United States
Environmental
Protection
Agency
v>EPA Presidential
Green Chemistry Challenge
Awards Program:
Summary of 2012 Award
Entries and Recipients
A U.S. EPA Program
An electronic version of this document is available at:
http: //www. epa.gov/greenchemistry
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of
Contents
Introduction [[[ 1
Awards [[[ 3
Academic Awards............................................ 3
Small Business Award. 5
Greener Synthetic Pathways Award 6
Greener Reaction Conditions Award 7
Designing Greener Chemicals Award 8
Entries from Academia ............................................ 9
Entries from Small Businesses ...................................... 15
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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 17 years of the awards program, EPA has received 1,492 nominations and
presented awards to 88 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 our 88 winning technologies are together responsible for:
• Reducing the use or generation of 825 million pounds of hazardous chemicals
• Saving 21 billion gallons of water
• Eliminating 7-9 billion pounds of carbon dioxide releases to air
And adding the benefits from the nominated technologies would greatly increase the program's
total benefits.
This booklet summarizes entries submitted for the 2012 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 2012 awards. Judging criteria
included health and environmental benefits, scientific innovation, and industrial applicability.
Six of the nominated technologies were selected as winners and were nationally recognized on
June 18, 2012, 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 2012 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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Synthesizing Biodegradable Polymers from
Carbon Dioxide Carbon Monoxide
Geoffrey
W.
Cornell University
Innovation and Benefits
Carbon monoxide and carbon dioxide derived from biomass or other carbon sources are ideal
feedstocks for chemicals, but there had been no efficient way to make them into valuable
polymers. Professor Coates developed a family of catalysts that convert carbon dioxide and
carbon monoxide into polymers. Novomer, Inc. is using his discoveries to develop a range of
innovative, high-performance products, including can and coil coatings, adhesives, foams,
and plastics.
Plastics improve our lives in countless ways, but they also pose a serious threat to our
environment. Virtually all plastics are derived from scarce fossil fuels that pose their own
danger, including oil well leaks and global warming induced by carbon dioxide (CO?). Of the
150 million tons of plastics made each year worldwide, only a small fraction is recycled. The rest
end up in landfills or worse as litter.
CO2 and carbon monoxide (CO) are ideal feedstocks for polymer synthesis. They can be
derived from many low-cost sources including biorenewable agricultural waste, abundant coal, or
even from industrial waste gas. The challenge with using them, however, lies in converting them
into useful products efficiently. Professor Geoffrey Coates has developed innovative processes to
synthesize plastics from inexpensive, biorenewable substances including carbon dioxide, carbon
monoxide, plant oils, and lactic acid.
Professor Coates has developed a new family of catalysts over the last decade that can effectively
and economically turn CC>2 and CO into valuable polymers. These catalysts have high turnover
frequencies, turnover numbers, and sclcctivitics. As a result, only a small amount of catalyst is
required leading to cost-effective commercial production for the first time. These catalysts can
also be used in highly efficient continuous flow processes.
Professor Coates has invented active and selective catalysts to copolymerize CO2 and epoxides
into high-performance polycarbonates. Professor Coates also invented a class of catalysts that
can insert one or two molecules of CO into an cpoxidc ring to produce (3-lactones and succinic
anhydrides. Both of these products have many uses in synthesizing pharmaceuticals, fine
chemicals, and plastics. Polymers made from CO2 and CO contain ester and carbonate linkages.
These polymers exhibit unique performance in current commodity plastic applications and in
some cases are ultimately biodegradable.
Professor Coates's work forms the scientific foundation of Novomer Inc., a start-up company
backed by venture capital. In 2010, Novomer and DSM announced an agreement to develop
coatings using the new polycarbonates made with Coates's catalysts. Prototype high-performance
industrial coil coatings are moving from development toward commercialization. There is potential
to develop a coating system to replace the bisphenol A (BPA) epoxy coatings that line most food
and drink cans worldwide. This discovery is important, as BPA is a suspected endocrine disrupter
that can migrate out of coatings over time. The novel polymer is currently sold to companies that
manufacture electronics because the thermally degradable nature of the polymer allows more
efficient production of electronic components. The new polycarbonate coating is expected to
require 50 percent less petroleum to produce and will sequester up to 50 weight percent COi-
Lifecycle analysis shows that at full market penetration, Novomer's materials have the potential to
sequester and avoid approximately 180 million metric tons of annual CO2 emissions.
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M.
Waymoyth,
Stanford
University
Dr. James L.
Hedrick,
Almaden
Center
Organic Catalysis: A Broadly Useful Strategy for Green
Polymer Chemistry
Innovation and Benefits
Traditional metal catalysts required to synthesize polyesters and other common plastics
end up trapped in the plastic, raising human health and environmental concerns. Professor
Waymouth and Dr. Hedrick discovered an array of alternatives—metal-free catalysts—
that are highly active and able to make a wide variety of plastics. Their discoveries include
catalysts that can depolymerize plastic and enable cradle-to-cradle recycling.
Catalysis is a foundation for sustainable chemical processes, and the discovery of highly active,
environmentally benign, catalytic processes is a central goal of green chemistry. Conventional
routes to polyesters rely on metal catalysts such as those derived from tin complexes, even though
the residual metal catalysts used for high-volumes plastics can have negative environmental
impacts in solid waste. For this reason, the European Union recently phased out many organotin
compounds. As a result, research on organic catalysts to replace the tin-based workhorse catalysts
has gained significant prominence in industrial settings related to important commodity polymers
such as siloxanes, urethanes, nylons, and polyesters.
Dr. James L. Hedrick and Professor Robert M. Waymouth have developed a broad class
of highly active, environmentally benign organic catalysts for synthesizing biodegradable and
biocompatible plastics. Their technology applies metal-tree organic catalysts to the synthesis
and recycling of polyesters. They discovered new organic catalysts for polyester synthesis
whose activity and selectivity rival or exceed those of metal-based alternatives. Their approach
provides an environmentally attractive, atom-economical, low-energy alternative to traditional
metal-catalyzed processes. Their technology includes organocatalytic approaches to
ring-opening, anionic, zwitterionic, group transfer, and condensation polymerization
techniques. Monomer feedstocks include those from renewable resources, such as lactides, as well
as petrochemical feedstocks. In addition to polyesters, Dr. Hedrick and Professor Waymouth
have discovered organocatalytic strategies (1) to synthesize polycarbonates, polysiloxanes, and
polyacrylates, (2) to chemically recycle polyesters, (3) to use metal-free polymers as templates
for inorganic nanostructures for microelectronic applications, and (4) to develop new syntheses
for high-molecular-weight cyclic polyesters. This team has shown that the novel mechanisms
ot enchainment brought about by organic catalysts can create polymer architectures that are
difficult to synthesize by conventional approaches.
The team also developed organic catalysts to depolymerize poly(ethylene terephthalate)(PET)
quantitatively, allowing recycling for PET from bottles into new bottles as a way to mitigate the
millions of pounds of PET that plague our landfills. Dr. Hedrick and Professor Waymouth also
demonstrated that their organic catalysts tolerate a wide variety ot functional groups, enabling
the synthesis of well-defined biocompatible polymers for biomedical applications. Because these
catalysts do not remain bound to the polymer chains, they are effective at low concentrations.
These results, coupled with cytotoxicity measurements in biomedical applications, highlight
the environmental and human health benefits of this approach. Professor Waymouth and Dr.
Hedrick have produced over 80 manuscripts and eight patents on the design of organic catalysts
for polymer chemistry with applications in sustainable plastics, biomedical materials, and plastics
for recycling.
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Using Metathesis Catalysis to Produce High-Performing,
Green Specialty Chemicals at Advantageous Costs
Elewance
Renewable
Inc.
Innovation and Benefits
Elevance employs Nobel-prize-winning catalyst technology to break down natural oils and
recombine the fragments into novel, high-performance green chemicals. These chemicals
combine the benefits of both petrochemicals and biobased chemicals. The technology
consumes significantly less energy and reduces greenhouse gas emissions by 50 percent
compared to petrochemical technologies. Elevance is producing specialty chemicals for many
uses, such as highly concentrated cold-water detergents that provide better cleaning with
reduced energy costs.
Elevance produces high-performance, cost-advantaged green chemicals from renewable oils. Its
processes use Nobel Prize-winning innovations in metathesis catalysis, consume significantly less
energy, and reduce greenhouse gas (GHG) emissions by 50 percent compared to petrochemical
technologies. The processes use a highly efficient, selective catalyst to break down natural oils and
recombine fragments. The core technology is based on the work of Nobel Laureate Dr. Robert H.
Grubbs. In 2011, Elevance expanded its proprietary technology with a licensing agreement with
XiMo AG to use proprietary molybdenum and tungsten metathesis catalysts based on the work of
Nobel Laureate Dr. Richard Schrock.
The resulting products are high-value, difunctional chemicals with superior functional
attributes previously unavailable commercially. These molecules combine the functional attributes
of an olefin, typical of petrochemicals, and a monofunctional ester or acid, typical of biobased
oleochemicals, into a single molecule. Conventional producers have to blend petrochemicals and
biobased oleochemicals in attempts to achieve these functional attributes simultaneously, which
when possible, increase their production costs. Elevance's difunctional building blocks change
this paradigm by creating specialty chemical molecules which simultaneously include desired
attributes enabled by both chemical families, such as lubricant oils with improved stability or
surfactants with improved solvency.
Elevance's low-pressure, low-temperature processes use a diversity of renewable feedstocks
that yield products and byproducts with low toxicity. Elevance's processes result in lower source
pollution, production costs, and capital expenditures than petrochemical refineries. Currently,
Elevance is the only company that can produce these difunctional chemicals. The company's
ability to manufacture biochemicals for multiple products reduces reliance on petrochemicals and
provides more effective, sustainable products to consumers.
The company makes difunctional molecules as part of its specialty chemical business. Elevance's
products enable novel surfactants, lubricants, additives, polymers, and engineered thermoplastics.
For instance, Elevance is producing specialty chemicals to enable cold water detergents that
have more concentrated formulations and improved solvency for better cleaning, to improve
sustainability metrics, and to reduce energy costs for customers and consumers. Other examples
include biobased anti-frizz and shine additives for leave-in hair care products to replace petroleum-
based petrolatum, alternatives to paraffin for high performance waxes, novel plastic additives for
poly(vinyl chloride) (PVC) and unique monomers for biobased polymers and engineered plastics.
Elevance has completed validation in toll manufacturing. It is building world-scale facilities
in Grcsik, Indonesia, and Natchez, Mississippi, with combined annual production capacity
over 1 billion pounds and exploring sites in South America. Elevance has also secured strategic
partnerships with value chain global leaders to accelerate rapid deployment and commercialization
for these products.
