction then
works to retain all wastes (manufacturing byproducts) in use as long as possible. These priorities
correspond to EPA's pollution prevention hierarchy.
On average, GM now recycles or reuses more than 97 percent of its waste materials and converts
the remaining less than 3 percent to energy, replacing fossil fuels at waste-to-energy facilities.
Within the United States, 13 facilities are landfill-free: they recycle, reuse, or convert to energy all
wastes from their normal operations. During 2010, these facilities diverted over 385,000 tons of
waste from landfills and avoided emissions equivalent to 2.1 million metric tons of carbon dioxide
(CC>2e). Currently, GM's process is part of 76 global automotive manufacturing operations that
reuse, recycle, or convert to energy all the waste they generate. During 2010, GM recycled or reused
2.5 million tons of byproduct materials worldwide.
Because environmental cross-industry collaboration and community stewardship are important,
GM directs its engineers to mentor other companies, industries, and communities. For example,
during the 2010 Gulf of Mexico oil spill, GM assembled an engineering team to recycle oil-
soaked, absorbent polypropylene booms recovered from the Alabama and Louisiana coasts. To
retain the chemical value of these booms, GM processed them into parts for the Chevrolet Volt.
To date, this technology has prevented over 100 miles of oil booms and the oil retained in them
from entering American landfills. It has also prevented 70 metric tons of CC^e from entering
the atmosphere.
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Simplified Total Kjeldahl Nitrogen Method for
Wastewater: A Green Alternative to Traditional
Kjeldahl Methodology
The Total Kjeldahl Nitrogen (TKN) test is commonly performed at municipal and industrial
wastewater treatment facilities to measure the concentrations of ammonia and organic nitrogen
compounds. The TKN method is, however, one of the most challenging, dangerous, labor-intensive
tests performed in wastewater treatment plants. This method requires digesting samples at high
temperatures for several hours with strong sulfuric acid to convert the nitrogen to ammonium
sulfate. Concentrated sodium hydroxide is then added to make the solution alkaline, and the
liberated ammonia is distilled into a receiving solution where it is measured by back titration with
sulfuric acid. The analysis requires equipment that is expensive, fragile, and space-consuming.
More recent TKN methods use metal catalysts such as mercury to speed the digestion and
improve recoveries (EPA 351.2 Rev. 2.0, 1993). Ion-selective electrodes, the spectrophotometric
phenate method, or the nesslerization method (which requires significant amounts of mercury)
are often used to measure the ammonia. The TKN method also suffers from poorly understood
interferences. Nitrate, the primary interference, can oxidize ammonia to form nitrous oxide
(N2O), causing negative interference. When sufficient organic matter is present, nitrate can be
reduced to ammonia, causing positive interference. To date, traditional methodologies have not
eliminated these interferences.
Hach Company has developed a rapid test that eliminates many of the weaknesses of traditional
TKN tests. Their Simplified TKN (s-TKN) method uses two simple measurements to calculate
the TKN value as the difference between the concentration of total nitrogen and that of nitrate
plus nitrite. The method does not require mercury. Sample and reagent volumes are less than
10 milliliters per test. Based on the estimate that nearly 5 million TKN tests are performed annually,
use of the s-TKN method could eliminate over 45 tons of mercury per year. In December 2009,
Hach commercialized its s-TKN™ method and prepackaged chemistry.
HFO-1234yf Refrigerant for Automotive Air
Conditioning with Low Global Warming Potential
Driven by the European Union (EU) F-Gas Directive to phase out the automotive refrigerant
HFC-134a, Honeywell and DuPont have jointly developed HFO-1234yf (i.e., CF3CF=CH2),
a refrigerant with low global warming potential (GWP). This is the first hydrofluoro-olefin
refrigerant developed for mobile air conditioning (MAC) systems. HFO-1234yf has a
100-year GWP of 4 versus that of HFC-134a at 1,430. A GWP of 4 easily meets the EU F-Gas
mandate that automotive refrigerants achieve GWP values under 150. HFO-1234yf also has
no ozone depletion potential. Due to its low GWP and high energy efficiency, it has excellent
lifecycle climate performance (LCCP). Based on LCCP calculations using the EPA-supported
GREEN-MAC-LCCP® Model, the potential global savings will be 5.2 million-5.9 million metric
tons per year of CC>2 (carbon dioxide) equivalents (CO2e) in 2017 when HFO-1234yf is fully
implemented.
DuPont and Honeywell completed extensive testing of the toxicity, materials compatibility,
stability, and air conditioning performance of HFO-1234yf. Tests also demonstrated its low
potential for ignition. DuPont and Honeywell worked closely with automobile manufacturers
and component suppliers to support refrigerant qualification programs of their customers.
Results were very favorable, demonstrating that HFO-1234yf substitution requires only minor
modifications to air conditioning systems designed for HFC-134a. Honeywell and DuPont have
also registered or submitted the chemical under EU's Registration, Evaluation, Authorization
and restrictions of Chemicals (REACH), EPA's Significant New Alternatives Policy (SNAP), and
Toxic Substances Control Act (TSCA).
Hach Company
Honeywell
International, Inc.
and DuPont
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IBM Corporation
Stop-Coat, inc.
Honeywell and DuPont provided information for Society of Automotive Engineers
(SAE) Cooperative Research sponsored by global automobile manufacturers to evaluate
HFO-1234yf and other candidates. The program included performance testing, material
compatibility testing, and assessments of environmental impact and risk. The SAE program found
that HFO-1234yf is a safe, environmentally beneficial replacement that could be implemented
globally. Global adoption of HFO-1234yf in all new vehicles would eliminate about 60 million
pounds of HFC-134a.