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Inc.
Professor Yi Tang,
Uniwersity of
California,
Los
An Efficient Biocatalytic Process to Manufacture Simvastatin
Innovation and Benefits
Simvastatin, a leading drug tor treating high cholesterol, is manufactured from a natural
product. The traditional multistep synthesis was wasteful and used large amounts of
hazardous reagents. Professor Tang conceived a synthesis using an engineered enzyme and a
practical low-cost feedstock. Codexis optimized both the enzyme and the chemical process.
The resulting process greatly reduces hazard and waste, is cost-effective and meets the needs
of customers. Some manufacturers in Europe and India use this process to make simvastatin.
Simvastatin, a leading cholesterol lowering drug, was originally developed by Merck under
the brand name Zocor®. In 2005, Zocor*' was Merck's best selling drug and the second-largest
selling statin in the world with about $5 billion in sales. After when Zocor'*1 went off patent
in 2006, simvastatin became the most-prescribed statin, with 94 million prescriptions filled in
2010, according to IMS Health.
Simvastatin is a semisynthetic derivative of lovastatin, a fungal natural product. Simvastatin
contains an additional methyl group at the C2' position of the lovastatin side chain. Introduction
of this methyl group in lovastatin using traditional methods requires a multistep chemical
synthesis. In one route, lovastatin is hydrolyzed to the triol, monacolin J, which is protected
by selective silylation, esterified with dimethylbutyryl chloride, and deprotected. Another route
involves protecting the carboxylic acid and alcohol, methylating the C2' with methyl iodide, and
deprotecting. Despite considerable optimization, these processes have overall yields of less than
70 percent, are mass-intensive due to protection/deprotection, and require copious amounts of
toxic and hazardous reagents.
Professor Yi Tang and his group at UCLA conceived a new simvastatin manufacturing process
and identified both a biocatalyst for regioselective acylation and a practical, low-cost acyl donor.
The biocatalyst is LovD, an acyltransferase that selectively transfers the 2-methylbutyryl side chain
to the C8 alcohol of monacolin J sodium or ammonium salt. The acyl donor, dimethylbutyryl-
S-methylmercaptopropionate (DMB-SMMP), is very efficient for the LovD-catalyzed reaction,
is safer than traditional alternatives, and is prepared in a single step from inexpensive precursors.
Codexis licensed this process from UCLA and subsequently optimized the enzyme and the
chemical process for commercial manufacture. Codexis carried out nine iterations of in vitro
evolution, creating 216 libraries and screening 61,779 variants to develop a LovD variant with
improved activity, in-process stability, and tolerance to product inhibition. The approximately
1,000-fold improved enzyme and the new process pushed the reaction to completion at high
substrate loading and minimized the amounts of acyl donor and of solvents for extraction and
product separation.
In the new route, lovastatin is hydrolyzed and converted to the water-soluble ammonium
salt of monacolin J. Then a genetically evolved variant of LovD acyltransferase from E. coli uses
DMB-SMMP as the acyl donor to make the water-insoluble ammonium salt of simvastatin. The
only coproduct of simvastatin synthesis is methyl 3-mercaptopropionic acid, which is recycled.
The final yield of simvastatin ammonium salt is over 97 percent at a loading of 75 grams per
liter of monacolin J. The nominated technology is practical and cost-effective. It avoids the
use of several hazardous chemicals including tert-butyl dimethyl silane chloride, methyl iodide,
and w-butyl lithium. Customers have evaluated the simvastatin produced biocatalytically and
confirmed that it meets their needs. Over 10 metric tons of simvastatin have been manufactured
using this new process.
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MAXHT^' Bayer Sodalite Scale Inhibitor
Innovation and Benefits
The "Bayer process" converts bauxite to alumina, the raw material for making aluminum,
Mineral scale deposited on the heat exchangers and pipes in Bayer process plants increases
energy use. Removing the scale requires stopping production and cleaning with sulfuric
acid. Cytec's product hinders scale growth. Eighteen plants worldwide are using MAX HT®
inhibitor, saving trillions of Btu (British thermal units) annually. Fewer cleaning cycles also
reduce hazardous acid waste by millions of pounds annually.
The Bayer process converts bauxite ore to alumina, the primary raw material for aluminum.
The process involves extracting alumina trihydrate from bauxite ore using hot caustic solution.
After separating out the insoluble solids, the alumina trihydrate is precipitated and the spent liquor
is recycled. Heat exchangers re-concentrate the liquor to the optimum concentration of caustic
and then heat it to the proper temperature for digestion. Silica present as silicates, primarily clay
materials, dissolves quickly in typical Bayer liquor used to digest alumina, resulting in the liquor
being supersaturated in silica, particularly after precipitation of the alumina trihydrate. The silica
in the liquor reacts with the caustic and alumina on the hot surfaces of the heat exchangers;
as a result, sodalite scale (i.e., crystalline aluminosilicate) builds up on the heat exchangers and
interstage piping in the process. This reduces the efficiency of the heat exchangers. Periodically,
Bayer process plant operators must take the equipment offline for cleaning that involves removing
the scale with sulfuric acid. The used acid is a waste stream that requires disposal. In addition to
the acid cleaning, much of the interstage piping requires cleaning with mechanical means such as
jackhammers to remove the scale.
Cytec developed its MAX HT'S' Bayer Sodalite Scale Inhibitor products for the Bayer process.
There are no other scale inhibitors on the market for this application. The active polymeric
ingredient contains silane functional groups that inhibit crystal growth by incorporation into
the crystal or adsorption onto its surface. The polymers have molecular weights in the range
10,000 and 30,000. Their synthesis involves polymerizing a monomer containing a silane group
or reacting polymer backbone with a reagent containing the silane group. Dosages range from
20 to 40 ppm. Assessments of these polymers under EPA's Sustainable Futures Program indicate
low overall concern for human health and the aquatic environment.
Eliminating sodalite scale from heater surfaces has many benefits. Heat recovery from the
steam produced in various unit operations is more efficient. Increased evaporation makes the
countercurrent washing circuit more efficient and reduces caustic losses. Reducing the use of steam
reduces emissions from burning carbon-based fuels. Finally, reducing the sulfuric acid used to
clean heaters reduces both worker exposure and waste. Typically, MAX HT*'1 inhibitor increases
the on-stream time for a heater from 8—10 days to 45—60 days for digestion and from 20—30 days
to over 150 days for evaporators.
There are about 73 operating Bayer process plants worldwide with annual capacities of
0.2—6 million tons of alumina per plant; most plants are in the 1.5—3 million ton range. Eighteen
Bayer process plants worldwide have adopted this technology; seven more plants are testing it.
Each plant using MAX HT* saves $2 million to $20 million annually. The realized annual energy
savings for all plants together are 9.5 trillion to 47-5 trillion Btu, which is the equivalent of about
1.1 billion to 7-7 billion pounds of carbon dioxide (CC>2) not released to the atmosphere. Fewer
cleaning cycles and less acid per cycle result in a realized annual hazardous waste reduction of
76 million to 230 million pounds for all plants together.
Cytec Industries Inc.
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Buckman
International, Inc.
Enzymes Reduce the Energy and Wood Fiber Required
to Manufacture High-Quality Paper and Paper board
Innovation and Benefits
Traditionally, making strong paper required costly wood pulp, energy-intensive treatment,
or chemical additives. But that may change. Buckman's Maximyze'8' enzymes modify the
cellulose in wood to increase the number of "fibrils" that bind the wood fibers to each other,
thus making paper with improved strength and quality—without additional chemicals
or energy. Buckman's process also allows papermaking with less wood fiber and higher
percentages of recycled paper, enabling a single plant to save $1 million per year.
The paper and packaging industry is an important part of the U.S. economy with product
sales of $115 billion per year and employment of about 400,000 people. Previously, papermakers
who needed to improve paper strength were limited to adding costly pulps, increasing mechanical
treatment that expends significant energy, or using various chemical additives such as glyoxalated
polyacrylamides and polyacrylamide copolymers.
Enzymes are extremely efficient tools for replacing conventional chemicals in papermaking
applications. Buckman's Maximyze® technology consists of new cellulase enzymes and
combinations of enzymes derived from natural sources and produced by fermentation. These
enzymes were not previously available commercially. Wood fibers treated with Maximyze®
enzymes prior to refining (a mechanical treatment unique to papermaking) have substantially
more fibrils that bind the wood fibers to each other. Maximyze® enzymes modify the cellulose
polymers in the wood fiber so that the same level of refining produces much more surface area
for hydrogen bonding, which is the basic source of strength in paper. As a result, Maximyze*
treatment produces paper and paperboard with improved strength and quality.
Maximyze'8' improves strength so the weight of the paper product can be reduced or some
of the wood fiber can be replaced with a mineral filler such as calcium carbonate. Maximyze®
treatment makes it possible to use higher percentages of recycled paper. Maximyze*' treatment
uses less steam because the paper drains faster (increasing the production rate) and uses less
electricity for refining. Maximyze'8' treatment is less toxic than current alternatives and is safer
to handle, manufacture, transport, and use than current chemical treatments. These and other
benefits are produced by Maximyze® treatment, a biotechnology that comes from renewable
resources, is safe to use, and is itself completely recyclable.
The first commercial application began with the production of fine paper within the past
two years. In 2011, a pulp and paper manufacturer in the Northwest began to add Maximyze*
enzymes to the bleached pulp used to produce paperboard for food containers. This change
increased machine speed by 20 feet per minute for a 2 percent increase in production. It also
reduced the level of mechanical refining by 40 percent for a substantial savings in energy. Finally,
it reduced the basis weight (density) of the paper by 3 pounds per 1,000 square feet without
changing the specifications for quality. Overall, Maximyze'8' treatment reduced the amount of
wood pulp required by at least 1 percent, which reduced the annual amount of wood needed to
produce the food containers by at least 2,500 tons. Buckman estimates that using Maximyze*
technology for this one machine can save wood pulp equivalent to 25,000 trees per year. Another
large mill producing fine paper has used Buckman's technology since January 2010 and saved
over $1 million per year. Since introducing this new technology, Buckman has expanded it and is
now applying it successfully in over 50 paper mills in the United States and beyond.
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Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of
Diary I Aldimines
Imines are essential intermediates in many pharmaceutical syntheses. For example, diaryl
aldimines are feedstocks for blockbuster drugs such as Taxol'*1 (used for chemotherapy) and
Zetia® (used to reduce cholesterol). Diaryl aldimines added to polyethylene increase its
photodegradation in the environment. Unfortunately, traditional syntheses of diaryl aldimines
often require hazardous solvents and include energy-intensive, multihour reflux steps. Although
some imine syntheses use more benign solvents or conditions, they still require long reaction
times, recrystallization, or other environmentally unfriendly procedures.
Recently, Professor Bennett found that ethyl L-lactate, an FDA-approved food additive, can
replace the hazardous solvents commonly used to synthesize imines. Her method is extremely
efficient under ambient conditions and requires less solvent than published methods. It has
a median yield of over 92 percent and a median reaction time of less than 10 minutes. The
resulting imines are usually pure enough without recrystallization, avoiding additional waste.
Professor Bennett's method "tunes" the polarity of ethyl L-lactate by adding water. The starting
materials remain dissolved, but the imine crystallizes out of solution as it forms. Although
traditional methods often drive reactions forward by removing water, Professor Bennett's
method drives the reaction forward by removing the product through crystallization. To date,
she and her undergraduate research students have synthesized nearly 200 imines using this
method; her students in teaching labs have made more than half of these in a green chemistry
project. In summary, the ethyl L-lactatc 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
published methods.
A patent application for this method was published in 2011. Professor Bennett is now studying
these imines in biological and other applications. All are fluorescent and some are photochromic.
Several show promise as fluorescent cell markers and antibacterial agents.
Sustainable Molecular Design through Biorefineries:
Biomass as an Enabling Platform for Safe
Oil- Thickening Agents (Amphiphiles)
Non-polymeric amphiphiles can form molecular gels or viscoelastic materials when they
self-assemble by noncovalcnt interactions such as surface tension and capillary action. Amphiphiles
can immobilize a large pool of organic or aqueous solvent into a gel. A wide variety of amphiphiles
are currently derived, at least in part, from nonrenewable resources. In addition, their synthesis
frequently requires multiple steps, energy-intensive purifications, and complex, expensive
catalysts. Structuring an amphiphile such as vegetable oil into a gel alters its physical properties
with or without altering its chemical properties. Current structuring agents and methods used for
food tend to increase the content of saturated fatty acids and tram-fatty acids in oils, which may
increase the risk of vascular and heart disease.
Professor John and his group have developed potent amphiphiles from biobased resources using
enzyme-mediated transesterification of sugar alcohols with fatty acid donors. Upon self-assembly,
these amphiphiles produce soft materials in aqueous and organic solvents. These amphiphiles
exhibit superior ability to structure vegetable oils without increasing their saturated fatty acids.
They are also nontoxic and biodegradable. The ease of synthesis and cheap raw materials translate
Professor
of
Chemistry &
Biochemistry,
State Uniwersity of
York Oneonta
and
Foundation
John,
of Chemistry, The
City College of the
City Uniwersity of
York
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of Chemistry,
Uniwersity of
California,
Minna fa ma,
of
Chemistry
Biochemistry, Texas
Tech Uniwersity
into low-cost production of efficient sugar-based amphiphilic gelators. In addition, these
self-assembled gels have a remarkable ability to trap highly volatile pheromones, and release
them slowly, so they remain effective longer. Another application is environmentally benign oil
spill recovery: when added to an oil-water mixture, Professor John's amphiphiles can selectively
partition into the oil phase and convert it to a gel. This technology offers the potential to replace
current oil structuring agents with safe, biobased amphiphiles resulting in enhanced performance
at lower cost.
Currently, Professor John is developing next-generation, biobased amphiphiles to
structure hydrophobic liquids such as vegetable oils and related compounds for food and
cosmetic applications. Several food and personal care companies have expressed interest in
licensing this technology.
Chemical Conversion ofBiomass into New Generations
of Renewable Fuels, Polymers, Value-Added
Products
The gradual decline of the prevailing, worldwide petroleum economy is creating an
extraordinary need for alternative technologies and, hence, 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 lignocellulose into its
monosaccharide components, then derive useful products from the monosaccharides efficiently
and inexpensively. The most successful schemes will be those that (1) produce the highest yields,
(2) minimize capital and operating expenses, and (3) allow feedstocks from the most sources.
In 2008, Professor Mascal and his group described a process that meets all three objectives.
Their method involves digestion of cellulose in a biphasic aqueous acid—organic solvent reactor
to give remarkably high yields of the novel organic platform chemical, 5-(chloromethyl) furfural
(CMF). The method works equally well on raw biomass, producing not only CMF from the
cellulose of the feedstock, but also furfural itself from the C5 sugar fraction (i.e., hemicellulose).
It uses all of the carbohydrate in the biomass without requiring that lignin first be stripped from
the lignocellulose.
Recently, Professor Mascal has upgraded his technology: it now produces an overall
89 percent yield from cellulose consisting of CMF (84 percent) and levulinic acid
(LA, the well-known carbohydrate breakdown product) (5 percent). The new process requires 20-
fold less solvent and recycles solvent after use. The same method processes sucrose into CMF and
LA in a remarkable 95 percent overall yield. The method also works well on oil seed feedstocks
and leads to a 25 percent increase in biodiesel production from safflower seeds. No other
method produces simple organic products directly from cellulosic materials with comparable
yields. Important CMF derivatives include biofuels, renewable polymers, agrochemicals, and
pharmaceuticals. The green tech companies Micromidas and Incitor technology have adopted
the technology with backing from major chemical and energy company partners.
Highly Efficient, Practical Mono hydro lysis of
Symmetric Diesters to Half-Esters
Half-esters have considerable commercial value: they are highly versatile building blocks for
polymers, dendrimers, and hyperbranched polymers that have applications in many industrial
products. Because the two ester groups in the symmetric diesters are 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
10
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are difficult to separate and therefore, generate a large amount of undesirable waste. Alternate
ring-opening reactions of cyclic acid anhydrides to halt-esters are also undesirable because they
require hazardous organic 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 easily made from inexpensive precursors. Water
is among the most environmentally friendly solvents and is the least expensive of all solvents.
Water-mediated desymmetrization of symmetric organic compounds is, therefore, of tremendous
synthetic value and can make a significant contribution to creating greener reaction conditions.
Professor Niwayama pioneered an environmentally safe, highly efficient, practical ester
monohydrolysis of symmetric diesters to half-esters. In this reaction, aqueous sodium hydroxide
(NaOH) or potassium hydroxide (KOH) is added to a symmetric diester suspended in water
at 0 °C that may also contain a small amount of an aprotic cosolvent such as tetrahydrofuran
(THF). Monohydrolysis occurs at the interface between the aqueous phase and the organic
phase containing the diester. The reaction produces pure half-esters in high to near-quantitative
yields without hazardous organic solvents or dirty waste products. Wako Chemicals USA and
Kishida Chemical Company have licensed the technology and 10 resulting half-esters are now
available commercially.
Improved Resource Use in Carbon Nanotube Synthesis
via Mechanistic Understanding
Carbon nanotube (CNT) production by catalytic chemical vapor deposition (CVD)
currently exceeds 300 tons per year and is growing. The current CVD process has very low yields
(3 percent or less) and high energy requirements. Emissions from ethene- and H?-fed CVD
reactors contain over 45 distinct chemicals including: the potent greenhouse gas, methane;
toxic and smog-forming compounds, such as benzene and 1,3-butadiene; and trace quantities
of polycyclic aromatic hydrocarbons. Eliminating thermal treatment of the feedstock gases may
prevent the formation of unwanted byproducts, reduce energy demands, and improve overall
control of the synthesis, but heating the feedstock gas is necessary to generate the critical,
previously unidentified, CNT precursor molecules required for rapid CNT growth.
Using in situ CNT height measurements and gas analysis, Professor Plata and her
group identified the heat-generated compounds correlated with rapid CNT formation
(e.g., propyne and but-l-en-3-yne). She then mixed each of these chemicals with typical feedstock
gases (C2H4 and H2) without preheating and tested them with a heated metal catalyst. She found
that several alkynes (e.g., ethyne, propyne, and but-l-en-3-yne) accelerate CNT formation. This
new mechanism for CNT formation features C—C bond formation between intact chemical
precursors, similar to polymerizations. It challenges the accepted hypothesis that precursors must
completely dissociate into C or C-2 units before '"precipitating" from the metal.
Using these mechanistic insights, Professor Plata can form high-purity CNTs rapidly. Her
technology improves yields by 15 fold, reduces energy costs by 50 percent, and reduces the
ethene and H? starting materials by 20 and 40 percent, respectively. It also reduces unwanted
byproducts by over 10-fold (translating to ton-sized reductions in toxic and smog-forming
chemicals and greenhouse gases). The reduced starting materials and energy requirements also
lower the cost of CNTs without sacrificing product quality. A commercial CNT manufacturer
has licensed this patent-pending work.
L.
Plata, Department
of Civil and
Environmental
Engineering,
Uniwersity
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Professor T. ¥.
(Baby) RajanBaby,
Department of
Chemistry, The Ohio
University
Subramaniam,
Department
of Chemical
Petroleym
Engineering,
University of
Kansas
Ethylene: A Feedstock for Fine Chemical Synthesis
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. Ideally, 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 can be 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-arylbutcnes, 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-diencs 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 20J?-derivatives,
(-)-desoxyeseroline, pseudopterosin A—F, G—J, and K—L aglycones, and helioporins. These
syntheses require fewer steps than traditional methods and produce uncommon configuradonal
isomers. In 2010 and 2011, Professor RajanBabu published five papers on this work.
A Truly Green Process for Converting Ethylene to
Ethylene Oxide
The LeFort process, the only industrial process currently used to make ethylene oxide (EO),
emits huge amounts of carbon dioxide (CC>2, about 3.6 million tons/year). This venerable
gas-phase technology also presents safety hazards due to the explosive potential of heated ethylene
and oxygen gases.
At the Center for Environmentally Beneficial Catalysis (CEBC), Professor Subramaniam and
his colleagues are developing an alternative green technology for EO manufacture. In the CEBC
process, a highly reactive oxidation catalyst, methyltrioxorhenium (MTO), transfers an oxygen
atom from hydrogen peroxide (HbC^) to ethylene with total selectivity, high conversion, no
substrate or solvent burning (to cause CO2 emissions), and no explosion hazard.
Despite requiring an H?O2 oxidant and rhenium-based catalyst that cost more than the LeFort
system's CH oxidant and silver catalyst, the CEBC process can potentially compete economically
if it has reliable in-service lifetimes of 2—3 months. Experiments indicate that the CEBC system
should be capable of this critical in-service lifetime. Mechanistic studies with isotopic tracers
identified only one detectable mechanism tor catalyst destruction and conditions necessary to
avoid it. CEBC will soon attempt long-term, continuous process operations.
The CEBC process has relatively high productivity (40—50 percent versus LeFort
10—15 percent) because it exploits the critical properties of ethylene to greatly increase its
solubility. For similar production capacities, the carbon footprint of the CEBC process is net
12
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23 percent lower than the LeFort process; thus, the additional carbon emissions from
manufacturing H2O2 are considerably less than the emissions eliminated by not burning
substrate or product. The CEBC process is the first economically competitive alternative to the
LeFort Process. The new EO process excels in conversion, selectivity, safety and sustainability,
and the two processes appear to be comparable in manufacturing costs and productivity. A U.S.
patent for this process was allowed in 2011.