Elimination of Perfluoroalkyl Sulfonates in IBM
Semiconductor Manufacturing Processes and Development
ofPFAS-Free Photo acid Generators
In 2002, EPA restricted new applications of perfluorooctane sulfonate (PFOS) compounds
because scientific evidence showed that PFOS persisted and bioaccumulated in the environment.
Because semiconductor manufacturers demonstrated limited release and exposure for PFOS,
however, EPA allowed PFOS compounds "as a component of a photoresist substance, including
a photoacid generator or surfactant, or as a component of anti-reflective coating, used in a
photolithography process to produce semiconductors or similar components of electronic or
other miniaturized devices."
Due to increasing concern over the environmental impacts of these compounds, however,
IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA). In 2006, IBM
issued a corporate directive to eliminate all PFOS and PFOA from its manufacturing processes
by 2010. IBM worked with chemical suppliers to identify and qualify a non-PFOS replacement
for the PFOS surfactant in buffered oxide etch (BOE) chemicals. In 2008, after a multiyear
investigation and extensive qualifications, IBM completed replacing the PFOS surfactant in all
BOE chemicals with perfluorobutane sulfonate (PFBS), which has overall lower environmental
concerns according to EPA.
IBM targeted replacement of specific photoresists and antireflective coatings (ARCs) that
contained PFOS or PFOA as a surfactant or photoacid generator (PAG). In January 2010, after
significant investment and qualification of replacement chemistries across many wet etch and
photolithography processes, IBM completed its conversion to non-PFOS/PFOA lithographic
chemicals. This change eliminates approximately 140 kilograms of PFOS and PFOA compounds
per year. IBM's conversion occurred without decreasing the product final wafer test yield,
increasing the volume of chemicals used in production, or increasing the cost of any chemicals
except one. IBM believes it is the only company in the world to eliminate PFOS and PFOA
compounds completely from semiconductor manufacturing. In February 2010, IBM announced
the development of PAGs free of perfluoroalkyl sulfonates (PFAS) for both dry and immersion
193-nm semiconductor photolithography processes.
Tru-Core® Protection System for Wood
Wood is the most widely used residential building material in the United States. Its
environmentally positive characteristics include excellence as a carbon sink, low embodied
energy, and high sustainability. Among its few shortcomings, however, is its relative lack
of durability due to its susceptibility to decay and insect attack. Treating wood with
preservatives and insecticides can improve its durability significantly, but methods for
delivering these protectants into wood are still largely based on old technologies that are
environmentally damaging.
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Kop-Coat developed Tru-Core® Protection System to treat wood in an environmentally positive
manner. The Tru-Core® system incorporates the principles of green chemistry in several ways. For
example, most conventional treatments for wooden window frames and doors use petroleum-based
solvent carriers, such as mineral spirits, that emit volatile organic compounds (VOCs). The Tru-
Core® process uses water as the carrier, resulting in a significant reduction in organic solvent use.
Because the Tru-Core® process uses only a small amount of water to carry the preservatives, it also
eliminates the energy-intensive step of re-drying wood after treatment.
The Tru-Core® system employs a unique chemical infusion process that includes nonvolatile,
highly polar bonding carriers (amine oxides in water) that penetrate the cellular structure of wood
to deposit and bind wood protection chemicals (preservatives and insecticides) within the substrate.
Buffers such as borates maintain a basic pH that inhibits the natural acids present in wood, allowing
the amine oxides and preservatives to penetrate rapidly. Tru-Core® extends the service life of wood,
an environmentally positive building material in its own right.
In 2010, the Tru-Core® technology received a U.S. patent and EPA registered it as a
wood preservative treatment. Because the Tru-Core® technology is effective, economical, and
environmentally sound, it is having significant commercial success in the United States and
other countries.
Kiehl's "Aloe Vera" Biodegradable Liquid Body Cleanser
By developing and commercializing Kiehl's "Aloe Vera" Biodegradable Liquid Body Cleanser,
L'Oreal launched the first ever Cradle to Cradle® certified biodegradable product within the
cosmetic industry. Inspired by the Cradle to Cradle® philosophy and in collaboration with the
Make It Right Foundation, L'Oreal formulated this product with green chemistry in mind. Cradle
to Cradle® certification is a multi-attribute eco-label of McDonough Braungart Design Chemistry
(MBDC). It assesses a product's safety to humans and the environment as well as its design for
future lifecycles. Kiehl's 'Aloe Vera" Biodegradable Liquid Body Cleanser received the Cradle to
Cradle® silver certification. This product received a gold score in material reutilization and silver
scores in the other four categories: material health, renewable energy use, water stewardship, and
social responsibility.
The ingredients in the Kiehl's 'Aloe Vera" formulation are water, sodium coco-sulfate, coco-
glucoside, sodium benzoate, potassium sorbate, glycerin, Aloe barbadensis leaf juice, citric acid,
sodium chloride, and fragrance. L'Oreal minimized the amount of ingredients to simplify and
optimize the use of each ingredient and avoid unnecessary ingredients. In formulating this product,
the company used ingredients in three main categories: coconut-derived surfactants for cleansing,
preservatives commonly found in food, and fundamental moisturizing ingredients with known
benefits. L'Oreal selected each ingredient not only to ensure biodegradability but also to ensure that
the product was not ecotoxic.
The product is packaged in 100 percent post-consumer recycled poly(ethylene terephthalate)
(PET) to minimize the production of plastic bottles from new materials. L'Oreal launched
this product in 2008. It donates all of the net profits from sales of this product to the Make It
Right Foundation.