A Novel Bacteriophage-based Test to Identify MRSAI
MSSA Acquired Infections
At the Colorado School of Mines (CSM), Professor Voorhees and his colleagues have developed
a bacteriophage (phage) amplification platform that rapidly identifies Staphylococcus aureus and
determines whether it is methicillin resistant (MRSA) or methicillin susceptible (MSSA) without
extensive bacterial culturing. CSM licensed the technology to Micro Phage, which was founded in
2002 by Professor Voorhees and Mr. Jack Wheeler to provide medical devices. These point-of-care
devices fulfill needs such as determining S. aureus susceptibility while reducing the nonrenewable
materials used in manufacturing and the generation of medical waste.
Phages are viruses that infect bacteria in a species-specific fashion and then multiply rapidly.
The amplification process can generate up to a 105 increase in phage and reduce incubation
times to 1—5 hours down from 24—48 hours for traditional microbiological culture assays. The
MicroPhage and CSM KeyPath™ test is conducted with modern chemical detection methods on
a millilitcr scale. The test resembles a typical immunoassay whereby a blood culture containing a
suspected pathogen is added to two reaction tubes: one containing phage and a nutrient media;
and the second containing phage, media, and methicillin. The test samples are mixed with the
tube contents and incubated, followed by analysis on a dual-track lateral flow immunoassay strip.
A positive result on the first track shows the presence of S. aureus, A positive result on the second
track shows that the S. aureus is also methicillin-resistant. The manufacturing and use of the
KeyPath™ kit address several of the 12 principles of green chemistry.
This phage amplification platform is the first and only rapid in vitro diagnostic test approved
by the U.S. Food and Drug Administration (FDA) to identify bacteria directly and determine
their antibiotic resistance or susceptibility. During 2011, the FDA gave 501 (k) approval for the
sale of these human diagnostic devices and sales began in the United States.
Biobased Polymers and Composites
Professor Richard Wool's research has shown that recent advances in green chemistry, genetic
engineering, composite science, and natural fiber development offer significant opportunities
for new, improved materials from renewable resources that are recyclable, biocompatible, and
biodegradable, thereby enhancing global sustainability. He typically makes composite resins from
highly saturated plant oils such as soy or linseed oils and makes pressure-sensitive adhesives,
coatings, and elastomers from high oleic oils. When he combines his biobased resins with
natural plant and poultry fibers, starch, and lignin, he can produce new low-cost composites,
pressure-sensitive adhesives, elastomers, and foams that are economical in many high-volume
applications. These high-performance composites are designed for use in energy-efficient solar
integrated roofs, wind foil blades, hurricane-resistant housing, sub-aqua hydro turbines, and
hydrogen storage, in addition to agricultural equipment, automotive sheet molding compounds,
civil and rail infrastructures, marine applications, electronic materials, and sports equipment.
Professor Wool makes foams, usually from various mixtures of oils depending on the required
rigidity, using carbon dioxide (CC>2) as the blowing agent. Recently, he developed a biobased
foam to replace polyurethane and its toxic precursors, methylene diphenyl diisocyanate (MDI)
and toluene diisocyanate (TDI). Professor Wool developed it in collaboration with Crey Bioresins;
currently, several packaging and automotive suppliers are exploring this foam.
Professor Kent
Voorhees,
Department of
Chemistry
Geochemistry,
of
MicroPhage, Inc.
P.
Composites
from
Resources
Center
for Composite
Materials,
University of
Delaware
13
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In collaboration with Crey Bioresins and Dixie Chemical TX, Professor Wool developed
biobased composite resins that have been in worldwide distribution since 2011. Also in
2011, Professor Wool invented eco-leather, made from natural fibers including chicken feathers,
flax, and plant oils. This breathable leather substitute can potentially replace 50 billion pounds
of toxic waste currently generated by the leather industry. Nike and Puma are exploring this
technology.
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Geothermal Heat Pumps: A Greener and More
Energy-Efficient Renewable Energy Resource
Because buildings account for nearly 40 percent of U.S. energy consumption and greenhouse
gas emissions, they are a prime target for energy conservation. Although geothermal heat
pumps (GHPs) save energy in the range of 30—60 percent compared to typical heating and
air conditioning units, their high initial cost and long payback period hamper their adoption.
Today's GHPs use propylene glycol—water or ethylene glycol—water mixtures as circulating fluids
in their ground source loops. Ethylene glycol is a toxic chemical that presents environmental risks
and disposal problems.
ACTA Technology has developed fluids containing nanoparticles (i.e., nanofluids) with
improved heat-transfer efficiency that can reduce the lifecycle cost of GHPs by 17 percent.
Adding nanoparticles to propylene glycol—water mixtures improves their heat transfer by
48 percent. ACTA also improves the heat transfer of Paratherm*' LR (a food-grade, heat-transfer
oil) by adding alumina nanoparticles at 2 percent by weight and a surfactant. The nanofluid
Paratherm'K LR is a better heat-transfer fluid than either ethylene or propylene glycol mixtures.
Because ACTA's nanofluids increase the heat transfer rate of the ground loop in a GHP, the
ground loop can be smaller and the GHP can pump less fluid. This technology reduces both the
initial and lifecycle costs.
ACTA manufactures nanoparticles by a pyrogenic (flame) process. The resulting fumed
nanoparticles have large surface-area-to-volume ratios that increase the heat-transfer rate and
decrease the thermal response time. They arc hydrophilic, with hydroxyl groups over approximately
40 percent of their surfaces. They are easily removed from nanofluids for recycling.
ACTA's technology offers circulating fluids for GHPs without the harmful effects of ethylene
glycol. These greener nanofluids could also improve the fuel economy of automobiles because
radiators could be smaller with less fluid to pump. ACTA applied for a U.S. patent for their
technology in 2011.
Producing Chemicals and Carbon from Waste Tires,
Plastics, Carpet, and Biomass
Vast amounts of waste tires, plastics, and biomass have been discarded in landfills because
there was no practical way to dcpolymcrizc them for reuse. BCD Group-II has developed
catalytic transfer hydrogenation (CTH), a modified base-catalyzed decomposition (BCD) process
that depolymerizes plastics, tires, rubber, other polymers, and biomass into chemicals or solid
products with carbon contents of at least 84 percent. The CTH process is non-oxidative. Unlike
pyrolysis and liquefaction processes that require temperatures of 450—700 °C, the CTH process
converts polymers into reusable chemicals and carbon at 130—300 °C within 30—90 minutes. The
proprietary reaction medium is composed of an alkali metal carbonate or hydroxide, a hydrocarbon
donor/solvent (usually a high-boiling aliphatic hydrocarbon), and a proprietary catalyst/water
absorption agent. Reactive hydrogen from the hydrogen donor breaks bonds between hctcroatoms
to produce monomers, oligomers, polymers from copolymers, and sodium salts of anions.
Products are also easily converted into syngas. Depolymerization of polyester, polyurethane,
polycarbonates, or carpets by existing technologies requires much higher temperatures, higher
pressures, and more expensive reagents.
CTH technology can replace coke, a traditional fuel in solid oxide fuel cells (SOFCs). Coke
production from coal requires processing for 16—24 hours at temperatures of around 2,000 °C.
The CTH technology produces carbon from tires and biomass that is useful as SOFC fuel.
ACTA Technology,
Inc.
Group-II, Inc.
15
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Blue Marble
Biomaterials LLC
Colonial Chemical,
Inc.
A U.S. patent application describing this technology was submitted (Provisional Application
# 61/571,383) on July 7, 2011. In 2011, BCD Group-11 and C-4 Polymer Inc., of Chagrin
Falls, OH, completed laboratory-scale studies to depolymerize and recover polypropylene from
copolymer waste generated by the food packaging and auto industries. BCD Group-II expects
to complete pilot-scale tests and initiate commercial development during 2012. Licensees of the
original BCD process and an India chemical firm have expressed interest in CTH technology;
the Environmental Business Cluster in Silicon Valley, California, will present this technology to
venture capitalists.
Greening the Design of Chemical Production with Microbes
Currently, chemical synthesis using energy-intensive processes and fossil-based materials
produces the majority of fine chemicals. In contrast, the biosynthesis of fine chemicals from
biobased feedstocks has demonstrated feasibility and promise, however, over the past few years.
Blue Marble Biomaterials is developing microbial systems to lower the carbon intensity and
improve the lifecycle sustainability of fine chemical production.
Blue Marble has developed a proprietary combination of microbes that produce a wide variety
of fine chemicals and chemical intermediates including carboxylic acids, esters, thiols, and other
organosulfur compounds in a single batch. Blue Marble's unique polyculture fermentation
uses no genetically modified organisms and resists environmental stress. This fermentation can
process low-cost, nonsterile lignin, cellulose, and protein-based waste byproducts from food,
forestry, and algae companies without chemical or thermal preprocessing. Using these feedstocks
for fermentation prevents landfilling or burning them and abates approximately 15.28 tons of
carbon dioxide equivalents (CC>2eq) per ton of feedstock. Compared to microbial systems that use
carbon- and energy-intensive virgin or preprocessed plant materials, Blue Marble's system recycles
waste biomass, capturing the carbon it contains.
In 2010, the company scaled up production to a commercial facility in Missoula, MT. This
facility is currently undergoing food-grade and kosher certification. It will operate at 100 percent
capacity in the first quarter of 2012. Each year, it will use 860 wet tons of feedstock to produce
414,900 kg of carboxylic acids, esters, thiols, and other organosulfur compounds. An on-site
water recycling system will reuse 75 percent of the water required for fermentation, saving
574,000 gallons of water per month. Finally, all biogas from the fermentation system will run
through an algae remediation system to reduce facility emissions by scrubbing CCH and methane.
Blue Marble is working with several major manufacturers in the flavoring, food, and personal care
industries and with Sigma-Aldrich Fine Chemicals toward global distribution of seven compounds.
Sugd^Nate: A Safer, Milder, Greener Surfactant
Although lauryl sulfate and its ethoxylated version, lauryl ether sulfate, are the two most
common anionic surfactants used in formulating shampoo, body wash, and other personal
care products, these ingredients are highly irritating to eyes and skin. Products formulated
with ethoxylated lauryl ether sulfate also contain various levels of 1,4-dioxin, a probable
human carcinogen. Finally, a large percentage of these surfactants are made from ethylene, a
nonrenewable petroleum feedstock.
Colonial Chemical has developed sulfonated alkyl polyglucosides as safer surfactants: they
replace lauryl alcohol with alkyl polyglucosides as the hydrophobic component. These unique,
patented surfactants represent a breakthrough in mild surfactant technology. They are naturally
derived, biodegradable raw materials that are nearly 90 percent renewable and could reach
100 percent renewable as development progresses. These new surfactants do not irritate eyes or
skin, allowing formulators of personal care products to use totally irritation-free ingredients.
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Unlike ethoxylated lauryl ether sulfates, Colonial Chemical's surfactants are completely free
of dioxin. An unexpected property is their ability to withstand microbial contamination.
Outside testing showed that Suga®Nate 160 has reasonably good antimicrobial activity at the
16 percent active level, which is a normal concentration for a primary surfactant in higher-end
shampoos. As a result, Suga®Nate can reduce or even eliminate the antimicrobial additives used
in formulations.
The Suga®Nate synthesis has added benefits: it is atom-economical; sodium chloride is
the only byproduct; and water is the only solvent. The relatively mild reaction conditions are
closer to ambient than those of competing surfactants, and there is no need for separation
or purification. The toxicity of these new surfactants is much lower than that of competing
products, and the new surfactants are even less toxic than their starting materials. In 2011,
Suga'*'Nate was certified as a biobascd product by the U.S. Department of Agriculture (USDA).
Glycerol ten-Butyl Ether (GTBE): A Bio fuel Additive
for Today
Current petroleum-based additives for boosting octane in gasoline improve the
miles-per-gallon (mpg) of vehicles, but not significantly. The traditional fuel additive,
methyl fert-butyl ether (MTBE), has been phased out in many states due to its toxicity and has
no obvious replacement.
Glycerol tert-butyl ether (GTBE) is a high-value, biobased fuel additive that improves the
combustion and efficiency of petroleum and biobased fuels. CPS Biofuels has developed a process
to make GTBE from waste glycerol, a low-value, high-volume byproduct of biodiesel production.
CPS makes GTBE by acid catalysis of glycerol and isobutylene or other appropriate olefins
followed by fractional distillation. Sulfuric add is the preferred acid catalyst. Although GTBE can
have up to three ether linkages, it is preferable to have at least one or two free hydroxyl groups to
hydrogen-bond with ethanol and help lower its vapor pressure.
GTBE is a biobased, nontoxic, biodegradable alternative fuel oxygenate and octane booster that
helps fuel combust more completely and improves fuel efficiency with cleaner resulting emissions.
It both improves gas mileage and reduces greenhouse gas (GHG) emissions; with petroleum diesel
fuels, it reduces up to 35 percent of particulates. It is useful as a fuel system icing inhibitor (FSII)
in military (JP-8) and commercial (Jet A) kerosene-type jet fuel. GTBE can replace PRIST*', the
existing jet fuel FSII, which is severely detrimental to human health.
CPS is focusing on improving the efficiency of the ElO and El 5 blends of biofuels for
the existing energy infrastructure. GTBE fuel additives are compatible with the U.S. energy
infrastructure, providing tremendous advantages over alternatives that require new production
facilities or new engines for vehicles. CPS recently completed manufacturing trials, and testing of
GTBE showed extremely efficient, essentially emission-free combustion and an octane rating over
120. GTBE has been commercially available as CPS PowerShot™ since January 2011.
Formaldehyde-Free, High-Strength Biocomposites fiom
Sustainable Resources
The formaldehyde and volatile organic compounds (VOCs) used to make conventional
coatings, binders, and laminates for the wood composites in furniture contribute significantly
to indoor air pollution. e2e Materials is commercializing biocomposite products that contain no
formaldehyde or VOCs and arc made without hydrocarbons or toxic feedstocks.
e2e's biocomposites are made from lignocellulosic bast fibers, soy protein, and plant
polysaccharides; they are biodegradable at the end of their useful lives. The long bast fibers, from
sources including kenaf, jute, flax, and hemp, are lightweight and contribute to higher strengths
in ways that the short wood fibers used in particleboard and medium-density fiberboard (MDF)
CPS Inc.
Inc.
17
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Ecology
Inc.
cannot. The soy protein and plant polysaccharidcs are feedstocks for a natural resin system that
binds the fibers together into biocomposites.
e2e's biocomposite material is 3—4 times stronger than today's wooden particleboard and
MDE e2e can mold its biocomposites into three-dimensional parts (i.e., net-shape them into
whole, structural components) that replace traditional 4 x 8-foot sheets. Net-shaping can create
stronger components by molding them as one part rather than assembling them from pieces.
The e2e biocomposites also retain screws better than wood composites. These features combine
to create stronger furniture while reducing the total amount of material and weight. e2e's
biocomposites are inherently fire-resistant because they contain a modified soy protein instead
of petrochemical resins. They use only 19 percent of the embodied energy of today's products
because the manufacturing process requires less energy and regionally integrated manufacturing
minimizes transportation costs.
Products made from todays wood composites have a $100 billion market. e2e is replacing
those products with higher performing, safer, more efficient, and more cost-effective
biocomposite-based products. These products complement its proprietary biocomposite core
with green, cost-effective coatings. Following successful pilot production in 2011 and responding
to strong demand for its commercial office furniture products, e2e recently announced a
100,000 square foot manufacturing expansion.
Generally Recognized as Safe (GRAS) Coatings
Using materials that are generally regarded as safe (GRAS) for human consumption, Ecology
Coatings has developed coatings that can be applied to food or used in food packaging. These
GRAS coatings protect food from outside elements, are safe for human consumption, and use
natural ingredients, not plastics or other chemicals derived from fossil fuels. GRAS coatings have
barrier properties to air, water, and solvents that will allow them to replace coatings originating
from fossil fuels, especially plastic coatings made using acrylates and mcthacrylatcs. GRAS
coatings have the potential to make food packaging greener and more sustainable by eliminating
toxic plastics. Their environmental friendliness could allow increased recycling of food packaging.
The coating includes a polypeptide such as albumin, a denaturing agent, and water as
the solvent. It can also include a natural gum, a flavoring agent, a dye, a de-foaming agent,
maltodcxtrin, and an oil. When the mixture is exposed to UV light, it cures and cross-links,
but does not coagulate. Used on food, the nominated coating will inhibit oxygen exposure and
increase shelf life. GRAS coatings on food packages will also resist grease and can substitute for
polyethylene or other petroleum-based coatings. Ecology Coatings' GRAS coating can also be
used as a photoinitiator with conventional UV-curable materials that are approved for direct
contact with food.
GRAS coating components in powdered form not only promote UV curing but can extend
the coverage of pigments. In this use, the nominated technology could replace silica fillers. Finally,
the GRAS coating can be used as a matting agent, which cures into the finished film and enhances
the UV-curing process. Combined with other biobased additives, the GRAS coating can produce
a rough surface that resists water and grease migration. In 2010, Ecology Coatings filed a patent
application for this technology.
Zero-Emission Production of the Green Lithium Ion
SuperPolymei® Battery
The lithium ion cell and battery industry is a multibillion-dollar business that also pollutes
the environment. The manufacturing process for lithium ion electrodes includes coating the
electrodes with the toxic solvent N-methyl pyrrolidone (NMP), then removing NMP by slow
18
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evaporation in a furnace up to 100 meters long. Although manufacturers attempt to recover
NMP, some escapes. NMP is listed as potentially causing birth defects by environmental agencies
in California, Japan, the European Union (EU), and elsewhere. The large quantities of toxic
solvents in cell and battery manufacturing also lead to high costs for capital equipment and plant
operations as well as uncertain future liabilities.
Electrovaya's SuperPolymer® batteries are based on a nanostructured lithiated manganese oxide
material that allows more energy to be stored in a smaller space, making applications smaller,
lighter, and more powerful. They also produce approximately 25 percent less carbon dioxide
(CC>2) over their lifecycle than do NMP batteries. Electrovaya developed a unique, nontoxic
process to manufacture its fuel cells that eliminates all solvents including NMP. Electrovaya has
also eliminated some energy intensive drying and solvent-recovery processes.
Electrovaya's SuperPolymer® batteries address the problem of energy generation and storage.
Advanced energy storage for plug-in hybrid electric vehicles and e-bikes can provide an alternative
to nonrenewable resources and reduce greenhouse gas emissions. Currently, Electrovaya is testing
its battery technology nationwide in a fleet of plug-in hybrid electric versions of Chrysler's RAM
pickup trucks and Minivans.
High-capacity energy-storage systems are essential if renewable sources are to supply a
significant portion of a grid's energy. Electrovaya's technology is useful for grid energy storage
systems to solve the power stability and energy storage problems associated with electricity
generated by renewable resources. Electrovaya recently delivered a 1.5 MW energy-storage system
to an electric utility in the Southwest United States for use with its photovoltaic operations.
Polymeric, Nonbalogenated Flame Retardants with Broad
Applicability in Multiple Industries
Traditional, halogenated, small-molecule flame retardant (FR) additives readily migrate
to the surface of plastic formulations, exposing humans to these often toxic chemicals and
diminishing their FR protection. Today, over 60 percent of FR plastic formulations are based
on halogen-containing additives like brominated and chlorinated hydrocarbons. Electronic
device manufacturers have instituted voluntary bans on halogen-containing FR additives; other
industries are also replacing them. Consequently, the plastics industry needs alternatives.
FRX POLYMERS® Inc. (FRXP) is the first company to develop polymeric forms of
phosphorus for use as nonmigrating, halogen-free FR additives that are also cost-effective. FRXP
converts diphenyl methylphosphonate (DPMP) into polymers with over 10 percent phosphorus.
These polymers have a limited oxygen index (LOI) of 65 percent, the highest LOI measured for
thermoplastic materials, indicating strong FR capability. They can be used alone or can deliver
FR performance and additional benefits to polycarbonate blends, polyesters, thermoplastic
polyurethane, unsaturated polyesters, epoxies, and polyureas. FRXP polymers can be used in
melt-processed fibers and blow-molded articles where previous FR additives could not. Being
polymeric, the FRXP materials allow the physical properties of plastics to remain essentially
unchanged. FR additives with phosphorus replacing bromine also should allow greater plastic
recycling.
The DPMP monomer synthesis has essentially quantitative yields. The polymer synthesis is
a solvent-free, melt-based process which only major byproduct, phenol, can be recycled into
starting monomers. FRXP expects less than 5 percent waste from its polymer and copolymer
production.
FRXP is scaling up its additives for use in electronic housings, industrial carpeting, textiles,
electrical connectors and switches, wires and cables, printed circuit boards, and transparent
laminates. Following Premanufacture Review under the Toxic Substances Control Act (TSCA),
the FRXP materials are proceeding toward global registration. FRXP plans to expand its current
polymer pilot plant from 50 to 100 metric tons per year (TPA) in early 2012 and is building a
2,500 TPA commercial plant for start-up in October 2013- 19
FRX Inc.