Positive Environmental Impact of Novel Crankcase
Lubricant Technology
Phosphorus in the form of zinc dialkyldithiophosphate (ZDP) is the most cost-effective antiwear,
antioxidant, and anticorrosion agent available for engine oil. Phosphorus, however, can enter engine
exhaust and decrease the ability of catalytic converters to reduce emissions. This effect, called
catalyst deactivation, makes it difficult for automotive manufacturers to meet EPA's requirements for
lengthy warranties on catalyst systems. To protect against wear and safeguard the catalyst, industry
L'Oreal USA
The Lubrizol
Corporation
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Monsanto Company
has restricted phosphorus in lubricants to 0.06—0.08 percent by weight. Even at these low levels,
however, phosphorus can volatilize and deactivate the catalyst.
Lubrizol has developed the HyperZDP™ System, a low-volatility ZDP. In partnership with
Valvoline, it has studied the performance of Hyper ZDP™ technology and that of conventional
ZDP technology. In Valvoline motor oils, HyperZDP™ reduced phosphorus deposition on the
exhaust catalyst by 30—50 percent after 100,000 miles. Road testing for 100,000 miles reduced
non-methane organic gases by 20 percent, NOx (nitrogen oxides) by 40 percent, and carbon
monoxide (CO) by 35 percent. Chassis dynamometer testing showed NOx reductions of
30 percent. Bench testing showed reductions in T50 across different catalysts. Lubrizol then
modeled T50 values for total hydrocarbons (THC), CO, and NOx as functions of catalyst
characteristics and phosphorus levels on the catalyst. The models showed the strongly beneficial,
statistically significant impact of Valvoline motor oils with HyperZDP™ on catalyst performance.
Environmental Resources Management Ltd. conducted a lifecycle analysis consistent with
ISO 14040. Compared to conventional ZDP, HyperZDP™ produced very significant reductions
in photochemical oxidation, acidification, global warming potential, and human toxicity along
with a minor reduction in aquatic toxicity and a minor increase in resource depletion.
After Lubrizol introduced its API SM/ILSAC GF-4 low-volatility ZDDP technology in 2004,
Valvoline began using it universally in passenger car motor oils. Lubrizol received a patent for this
technology in 2010.
Revolutionizing Insect Control:
Bacillus thuringiensis (Bt) Technology
Insect pests have limited food crop production for centuries. Insecticidal chemicals were the
most technologically advanced tools for insect control until the 1980s. Unfortunately, these
chemicals had undesirable environmental effects, were toxic to some nontarget organisms, and
required repeated applications to crops.
Monsanto's successful scientific research in innovative biotechnology since the 1980s has led
to replacing the chemical manufacturing of pesticides with biological manufacturing mechanisms
that create natural pesticides in the crops themselves. Unlike traditional pesticide technology,
Monsanto's recently patented technology uses effective insect control found in nature. Bacillus
thuringiensis (Bt), a ubiquitous soil microbe, produces specific insecticidal toxins called Cry
(crystal) proteins. Using biotechnology, Monsanto combined its knowledge of Cry proteins with
pioneering plant molecular genetics to create plants that express these highly specific toxins. The
resulting plants control pests by making Bt Cry proteins themselves. These plants reduce the need
for chemical pesticides, and the specificity of Cry proteins ensures that only target organisms are
affected and not humans, animals, or nontarget beneficial insects.
Monsanto is applying its Bt technology to many plant varieties, increasing crop yields, and
reducing the need for harsh chemical pesticides. In 2006, Bt crops reduced pesticide use by
9.56 million pounds in the United States. From 1996 to 2006, the commercialization
of Bt technology contributed to an increase in national farm income from $8.76 million
to $707 million.
Farmers planting insect-resistant crops experience improved safety and health because they
handle less pesticides and apply them less frequently. Farmers also handle fewer containers, use
less fuel, and decrease their aerial spraying. These factors benefit the environment, increase yields,
and enhance farmers' lives. In 2010, biotechnology-derived, insect-resistant crops developed with
Monsanto's technology represented 63 percent of all corn and 73 percent of all cotton grown in
the United States.
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Enabling a Sustainable Biorefinery with Green Chemistry:
Enzymatic Hydrolysis of Lignocellulosic Biomassfor the
Production of Advanced Biofuels and Renewable Chemicals
Plant cell walls are a complex matrix of cellulose, hemicellulose, and lignin. Hydrolyzing this
recalcitrant lignocellulosic material efficiently is critical to obtaining high-quality sugar streams as
feedstocks for fermentation or chemical synthesis to make fuels and chemicals.
Novozymes has taken a major step towards enabling the commercial production of biofuels
and renewable chemicals from biomass. The Novozymes Cellic™ CTec2 technology employs
enzymes to achieve high sugar yields from a variety of feedstocks (e.g., corn stover, wheat straw,
and perennial grasses). A key breakthrough was Novozymes's unexpected discovery that a family
of proteins (GH61) from Thielavia terrestris plays a significant role in lowering the amount of
cellulase enzymes needed to hydrolyze lignocellulose. Novozymes incorporated a highly active
GH61 protein into the CTec2 enzyme cocktail secreted by genetically engineered Trichoderma
reesei, a cellulolytic fungus. CTec2 significantly improves the efficiency of biomass conversion
over previous enzyme cocktails. It enables the production of cellulosic biofuels that can reduce
greenhouse gas emissions by 115—128 percent compared to gasoline. Novozymes also developed
a companion product, HTec2, with increased xylanase for feedstocks with high levels of
insoluble xylan.
In the near term, biofuels are the only form of renewable energy that can substantially reduce
greenhouse gas emissions from transportation. Novozymes is supporting its partners in scaling
up proven technologies to produce these biofuels. The Novozymes CTec2 enzyme technology, in
combination with process improvements by its partners, allows major reductions in enzyme doses.
This breakthrough makes Novozymes CTec2 the first commercially viable enzyme technology for
cellulosic ethanol production. This technology supports U.S. goals articulated in the Renewable
Fuels Standard by providing a practical way to expand ethanol production from corn starch
to cellulose as a feedstock. In 2010, Novozymes launched CTec2, placing the cost of enzyme
technology within the commercially feasible range of $0.24—0.50 per gallon of ethanol.
New Lead-Free Materials to Replace Existing
Primary Explosives
Lead azide (LA) and lead styphnate (LS) are widely used in ordinance as priming mixtures
for propellants and as detonators for secondary explosives. Annually, the U.S. Army requires
well over 1,000 pounds of LA. The United States uses 60,000—80,000 pounds of LS containing
approximately 30,000 pounds of lead annually as percussion primers in military and commercial
small-caliber ammunition. During use and disposal, these compounds release lead, a toxic heavy
metal, into the environment. Further, their manufacture requires toxic or carcinogenic materials.
In 1993, President Clinton issued Executive Order 12856 to reduce or eliminate the
procurement of hazardous substances and chemicals by federal facilities. In compliance, the
CAD/PAD group (i.e., Cartridge Activated Device/Propellant Activated Device group) at the
Naval Surface Warfare Center-Indian Head (NSWC-IH) began a program to replace LA and
LS with substitutes free of mercury, lead, and barium. Pacific Scientific Energetic Materials Co.
(PSEMC) in Chandler, Arizona has been a leader in developing drop-in replacements for LA and
LS that incorporate no toxic or environmentally undesirable elements. Because LA and LS have
specific and complex properties, PSEMC spent over ten years developing environmentally benign
replacements for these materials from concept through synthesis to qualification.
DBX-1 (Cu1 5-nitrotetrazolate) is an LA replacement that has undergone qualification testing
and is being scaled up to production levels for commercial and military uses. DBX-1 offers high
oxidative, hydrolytic, and thermal stability, improved safety characteristics and compatibility, and
output performance equal to or exceeding that of LA.
Novozymes North
America, inc.
Pacific Scientific
Energetic
Materials Co.
-------
PPG
industries, inc.
Rochester Midiand
Corporation
KDNP (potassium 5,7-dinitro-[2,l,3]-benzoadiazol-4-oleate-3-oxide) is an LS replacement
suitable for service use; it qualified for weapons development in 2009. KDNP has high thermal
stability, improved safety and compatibility, and output performance equal to or better than that
of LS. PSEMC has applied for several patents on both KDNP and DBX-1.
Waterborne Refinish Coatings Manufacture
Paints and solvents account for approximately 12 percent of all emissions of volatile organic
compounds (VOCs). The traditional, solventborne paints that automobile body repair shops
have used for automotive refinishing emit relatively large amounts of VOCs. The California Air
Resources Board (GARB) enacted legislation in January 2010 to reduce VOCs for all automotive
refinishing products. Most notably, it reduced the limit on VOCs in basecoat to 3.5 pounds per
gallon (420 grams per liter). The rest of the United States is expected to adopt similar limits in
the near future.
Waterborne and solventborne paints perform similarly in color accuracy, smoothness, and chip
resistance. Although the main current motivators of market growth for waterborne coatings are
VOC regulations in California and Canada, many automotive refinishers use PPG's waterborne
finish products solely for their perceived superior performance.
PPG developed waterborne finish in Europe in the early 1990s. In spring 2010, PPG established
an innovative waterborne manufacturing process and facility in Delaware, Ohio. This facility
is designed such that all raw materials, production, filling, quality assurance, and utilities are
located nearby. The design reduces product loss, contamination, and waste. The waterborne finish
produced at this facility will contain approximately 0.15 pounds of VOCs per gallon.
The company's expansion to the North American market allows PPG to create an additional
3 million liters per year of its high-quality, environmentally friendly waterborne refinish paint.
During 2012, this production volume will avoid the emission of 3,097 metric tons of carbon
dioxide equivalents (CO2e). PPG expects the use of waterborne finish to double in the next five
years.
Any body shop that replaces solventborne finish with waterborne finish will release 80 percent
fewer VOCs to the atmosphere. More than 25,000 auto body repair shops in 50 countries (nearly
5,000 in the United States) now use PPG's waterborne refinish coatings.
Enhance O2 Soil Remover for Commercial Fryers
Current technologies for cleaning commercial deep-fat fryers use acid, bleach, and caustic
chemicals to break down the adhesion of protein-based fryer soils chemically and lift the soils away
from the fryer surface. These technologies may leave hazardous chemical residues behind. They
also may not remove all the original soils, which can then support additional bacterial growth and
produce off-tastes. Traditional cleaning methods may also lead to employee contact with harsh
acids, bleaches, or bases and to disposal problems after the cleaning process.
Rochester Midland Corporation's (RMC's) Enhance O2 formulation represents a revolutionary
advance in the removal of charred soils from the surface of steel commercial fryers. These soiled
fryers typically harbor baked-on hydrocarbon, protein-based surface contamination that both
presents a potential food source for bacteria and limits effective heat transfer.
Enhance O2 uses environmentally friendly, renewable hydrogen peroxide and selected trace
surfactants to oxidize and break down these protein-based fryer soils. Enhance O2 is a natural,
green product. Once hydrogen peroxide does its soil removal job, it decomposes to water and
oxygen gas, eliminating disposal issues at the plant. In addition, hydrogen peroxide is a known,
traditional disinfectant for skin cuts and sterilization processes.
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In one case study, Enhance O2 reduced caustic use by one-half in five large cookers and
one chiller making pasta at Windsor Foods. Enhance O2 also eliminated an acid wash. Overall
process improvements, including Enhance O2, reduced chemical, labor, and water costs by
$25,000 annually.
RMC received a U.S. patent for its technology in March 2009 (Patent No. 7,507,697).