-------
Technology, Inc.
InfiChem Polymers,
LLC
Conserving Water and Eliminating Chemical Treatment
in Cooling Towers
Commercial HVAC and industrial cooling towers evaporate water to transfer heat to the
atmosphere. These systems use roughly 5 trillion gallons of water annually in the United
States, The aqueous environment in cooling towers presents four significant challenges
to sustained efficient operation: mineral scaling, corrosion, biological activity, and water
conservation. Traditional control measures require chemicals specific to each problem, many of
which are hazardous.
H-O-H Water Technology's ''Green Machine" is generating significant resource savings,
eliminating traditional chemical additives, and reducing chemical hazards and pollution. In
the Green Machine, carefully engineered electrolytic extraction of calcium carbonate from
recirculating cooling water controls deposit formation on heat exchangers and other surfaces.
Electrolysis of ion-rich water produces exploitable chemicals in situ so the system requires no
external reagents other than electricity.
The Green Machine contains steel tubes that constitute the cathodes of an electrolytic cell,
where water is reduced to form molecular hydrogen and hydroxide ion and where calcium
carbonate subsequently accumulates. Centered in each tube typically is the anode of the
electrolytic cell: a titanium rod coated with ruthenium and iridium oxides called a dimensionally
stable anode (DSA). The coating of the anode drives the oxidation of water to produce molecular
oxygen, hydrogen ions, and higher oxygen species such as hydroxyl free radicals and ozone. DSA
technology allows the efficient splitting of water at a low practical voltage potential. Recently,
H-O-H supplemented DSAs with anodes coated with boron-doped, ultrananocrystallinc
diamond (BD-UNCD), which controls troublesome calcium carbonate deposition, forms
chlorine in situ, and degrades organic components more efficiently. Microbiological control in
cooling water is significantly more efficient as well.
During 2011, Green Machines installed in 127 cooling water systems totaling 86,660 tons
of cooling capacity saved a total of 248 million gallons of make-up water including 44.7 million
gallons due to the new BD-UNCD technology.
InfiGreen Polyols
Polyurethane manufacturers are seeking to pursue sustainability by reducing their carbon
footprint, improving their green image, and cutting costs. The growing market for the polyols
used to make polyurethane is currently about 11 billion pounds, but has few green options.
Biobased polyols (primarily soy-based polyols) reduce polyurethane's carbon footprint, but have
significant consequences including higher prices for food and agricultural land. In addition,
polyurethane manufacturing generates significant amounts of scrap, and virtually all post
consumer polyurethane scrap goes into landfills.
With InfiGreen™ polyols and recycling technology, InfiChem Polymers is providing
sustainable, green, economical raw materials that are not biobased and do not divert land from
food production. This technology transforms polyurethane foams into InfiGreen1 M polyols with
over 60 percent recycled content for reuse in polyurethanes. The process liquefies scrap foam in
a reaction with glycol, and then transposes it into various InfiGreenIM polyols by propoxylation
or patent-pending chemical steps; it typically generates less than one percent waste. InfiChem
Polymers demonstrated its process on a pilot scale with both flexible and rigid foam scrap.
Substituting one pound of conventional petroleum-based polyols with InfiGrccn"™ polyols
reduces the carbon footprint by approximately two pounds of carbon dioxide (CC*2).
Polyurethane manufacturers can benefit from closed-loop recycling of their polyurethane
production scrap, which can significantly reduce their landfill costs and provide them with
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InfiGreen™ polyols at prices typically below those for conventional petroleum-based and
biobased polyols.
InfiGreen™ polyols are currently used in automotive seat cushions and in the construction
industry. InfiChem Polymers expects to reach its current capacity of one million pounds
of InfiGreen1 M polyols in late 2011; within 5 years, it expects sales of 50 million pounds in
NAFTA countries. With projected worldwide production of 180 million pounds of InfiGreen™
polyols, the company will consume approximately 106 million pounds of polyurethane scrap or
approximately 0.03 percent of all polyurethane produced.
Development Commercialization of Okie Estolide Esters
Each year, 2.4 billion gallons of lubricants are used in the United States, according to industry
and EPA estimates. Lubricants comprised of sustainable carbon that perform well in demanding
applications are in high demand. Naturally occurring vegetable oils (triglycerides) provide
excellent lubricity and have high viscosity indexes; they are also biodegradable, nontoxic, and
economically attractive. Their oxidative and hydrolytic instability and their poor performance
at low temperatures, however, exclude their use in passenger-car motor oils (PCMOs) and low
temperature environments.
LubriGreen has overcome the inherent disadvantages of vegetable oils and preserved their
favorable properties by derivatizing fatty acids from triglycerides into estolides, which are
oligomers of fatty acids. Patented oleic estolide esters are central to LubriGreeris technology.
Their synthesis proceeds by an acid-catalyzed Sx,-1 addition of the carboxyl of one fatty acid to the
site of unsaturation on another to form an estolide. (The catalyst is a recoverable, reusable organic
superacid.) The free acid estolides are then cstcrificd with a branched alcohol. The novel structure
of oleic estolides gives them excellent lubricity high viscosity indexes, and good cold temperature
properties. Like triglycerides, oleic estolides are beneficial in environmentally sensitive settings
because they are biodegradable and nontoxic. Because the estolides are fully saturated and their
secondary esters create a steric barrier to hydrolysis, they have good oxidative and hydrolytic
stability. Estolides are viable for the most severe lubricant and industrial applications, including
PCMOs, hydraulic fluids, greases, gear oils, metal working fluids, and dielectric fluids.
Estolides have the potential to displace a significant portion of the lubricant market,
reducing emissions and the release of hazardous chemicals into the environment. Test results
show that oleic estolide esters may also have advantages in performance and fuel efficiency over
petroleum-based PCMOs. LubriGreen is currently working with the world's largest formulators,
lubricant distributors, and others to commercialize its products during 2013.
Biobased Chemicals from Low-Cost Lignocellulosic Sugars
Most fermentation routes that produce industrial chemicals require glucose as the main
carbon source. These fermentations have significant disadvantages, however, due to the high cost
of glucose, the volatility of the sugar markets, and competition with the food and feed industries.
The substitution of inexpensive, abundant lignocellulose feedstocks for glucose can create a great
advantage for producing organic chemicals.
Lignocellulosic hydrolysates contain a variety of 5- and 6-carbon sugars as well as toxins
such as acetic acid, furfural, and 5-hydroxymethylfurfural (HMF). Because these toxins can
inhibit bacteria from metabolizing sugars to products, companies usually must remove them
by "detoxification" of the hydrolysates in a process that adds unit operations and cost to the
fermentation. Efficient fermentation of lignocellulosic hydrolysates requires microorganisms that
can metabolize both 5- and 6- carbon sugars as well as tolerate the toxins present in hydrolysates.
LubriGreen
My riant Corporation
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Myriant has successfully developed a proprietary process including evolved E. coli strains that
are able to metabolize multiple sugars simultaneously and can ferment lignocellulosic hydrolysate
without any detoxification. These proprietary biocatalysts are capable of fermenting low-cost,
non-food, lignocellulosic hydrolysate sugars as well as clean sugars to produce organic acids
including lactic acid and succinic acid.
Lifecycle studies comparing Myriant's biosuccinic acid technology to petroleum-derived
succinic acid showed a potential reduction in greenhouse gases (GHGs) of more than 50 percent,
Myriant's biosuccinic acid and biolactic acid will be used as drop-in and replacement chemicals
in current petroleum-based markets, Myriant is developing processes to manufacture biobased
butanediol, pyrrolidone, and acrylic acid.
In 2009, Myriant was awarded $50 million from U.S. Department of Energy (DOE),
which is supporting the company's commercialization of its lignocellulosic biosuccinic acid and
construction of a 30 million pound capacity biosuccinic acid facility in Lake Providence, LA.
This facility will use primarily £ coli strain KJ122 to produce succinic acid from sorghum flour.
inc. i High-Performance Polyohfrom CO2 at Low Cost
The vast majority of polyols currently used in coatings, foams, adhesives, elastomers, and
thermoplastic polyurethanes are derived exclusively from petrochemicals. Novomer has developed
a proprietary technology platform that transforms waste carbon dioxide (CCb) into very precise,
high-performance polyols at lower cost than polyols from either petroleum or natural oils.
Novomer's polyol technology platform combines several innovations. Novomer has developed
a breakthrough cobalt-based CO2~-epoxidc catalyst that is over 500-fold more active and far more
precise than past zinc-based catalysts. In 2011, Novomer modified its catalyst system with resin
bed technology to recover and recycle the catalyst without losing activity or selectivity, Novomer
wras also the first to develop lowr-molecular-wreight CC>2-based polyols using chain-transfer agents,
The manufacturing process for Novomer's CC^-based polyols is a proven, low-cost, synthetic
technology based on chemistry. It can be completed in existing chemical industry infrastructure
under mild reaction conditions with conversions of over 90 percent in short timeframes. Using
CO? cuts raw material costs nearly in half, yielding a significant cost advantage.
The environmental and human health benefits of Novomer's CO2-based polyol technology
platform are considerable. Because these polyols contain 40—50 percent CO2 by weight,
they can potentially sequester 10 billion pounds of CO2 per year in targeted polyol markets.
More important, they enable the chemical industry to eliminate 10 billion pounds per year of
petroleum-based raw materials, a source reduction that impacts the entire petrochemical value
chain. In addition, because Novomer polycarbonate polyols contain no bisphenol A (BPA), they
can potentially eliminate the use of BPA-containing resins in food-contact coatings.
Novomer is commercializing its polyols in several markets. Jointly with the Dutch company,
DSM, Novomer will introduce its first large-scale commercial polyol product for coil coating
applications in 2012. In partnership with industry-leading polyol producers, formulators, and
end users, Novomer is developing additional polyol products for footwear foams, rigid insulating
foams, and polyurethane adhesives.
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Electrodialysis Chromatographic Separation
Technology for Chlorine-Free Production of Potassium
Hydroxide and Hydrochloric Acid
The United States consumes approximately 2 billion pounds of potassium hydroxide (KOH)
per year. The traditional chloralkali process for KOH uses electrolysis of potassium chloride in
water and produces chlorine gas (C13), hydrogen gas (H2), and KOH. C13 is a hazardous air
pollutant (HAP) that faces declining demand due to the phase-out of chlorinated chemicals.
NSR has commercialized the first environmentally friendly, cost-effective alternative to the
chloralkali process in decades. NSR's new process manufactures 45—50 percent KOH and
7 percent hydrochloric acid (HC1). The process uses NSR's novel electrodialysis lonSel™ stacks,
which include bipolar membranes of specialty polystyrenes modified with ion exchange groups.