PRS Water Damage PreClean: Biological Cleaning for
Restoration and Remediation
When common structural members such as wood and concrete become contaminated by gray
or black water, they typically harbor residues that produce undesirable malodors and are a potential
food source for bacteria, mold, and mildew. Current technology uses petroleum-derived detergents
and harsh chemicals to penetrate interstitial structural pores, break down odoriferous residues
chemically, and abate the proliferation of mold and mildew. After use, current technology may
leave undesirable odors, residual harsh chemicals, and even residues of the original contaminants
that may continue to grow bacteria and mold.
Rochester Midland Corporation (RMC) has developed PRS Water Damage PreClean
(PRS PreClean) to remediate contaminated, waterlogged structures. PRS PreClean uses an
environmentally friendly, renewable detergent and special nonpathogenic bacteria in a pH-neutral
aqueous solution to access and digest malodor-causing residues. Unlike traditional cleaners, PRS
PreClean penetrates porous structures easily, allowing its bacteria access to the residues. The
bacteria germinate and metabolize the residues in situ.
PRS PreClean is a natural, green product: its active component is living, naturally occurring,
noninfectious bacteria, and its principal surfactant is naturally derived. Because bacteria carry
out the necessary chemical reactions, there is no need to introduce harsh acids or bases into the
environment. As a result, PRS PreClean eliminates significant amounts of hazardous materials. In
one case study, PRS Pre-Clean reduced both surface solids and bottom solids in septic tanks. In
a second case study, Enviro Care Liqui Bac (a one-half concentrate of PRS PreClean) remediated
damage to concrete floors, carpet, and wall cavities caused by a sewage leak in a house. After
treatment, workers removed all porous building materials and cleaned nonporous materials
thoroughly with disinfectant and vacuums. Subsequent testing showed no sewage bacteria.
In 2010, this technology received EcoLogo CCD-112 certification for Biological Digestion
Additives for Cleaning and Odour Control.
Greener Chemistry Processes for Large-Scale Manufacture
ofPolyamino Acids
Polyamino acids have properties that mimic proteins and make them ideal for targeted drug
delivery. They are water-soluble, selective, biodegradable, low-toxicity molecules with a wide
range of molecular weights. Their production, however, involves both unstable, intermediate
amino acid TV-carboxyanhydrides (NCAs) and polymer processing. Traditionally, these steps
require large quantities of hazardous chemicals including phosgene, hydrogen bromide—acetic
acid, acetone, and dioxane.
Sigma-Aldrich has developed novel manufacturing processes for polyamino acids that minimize
hazardous chemicals, improve efficiency, and increase product quality. For NCA production,
Sigma-Aldrich eliminated NCA recrystallizations and reduced manufacturing runs by over
30 percent. They reduced phosgene and tetrahydrofuran by 30 percent and ethyl acetate and
hexane by 50 percent, which reduced hazardous waste. Finally, they increased consistency in
quality and yield.
Rochester Midland
Corporation
Sigma-Aldrich
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Tandus Flooring
UOP LLC
Sigma-Aidrich also applied green chemistry to manufacturing poly-L-glutamic acid, a major
drug-delivery polymer, which requires hazardous operations with hydrogen bromide—acetic acid
or hydrogenation as well as highly flammable solvents. Replacing a benzyl protecting group with
an ethyl group allowed them to replace hazardous chemicals with water-based chemicals, decrease
cycle time by over half, decrease energy use and greenhouse gas emissions, and improve the scale-
up potential 10-fold.
Sigma-Aldrich achieved similar savings with new processes for polylysine polymers and
polyamino acid copolymers. For polylysine polymers, Sigma-Aldrich used only half the previous
amount of hazardous chemicals (dioxane, hydrogen bromide—acetic acid, and acetone), but
increased the yield from 10—30 percent to 43—53 percent. Sigma-Aldrich halved production runs,
which is saving hundreds of gallons of hazardous chemicals, generating less waste, and saving
energy. They also switched polyamino acid copolymer production to water-based systems that
eliminate benzyl bromide, a hazardous lachrymator byproduct.
Sigma-Aldrich believes its contributions will lead to efficient chemotherapeutic treatments for
diseases such as cancer, multiple sclerosis (MS), and diabetes and pave the way for greener chemical
industry practices.
Ethos™Modular Commercial Floor Coverings
For years, recyclers have recovered glass from recovered windshields and sold it into other
markets. In contrast, most of the polymeric poly(vinyl butyral) (PVB) film recovered from used-
car windshields and other safety glass has been sent to landfills or burned for energy. PVB is a
thermoplastic terpolymer of vinyl acetate, vinyl alcohol, and vinyl butyral.
Tandus Flooring is the first manufacturer to use the abundant PVB waste stream and recycle
it into a high-performance carpet backing. Ethos™ secondary backing is made from PVB film
reclaimed from windshields and other safety glass. Tandus has developed a patented technology
for recycling post-consumer carpet and manufacturing waste into recycled-content backing for
new floor coverings. Ethos™ backing is an alternative to other structured carpet backings such as
poly(vinyl chloride) (PVC), ethylene—vinyl acetate (EVA), polyurethane, polyolefin, and bitumen.
Producing carpet backing from recycled material reduces the energy and environmental impacts
associated with extracting, harvesting, and transporting virgin raw materials.
Tandus evaluated PVB against 10 other polymer-based materials using stringent performance
and environmental criteria. In these tests, PVB was superior to the other polymers in material
availability, recyclability, reduction of virgin resources, avoidance of hazardous emissions (e.g.,
dioxin), and elimination of chemicals of concern such as chlorine, fly ash, and phthalate plasticizers.
In addition, ethos™ backing has extremely low environmental lifecycle impacts and has very low
volatile organic compounds (VOCs). In a fire, ethos™ does not generate hydrochloric acid (HC1)
or dioxins, as do other carpet backings.
Initially, Tandus successfully introduced a six-foot-wide ethos™ cushion backing to meet the
needs of Kaiser Permanente for high-performance, PVC-free carpet. This product is recyclable
into Tandus's existing carpet-recycling process. More recently, the company introduced ethos™
modular, which has been commercially available since November 2009 at a price equivalent to
PVC-containing modular products.
Diesel and Jet Fuel from Renewable Resources That Is
Fungible with Petroleum Fuels
Two roadblocks preventing the widespread use of renewable sources in transportation fuel are
the incompatibility of current renewable fuels with the existing fuel distribution infrastructure
and their incompatibility with current petroleum-based fuels. The primary components of
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current renewable transportation fuel are ethanol and fatty acid methyl esters (FAMEs). Because
neither of these components is compatible with the existing infrastructure, they must be splash-
blended at fuel distribution terminals. Further, their incompatibility with current gasoline, jet,
and diesel engines limits them to about 10 percent by volume. This presents a huge hurdle to their
commercial acceptance.
Scientists and engineers at UOP (a Honeywell Company) have developed the innovative
approach of hydroprocessing biofeedstocks into transportation fuels. Hydroprocessing uses
hydrogen to remove the oxygen from biofeedstocks by decarboxylation and hydrodeoxygenation,
producing fuel and leaving propane, water, and carbon dioxide (CC>2) as byproducts. With
new catalysts and process-flow schemes, UOP can produce both diesel and jet fuels from many
biofeedstocks including jatropha, camelina, algal oil, animal fats, and used cooking oil. Their
products are compatible with the existing refinery infrastructure, technology, and distribution
network. Even more important, UOP's bioproducts can be blended directly into current fuels
without modifying the jet or diesel engines or the delivery infrastructure. Although the processes
to make diesel and jet fuels are similar, the detailed flow schemes and catalysts are different because
the two fuels have different specifications. A lifecycle analysis (LCA) estimates greenhouse gas
(GHG) savings at 84 percent for Green Jet Fuel™ and 89 percent for Green Diesel™.
In developing the UOP/Eni Ecofming™ process for Green Diesel™, UOP and Eni SpA took
these inventions from concept to full process design. They have now licensed their process to four
refiners. Several organizations are partnering with UOP to bring renewable jet fuels to market.
UOP and Eni have filed 30 U.S. patent applications for their Ecofming™ technologies.
Klean-Strip * Green ™ Safer Paint Thinner
Petroleum distillates present risks to human health and the environment, such as air pollution
from volatile organic compounds (VOCs), health hazards from inhalation and skin contact, and
fire hazards during manufacture, use, storage, and transport. Although consumers can foresee these
hazards and government regulators, industry, and the marketplace deem them to be acceptable
and reasonable, Barr sought to develop a safer, more environmentally friendly alternative.
Klean-Strip® Green™ Safer Paint Thinner is a formulation of Type IIC mineral spirits suspended
in water with a small amount of oleic acid emulsifier. It contains 67 percent lower VOCs than
regular paint thinner. The mineral spirits are a safer petroleum distillate without any hazardous
air pollutants (HAPs). Consumers of Klean-Strip® Green™ Safer Paint Thinner report lower odors
and less skin irritation than with regular paint thinner. Klean-Strip® Green™ Safer Paint Thinner
is nonflammable and noncombustible; therefore, it poses no fire hazards. Its lower VOC content
means that it is less volatile than regular paint thinner, so indoor air pollution is less of a problem
for consumers. Unlike regular paint thinner, Klean-Strip® Green™ Safer Paint Thinner is not a
hazardous waste under the Resource Conservation and Recovery Act (RCRA), not a hazardous
substance under the Comprehensive Environmental Response, Compensation, and Liability
Act (CERCLA) and the Superfund Amendments and Reauthorization Act (SARA), and not a
hazardous material under Department of Transportation regulations.
Other environmental benefits include less dependence on nonrenewable resources such as
petroleum because 67 percent of the product is water, a renewable resource. Because water is readily
available at Barr's manufacturing site, there are fewer transportation risks and environmental
impacts (i.e., air pollution) associated with raw material supply. Since its introduction in 2007,
this product has had average annual sales of 8 million pounds, eliminating the use and VOC
emissions of 5 million pounds of petroleum distillate.
WM Barr &
Company, inc.
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index
Award winners are indicated with asterisks.
inc. and David Department of
Science and Engineering, Case Western
Reserve University
AeroClay*: A Green Aerogel for Industry 12
AkzoNobel Functional Chemicals, LLC
GLDA: The Greener Chelate; Sustainable, Safe, and Strong 31
Albemarle Corporation
Concrete-Friendly'1" Powdered Active Carbon (C-PAC™) for Safely Removing Mercury
from Air 31
Argonne National Laboratory
Upcycling Plastic Bags into More Valuable Products 32
Ashland Performance Materials
Envirez™ Technology: Incorporating Renewable and Recycled Feedstocks into
Unsaturated Polyester Resins 32
Corporation
Green Sense514 Concrete 33
Bennett, Jacqueline, Department of Chemistry and Biochemistry,
State University of New York Oneonta
Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis ofDiarylAldimines 9
*BioAmber, Inc.
Integrated Production and Downstream Applications of BiobasedSuccinic Acid 4
Case Western Reserve University, Department of Macromolecular
Science and Engineering, David Schiraldi and Aeroclay, inc.
AeroClay®: A Green Aerogel for Industry 12
Champion Technologies, Inc.
Lysine-Based Phosphonate Scale Inhibitor with Improved Biodegradation and
Maintained Performance. 34
Chemical Safety Software
Source Reduction through Software Technology 17
Colonial Chemical, inc.