The novel design of lonSel™ stacks allows the cells to operate at high efficiency consume
40 percent less energy, and generate high-purity products. The process rearranges ions in solution
and is particularly suited to recycling salts generated in other applications including those
from the pulp and paper industries and from the environmental control systems in coal-fired
power plants.
NSR's process yields high-purity, food-grade products without mercury (a health hazard to
children) or oxidizing species like chlorate and hypochlorite. The lower energy consumption per
unit of KOH made by NSR's process allows smaller plants to produce equivalent amounts of
HC1 and KOH profitably. Smaller plants cost less, can be built close to end-users, and reduce
transportation hazards. NSR supplies food grade 7 percent HC1 to Archer Daniels Midland by
pipeline. This efficient transfer eliminates the unnecessary transport and accidental release of
fuming 35 percent HC1.
NSR's single plant eliminated the production of 2 million pounds of C17 during 2011; at
full capacity, it would eliminate the production of 10 million pounds per year of C12. NSR's
technology could potentially eliminate the production of billions of pounds of unnecessary C12.
each year.
Producing Industrial Chemicals by Fermenting Renewable
Feedstocks at a Lower Cost
Chemical producers are searching to meet growing worldwide demands for many of today's
industrial chemicals with renewable feedstocks and environmentally sustainable methods. The
transition to renewable feedstocks has been slow, however, because environmentally sustainable
processes must be cost-competitive with traditional petroleum-based chemicals.
OPX Biotechnologies (OPXBIO) has developed a proprietary platform technology called
Efficiency Directed Genome Engineering (EDGE™). This technology allows OPXBIO to
develop and engineer microorganisms and bioprocesses faster and less expensively than traditional
methods. OPXBIO can now develop multiple chemicals cost-effectively from multiple renewable
feedstocks.
In 2011, OPXBIO developed a bioprocess for biobased acrylic acid (bioacrylic acid). OPXBIO
used its EDGE1M process to engineer both a microorganism to produce 3-hydroxypropionic
add (3-HP) and a process to manufacture bioacrylic acid renewably. A key focus was
developing a microbial strain with increased cellular pools of malonyl-CoA, the first committed
intermediate in the 3-HP production pathway. Many commercial products may be derived from
malonyl-CoA, including fatty acids (and hence long chain alkanes), polyketides, and 3-HP.
Technologies,
Inc.
OPX
Biotechnologies,
Inc.
23
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Performance
LLC
An initial lifecycle analysis (LCA) indicates that OPXBIO's process for bioacrylic add would
reduce greenhouse gas emissions by more than 77 percent and crude oil use by 82 percent
compared to traditional acrylic acid synthesis from propylene. If the entire global market for
acrylic acid (4.5 million tons annually) were replaced with OPXBIO's bioacrylic acid, greenhouse
gas emissions would be reduced by more than 5 million tons annually, and industry's use of crude
oil would decrease by approximately 2.5 million tons.
In 2011, OPXBIO scaled up its process and demonstrated the fermentation and primary
purification of 3-HP at 3,000 liters. If dextrose feedstock costs $0.14 per pound, metrics
predict a commercial cost of bioacrylic acid at approximately $0.75 per pound. This cost is
competitive with the average cost ot petroleum-based acrylic acid in 2011, making the process
both environmentally and economically sustainable.
BURN-OUT™ Durable, Green, Nontoxic Flame Retardant
Each year, an estimated 4 billion pounds of polybrominated diphenyl ethers (PBDEs) are
used in flame retardant (FR) applications. There is growing evidence, however, that PBDEs
are toxic.
Performance Chemical has developed Burn-Out™ FR, a totally green, nontoxic, durable
replacement for PBDEs and other persistent, bioaccumulative, toxic FRs. The Burn-Out™
compound is made of materials that comply with U.S. Food and Drug Administration (FDA)
regulations for indirect food contact and safe for disposal. Phosphorus and nitrogen arc its
active ingredients; it is formaldehyde-free. In a fire, Bum-Out™ FR forms an intumescent,
thermal-insulating carbonaceous char that acts as a barrier between the burning and unburned
material. Inert gases, mostly carbon dioxide (CC>2) and water, dilute the combustion gases and
cool the surface. Phosphorous-containing compounds react to form phosphoric acid and cause
charring. The Burn-Out™ compound releases nitrogen gas and dilutes the flammable gases in
synergy with the phosphorus.
Burn-OutIM FR resists water, alcohol, oil, and grease, yet cleans up with soap and water.
Burn-Out™ FR contains ingredients that resist the growth of bacteria and fungi. In insulation
materials, Burn-Out™ FR resists the formation of airborne Legionella bacteria, which can
multiply in water systems and are a source of Legionnaires' disease.
In customer formulations, Burn-Out™ FR compounds offer potential cost savings of
20— 50 percent compared to current FRs containing halogen and PBDE—antimony. Performance
is equal to or exceeds that of other products. Burn-Out™ FR reduces landfill disposal costs
associated with hazardous materials.
Burn-Out1 M FR may be used in virtually all aqueous systems and many polymer systems.
Applications include paper, corrugated packaging, woven and nonwoven textiles, insulation,
ceiling tiles, construction materials (e.g., wood, urethane insulation, and steel intumescent
coatings), adhesives, paints, and other FR coatings, especially in the automotive, military,
and marine markets. Performance Chemicals is planning to test Burn-Out™ FR in
bedding and mattresses. Performance Chemicals commercialized Burn-Out™ FR in 2011.
RPS Environmental
Solytions, LP
Zero-VOC Cleaning and Remediation Technology
The pollutants in indoor environments can actually reach higher levels than those found
outdoors. Although several factors contribute to indoor air quality, fumes and residues from
the cleaning chemicals currently used in our homes, offices, and schools have a significant
negative effect on the quality of the air we breathe. Many common cleaners contain
dangerous and harmful chemicals that are carcinogens, neurotoxins, hormone disrupters, and
reproductive toxins.
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RPS Environmental Solutions has developed products without volatile organic compounds
(VOCs) or harsh chemicals that it is currently using in a wide range of cleaning products from
degreasers and odor eliminators to adhesive removers and pet care products. These products
are hypoallergenic, rapidly biodegradable, and have undergone rigorous testing to ensure the
greatest possible safety and efficacy. RPS carefully manages the entire lifecycle of its products from
manufacturing in a zero-discharge facility to using minimal-impact packaging. Independent
laboratory testing with the American Society for Testing and Materials International (ASTM)
D 4488 protocol for cleaning efficacy shows RPS's products to be 3.5 times more effective than
those of the leading ''green" competitor, over twice as effective as those of the most-recognizable
name-brand competitors, and over 30 percent more effective than those of the most powerful
competitor. Although many competitive products compromise safety for effectiveness, RPS
cleaning products are both safer and more effective than those of their competitors.
RPS technology has leveraged hydration—dehydration, metal ion reaction, surface charge
modification, and the mechanics of conversion to provide cleaning and remediation products
that are safer for use near people, pets, and plants. RPS technology not only eliminates the need
to produce many dangerous chemicals, but can actually remediate environmental damage caused
by many harmful substances and improve human health by improving indoor air quality. RPS
expanded and launched several product lines during 2011; RPS products have been recognized
by EPA's Design for the Environment partnership program.
Sodium Silicide: A New Alkali Metal Derivative for Safe,
Sustainable, and On-Demand Generation of Hydrogen
Sodium silicide (NaSi) is a stabilized, alkali metal silicide powder that reacts with any
water solution to generate hydrogen instantly. SiGNa's patented NaSi powder is modified to
delocalize the electrons across the clathrate, forming an air-stable, free-flowing powder.
In a fuel cell, NaSi produces pure hydrogen gas as needed at pressures lower than those in
soda cans. NaSi overcomes the most-significant challenges that have prevented lowr-temperature
proton exchange membrane (PEM) fuel cells from commercialization: storing high-pressure
hydrogen and building costly infrastructure. NaSi is clean, sustainable, inexpensive, easily
transportable, and safe for indoor use. Fuel cells powered by NaSi produce only hydrogen
and wrater vapor; they create no greenhouse gases, toxic byproducts, or harmful emissions.
Recyclable fuel cartridges deliver NaSi to any PEM fuel cell; once the NaSi is spent, the
nontoxic, environmentally benign residue can be recycled as an industrial feedstock.
SiGNa's NaSi technology offers significant environmental benefits throughout its lifecycle.
NaSi is manufactured from 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 can
reduce the release of greenhouse gases (GHG) by nearly 14 percent and significantly reduce
the amount of toxic materials entering the waste stream.
SiGNa's novel hydrogen-storage approach can enable cost-effective back-up and portable
fuel cells for the medical, military, transportation, disaster relief, and consumer electronics
industries. SiGNa's technology is proving that hydrogen fuel cells are not only commercially
viable, but even more high-performing and cost-effective than batteries or small 1C engines. For
example, NaSi can replace the combustion engine/gas back-up in battery-hybrid cars to extend
their range by 50 miles. Also, e-bikes powered by NaSi can go 3—4-times farther than bicycles
powered by lithium batteries. During 2011, licensee myFC commercialized PowcrTrekk, a
portable hydrogen charger, in Europe.
Chemistry,
Inc.
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Verdezyne, Inc.
Biobased Adipic Acid for Renewable Nylon
Polyurethane Resins
¥H Biotechnology,
Inc.
Adipic acid (CgHioCX}) is an important industrial dicarboxylic acid with an estimated global
market of $6,5 billion. It is a feedstock for nylon 6,6 and polyurethane resins. It is currently
produced from petrochemicals by the nitric acid catalyzed oxidation of cyclohexane. This process
generates a waste gas stream including nitrous oxide, non-methane volatile organic compounds
(VOCs), carbon monoxide, and nitrogen oxides. The production of adipic acid from renewable
resources would result in substantial reductions of environmental pollutants.
Verdezyne has engineered an industrial strain of the yeast Candida to produce adipic acid
from natural plant-based oils. This yeast normally grows on fatty acids as its sole carbon
source by cyclic degradation through its [3-oxidation pathway. A Candida strain in which
this pathway is completely blocked can convert these substrates to the corresponding
dicarboxylic acids by selective oxidation of terminal methyl groups through its co-oxidation
pathway to produce diacids with a chain-length distribution that precisely mimics that of its
plant-based oil feedstock. By engineering both the (3-oxidation and w-oxidation pathways of
yeast, Verdezyne has enabled the highly selective production of adipic acid from any plant-based
oil. This engineered strain tolerates saturating concentrations of adipic acid in the fermentation
broth, growing at the same rate and to the same density as in its absence.