SugtfNate: A Safer, Milder, Greener Surfactant 17
Colorado School of Mines, Department of Chemistry, Kent J.
Voorhees and MicroPhage, inc.
Bacteriophage-based Test for MRSA/MSSA Infections Acquired in Hospitals 14
Commercial Fluid Power LLC
Elimination ofHexavalent Chromium from Hydraulic and Pneumatic
Tubing and Bar 18
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Cooper Power Systems
Green Chemistry for High-Voltage Equipment: The Research, Development, and
Application of Soy-Based Dielectric Coolant 34
Cytec industries inc.
iSUSTAIN® Green Chemistry Index Tool for Sustainable Development 35
MAXHT® Bayer Sodalite Scale Inhibitor 35
Saturated Polyester-Phenolic Resin Systems for Bisphenol A-Free Interior Can Coatings
for Food Packaging 36
Waterborne, Ambient-Cure, Stain-Blocking Primer 36
Desiiube Technoiogy and United Soybean Board
High-Performance, Soy-Based Metalworking Fluids 18
inc.
ReNew Air Scrubber Technology 37
Dober Chemicai Corporation
A Safer, Less Toxic, Reliable, and Green Water Treatment by
Smart Release* Technology 19
The Dow Chemicai Company
INFUSE™ Olefin Block Copolymers 38
DoPont and Honeyweii international inc.
HFO-1234yfRefrigerant for Automotive Air Conditioning with Low Global
Warming Potential 45
Earth Friendiy Products
Earth Conscious Chemistry: Eliminating 1,4 Dioxane in Cleaning Products 20
Ecoiab inc.
DryExx Conveyor Lubricant Program 38
Low- Temperature Cleaning In Place 39
E. i. do Pont de Nemours and Company
Chlorantraniliprole: Greener Chemistry for Sustainable Agriculture 39
Development of a Commercially Viable, Integrated Cellulosic Ethanol Technology 40
Pioneering Industrial Biotechnology to Meet Global Needs for a Cost-effective, Drop-in,
Renewable Fuel and Chemical 40
Eii Liiiy and Company
Continuous Processing Enables a Convergent Route to a New Drug Candidate:
LY2624803*H3PO4 41
Grignard Reactions Go Greener with Continuous Processing 42
Finn, M.G., The Scripps Research institute
Metal Adhesive Polymers from Cu1-Catalyzed Azide-Alkyne Cycloaddition:
A New Approach to Solder Replacements 9
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FIVIC Corporation
VigorOx® Biocide: Advancing Environmentally Responsible Energy Production 42
Foam Supplies, inc.
Ecomate®: Environmentally Benign Blowing Agent for Polyurethane Foams 43
FRX Polymers Inc.
Polymeric, Non-Halogenated Flame Retardants with Broad Applicability in
Multiple Industries 20
Fuel Energy Service Corporation
Surachi Fuel Technology 21
Genco, Joseph, Adriaan van Heiningen, Hemant Pendse, and
Peter van Waisom, Forest Bioprodocts Research institute.
University of Maine
Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value
Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel 13
Genencor
Gentle Power Bleach™: A Revolutionary Enzymatic Textile Bleaching System 43
General Motors
Applying Green Chemistry Principles to Enable Zero-Waste Manufacturing 44
*Genomatica
Production of High-Volume Chemicals from Renewable Feedstocks at Lower Cost 5
Hach Company
Simplified Total Kjeldahl Nitrogen Method for Wastewater: A Green Alternative to
Traditional Kjeldahl Methodology 45
Hedrick, James L., Almaden Research Center and Robert M.
Waymooth Department of Chemistry, Stanford University
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 14
Honeywell international, inc. and DoPont
HFO-1234yf Refrigerant for Automotive Air Conditioning with Low Global
Warming Potential 45
IBM Almaden Research Center, James L. Hedrick and Robert M.
Waymooth, Department of Chemistry, Stanford University
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 14
IBM Corporation
Elimination of Perfluoroalkyl Sulfonates in IBM Semiconductor Manufacturing
Processes and Development ofPFAS-Free Photoacid Generators 46
JEEN international Corporation
Polyelectrolytes: Reduce Your Carbon Footprint Using an Eco-Friendly Technology to
Disperse Wax in Water without Heat 21
Kop-Coat, Inc.
Tru-Core® Protection System for Wood 46
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*Kraton Performance Polymers, Inc.
NEXAR™ Polymer Membrane Technology 6
*Lipshutz, Bruce H., University of California, Santa Barbara
Towards Ending Our Dependence on Organic Solvents 3
L'Oreal USA
Kiehl's "Aloe Vera" Biodegradable Liquid Body Cleanser 47
The Lubrizol Corporation
Positive EnvironmentalImpactof~NovelCrankcase Lubricant-Technology 47
Mascal, IViark, Department of Chemistry, University of
California, Davis
High-Yield Conversion ofBiomass into a New Generation ofBiojuels and
Value-Added Products 10
IViicroPhage, Inc. and Kent J. Voorhees, Department of Chemistry,
Colorado School of Mines
Bacteriophage-based Test for MRSA/MSSA Infections Acquired in Hospitals 14
Monsanto Company
Revolutionizing Insect Control: Bacillus thuringiensis (Bt) Technology 48
Nanotech Industries, Inc.
Green Polyurethane™. 22
Natural State Research, Inc.
Conversion of Waste Plastics into Fuel 22
Niwayama, Satomi, Department of Chemistry and Biochemistry,
Texas Tech University
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters 10
Novomer, Inc.
Catalytic Transformation of Waste Carbon Dioxide into Valuable Materials 23
Novozymes North America, Inc.
Enabling a Sustainable Biorefinery with Green Chemistry: Enzymatic Hydrolysis of
Lignocellulosic Biomassfor the Production of Advanced Biofuels and
Renewable Chemicals 49
Technologies, Inc.
A Novel, Energy-Efficient, Emission-Free Route to Produce Potassium Hydroxide 24
The Ohio State University, Department of Chemistry,
T.V. RaJanBabu
Ethylene: A Superior Reagent for Enantioselective Functionalization ofAlkenes 11
Orono Spectral Solutions
Device and Method for Analyzing Oil and Grease in Wastewater without Solvent. 24
Pacific Scientific Energetic Materials Co.
New Lead-Free Materials to Replace Existing Primary Explosives 49
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Pendse, Hemant, Joseph Genco, Adriaan van Heiningen, and
Peter van Walsum, Forest Bioproducts Research Institute,
University of Maine
Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value
Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel 13
Piedmont Biofuels industrial, LLC
Enzymatic Catalysis for Biodiesel Production 25
Polar industries, inc.
Zero-VOC, BioBased HiOmegcf Linseed OilEpoxies, Adhesives, andAlkydResins as
Replacements for Epichlorohydrin-Epoxy Resins and Other VOC-containing Coatings,
Paints, Adhesives, and Epoxies 25
PPG industries, inc.
Waterborne Refinish Coatings Manufacture 50
RaJanBabu, T.V. (Babu), Department of Chemistry,
The Ohio University
Ethylene: A Superior Reagent for Enantioselective Functionalization ofAlkenes 11
Rochester Midland Corporation
Enhance O2 Soil Remover for Commercial Fryers 50
PRSWater Damage PreClean: Biological Cleaning for Restoration and Remediation . . .51
Savage, Phillip E., Chemical Engineering Department,
University of Michigan
Terephthalic Acid Synthesis at High Concentrations in High-Temperature
Liquid Water 12
Schiraldi, David, Department of Macromolecular Science and
Engineering, Case Western Reserve University and Aeroclay, Inc.
AeroClay*: A Green Aerogel for Industry 12
The Scripps Research institute, M.G. Finn
Metal Adhesive Polymers from Cu1-Catalyzed Azide-Alkyne Cycloaddition:
A New Approach to Solder Replacements 9
*The Sherwin-Williams Company
Water-based Acrylic Alkyd Technology 7
Sigma-Aidrich
Greener Chemistry Processes for Large-Scale Manufacture ofPolyamino Acids 51
SiGNa Chemistry, inc.
Sodium Silicide: On-Demand Hydrogen Generation for Back-Up Power and
Portable Fuel Cells 26
Solvair LLC
Solvair Cleaning System 26
59
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Stanford University, Department of Chemistry, Robert M.
Waymooth and James L. Hedrick, IBM Aimaden Research Center
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 14
State University of New York Oneonta, Department of Chemistry
and Biochemistry, Jacqueline Bennett
Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis ofDiaryl Aldimines 9
Steward Advanced Materials
Development and Commercial Application ofSAMMS*: A Novel Compound that
Adsorbs and Removes Mercury and Other Toxic Heavy Metals 27
Tandos Flooring
Ethos™ Modular Commercial Floor Coverings 52
Tang, Yi, Department of Chemical and Biomolecolar Engineering,
University of California, Los Angeles
An Efficient, Biocatalytic Process for the Semisynthesis of Simvastatin 13
Terrabon. Inc.
Conversion of Municipal Solid Wastes to Drop-In Fuels and Chemicals 28
Texas Tech University, Department of Chemistry and
Biochemistry, Satomi Niwayama
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters 10
Timber Treatment Technologies, LLC
TimberSIL® 28
Tower Oil & Technology Co.
Saf-T-Vanish*: AZero-VOC, Green Replacement for Petroleum Solvent Vanish Oils . . .29
United Soybean Board and Desilobe Technology
High-Performance, Soy-Based Metalworking Fluids 18
University of California, Davis, Department of Chemistry,
Mark Mascal
High-Yield Conversion ofBiomass into a New Generation ofBiofuels and
Value-Added Products 10
University of California, Los Angeles, Department of Chemical
and Biomolecolar Engineering, Yi Tang
An Efficient, Biocatalytic Process for the Semisynthesis of Simvastatin 13
*University of California, Santa Barbara, Bruce H. Lipshotz
Towards Ending Our Dependence on Organic Solvents 3
University of Maine, Forest Bioprodocts Research Institute,
Adriaan van Heiningen, Joseph Genco, Hemant Pendse, and Peter
van Walsom
Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value
Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel 13
60
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University of Michigan, Chemical Engineering Department,
Phillip E. Savage
Terephthalic Acid Synthesis at High Concentrations in High-Temperature
Liquid Water 12
UOP LLC
Diesel and Jet Fuel from Renewable Resources That Is Fungible with Petroleum Fuels . . . 52
van Heiningen, Adriaan, Joseph Genco, Hemant Pendse, and
Peter van Walsom, Forest Bioprodocts Research Institute,
University of Maine
Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value
Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel 13
van Walsom, Peter, Joseph Genco, Adriaan van Heiningen, and
Hemant Pendse, Forest Bioprodocts Research Institute, University
of Maine
Pre-Pulping Extraction of Hardwood Chips to Recover Hemicelluloses as a High-Value
Renewable Chemical Feedstock that Reduces Waste and Saves Fossil Fuel 13
Voorhees, Kent J., Department of Chemistry, Colorado School of
Mines and MicroPhage, Inc.
Bacteriophage-based Test for MRSA/MSSA Infections Acquired in Hospitals 14
Waymooth, Robert M., Department of Chemistry, Stanford
University and James L. Hedrick, Almaden Research Center
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 14
WM Barr & Company, Inc.
Klean-Strip® Green'1" Safer Paint Thinner. 53
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