In addition, Verdezyne has developed fermentation and downstream purification processes
to recover polymer-grade bioadipic acid from the fermentation broth and has synthesized nylon
6,6 fibers and pellets from bioadipic acid. The advantages of Verdezyne's biobased technology over
petroleum-based manufacturing include lower cost, sustainable feedstock supply, and a smaller
environmental footprint. Verdezyne estimates that its production costs will be 30—35 percent
lower than the petrochemical process. Verdezyne recently opened a pilot plant in Carlsbad, CA
to demonstrate the scalability of its process, validate its cost projections, and generate enough
biobased adipic acid for commercial market development.
Bacteriocins: A Green, Antimicrobial Pesticide
Pesticides are used worldwide to protect crops and structures, manage pests, and prevent
the spread of disease. Pesticides are intended to be toxic, but only to their target organisms.
Their intrinsic properties, however, lead these pesticides to pose risks for human health and the
environment. There is a continuing need for safer pesticides to replace those that are toxic to
nontargct species.
Through evolution, bacteria have acquired the ability to produce molecules such as bacteriocins
that inhibit other microorganisms. Bacteriocins are gene-encoded, ribosomally synthesized,
antimicrobial peptides that are often small in size (20—60 ami no acid residues). Bacteriocins
combine with negatively charged surface constituents of target bacteria, creating transmembrane
pores that make the target bacterial membrane permeable and thus kill the bacteria. Bacteriocins
are not toxic to eukaryotic organisms. They are generally recognized as safe (GRAS) by the
U.S. Food and Drug Administration. Moreover, they are currently considered for therapeutic
applications such as the development of new vaccines against pathogenic, multidrug-resistant
bacteria and as cytotoxic agents against human cancer cells.
VH Biotechnology has developed a novel, green bacteriocin composition for use as a
microbicide in commercial applications including pulp and paper mills, fuels, biofuels, cooling
water systems, and poultry farms. The bacteriocins are obtained by standard fermentation using
lactic acid bacteria. Two paper mills using these bacteriocins showed much lower bacterial counts.
In diesel fuel, bacteriocins reduced microbial levels by 99.95 percent over controls; in gasoline,
the reduction was 89 percent. When used to sanitize water on poultry farms, bacteriocins at
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100 grams per cubic meter of water were able to match the performance of chlorine at 12 grams
per cubic meter. VH Biotechnology developed this technology in 2008 and filed a U.S. patent
application for it in March 2010.
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Concrete-Friendly™ Powdered Active Carbon (C-PACM)
to Remove Mercury from Flue Gas Safely
Coal-fired power plants emit 45 tons of gaseous mercury into the air and produce
65-5 million metric (MM) tons of fly ash annually in the United States, Fly ash has a composition
similar to that of volcanic ash, and is an excellent replacement for cement in concrete. Currently,
about half the concrete produced in the United States contains fly ash. Of the 65.5 MM tons
of fly ash generated in 2008, more than 11.5 MM tons were used in concrete and 16.0 MM
tons were used in structure fills, soil modification, and other applications. According to EPA's
2008 report to Congress, federal concrete projects used 5-3 MM tons of fly ash in 2004 and
2005 to replace cement, saving about 25 billion megajoules of energy, saving 2.1 billion liters of
water, and reducing carbon dioxide (CCn) emissions by about 3.8 MM tons.
Powdered activated carbon injection (ACI) is a conventional technology that injects mercury
sorbents into flue gas in power plants and captures the mercury-laden sorbents in fly ash.
Although this reduces mercury emissions, the resulting fly ash is unsuitable for concrete and
requires disposal in landfills. It mercury contamination made all fly ash unsuitable tor use in
concrete, the 11.5 MM tons now used in concrete each year would require more than 33 million
cubic feet of new landfill space at a cost of about $196 million.
Albemarle designed, synthesized, developed, and commercialized its novel Concrete Friendly
mercury sorbcnt, Concrete-Friendly™ Powdered Active Carbon (C-PAC™) . C-PAC™ is
activated carbon with tailored pore structures and surface properties. Albemarle manufactures
C-PAC 1Mfrom renewable carbon sources using a greener synthesis that includes gas-phase catalytic
bromination. C-PAC1M removes large amounts of mercury from air, preserves the quality of fly
ash for concrete use, safely sequesters the mercury in the concrete, and eliminates the need for
new landfill space. Several power plants across the United States currently use C-PAC1M.
Upcycling Waste Plastic Bags into Valuable Carbon
Nanotubes Carbon Spheres
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 discovered, implemented, and
patented an environmentally friendly process to remediate or upcycle waste plastic bags (WPBs)
into CSs and CNTs. Argonne's solvent-tree, solid-state-controlled pyrolytic process heats WPB of
single or mixed types to 700 °C in a sealed chamber to produce pure CSs or CNTs. Systematic
characterization of the atomic structure, composition, and morphology ot the CSs and CNTs with
advanced, structural, spectroscopic, and imaging techniques has elucidated, the mechanism of CS
and CNT formation.
With no catalyst, the process yields smooth CSs of 2—10 microns in diameter that are
conductive and paramagnetic. They can be used in toners and printers, as additives for lubricants,
and in the tire industry. Industrial collaborators, Superior Graphite and ConocoPhillips, have
heat-treated CSs at higher temperatures; this improves their electrochemical performance as
anodes for lithium-ion batteries.
With a ferrocene catalyst, the process yields CNTs that Argonne has successfully tested 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 "WPBs.
Albemarle
Corporation
Argonne
Laboratory
29
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Armstrong World
Industries, Inc.
Armstrong World
Industries, Inc.
The process uses less energy to manufacture these materials than existing methods; it also
replaces a petrochemical feedstock with WPBs. By diverting plastic bags from landfills or toxic
incineration factories, this process reduces air and water pollution, ultimately reducing the hazards
to public health and environment.
Argonne has designed and built a prototype reactor with 80 cubic centimeter capacity
and optimized the reaction conditions. Argonne is working with Grupo Simplex and
G2 NanoTcchnologies, LLC to commercialize this technology.
BioBased Tile®: A Non-PVC Flooring Made with
Rapidly Renewable Resources
Historically, resilient vinyl composition tile (VCT) flooring has been manufactured with
binders derived from fossil fuel. Poly(vinyl chloride) (PVC) is the primary binder used to combine
plasticizers, processing aids, stabilizers, limestone, and pigments into resilient flooring. Other
binders include polyolefins, ethylene acrylic resins, and synthetic rubbers.
In 2008, Armstrong commercialized BioBased Tile'*' flooring, a revolutionary flooring product
that uses natural limestone and a proprietary polyester binder made from rapidly renewable
materials. Armstrong developed BioBased Tile® specifically to provide a PVC- and phthalate-
free alternative to VCT tor K-12 education applications. Armstrong is the first manufacturer in
over 100 years to develop a biobased polymer as a binder for a hard-surface flooring product.
The new binder created a new category of floor tile that couples improved indoor air quality and
environmental benefits with improved performance and affordability.
The polymer binder contains 13 percent biobased content from rapidly renewable corn, which
reduces reliance on fossil fuels and lowers the carbon footprint. It was built on technologies that
previously won Presidential Green Chemistry Challenge Awards (i.e., biobased polylactic acid
and 1,3-propanediol) to replace phthalate-plasticized PVC. The consumer product also contains
10 percent preconsumer recycled limestone. Each year, replacing VCT with BioBased Tile® flooring
could save 140 million pounds of virgin limestone, eliminate 336,000 pounds of volatile organic
compounds (VOCs) from manufacturing, capture 44 million pounds of carbon dioxide (CC>2)
from the atmosphere in biobased components, and reduce energy consumption equivalent to
475 billion Btu (or 56 million pounds of CC>2).
BioBased Tile® flooring is certified by Floor Score with no detectable VOCs. It contains
no materials listed in the table of Chronic Reference Exposure Levels (CRELs) established by
California's Office of Environmental Health Hazard Assessment (OEHHA). For green building
initiatives, BioBased Tile® contributes up to four points toward LEED certification and will be
NSF 332 certified in January 2012.
Breakthrough Formaldehyde-Free Coating for Ceiling Tiles
Ceiling tiles can sag if they are not engineered to resist humidity. Armstrong and other
ceiling tile manufacturers have historically applied rnelamine—urea—formaldehyde or other
formaldehyde-based resins as back coats to prevent ceiling tiles from sagging. Although
formaldehyde is key ingredient in many building products, there is now great concern for its use.
Formaldehyde is a colorless, flammable, odorous gas that is a classified as a "known carcinogen"
by the International Agency for Research on Cancer (IARC) and as "reasonably anticipated to be
a human carcinogen" by the National Toxicology Program (NTP).
Armstrong World Industries has developed a formaldehyde-free, waterborne coating that can
be applied to the surface of any fibrous panel such as a ceiling tile to prevent sagging. Armstrong
did extensive research to develop a new coating that expands hydroscopicly at high humidity to
resist sag, maintains a high modulus even at high humidity, and is compatible with other coatings
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and fillers. The new coating system includes a binder based on a combination of dextrose and
ammonia-neutralized polyacrylic acid.
Armstrong will use its newly invented coating technology to replace all formaldehyde resin
ceiling tile applications. By implementing this new technology globally, Armstrong will eliminate
8.3 million pounds of formaldehyde resins, 416,000 pounds of formaldehyde air emissions,
and 134,000 pounds of triethylamine air emissions annually. Eliminating formaldehyde resin
(1) avoids employee formaldehyde exposure at four Armstrong manufacturing facilities in the
United States and five international facilities; (2) eliminates formaldehyde and triethylamine stack
emissions associated with the cross-linking process for the traditional melamine—formaldehyde
ceiling tile back coat; (3) eliminates potential formaldehyde emissions from finished products after
installation; and (4) reduces lifecycle assessment impacts associated with upstream production
of formaldehyde. Armstrong has already successfully converted several key products to the new
technology and is converting its remaining products.
Envirez* Technology: Incorporating Renewable
Recycled Feedstocks into Unsaturated Polyester Resins
Unsaturated polyester resins are key components of fiber-reinforced plastic thermoset
composites. The annual production of these resins in North America is approximately 1 billion
pounds. Historically, these resins have been made almost exclusively from virgin petrochemicals.
Expanding on the pioneering work of Professor Richard Wool at the University of Delaware,
Ashland developed Envire"/™ resins, a novel, versatile family of unsaturated polyester resins made
from either renewable or recycled raw materials or both. Ashland uses biobased building blocks
including soybean oil, ethanol, 1,3-propanediol, and other proprietary monomers from soybeans,
corn, and other renewable raw materials. Additional building blocks for Envirez1M resins are
recycled monomers and polymers including postconsumer poly(ethylene tcrcphthalatc) (PET).
Ashland recently developed the first EnvirezIM resins that employ recycled raw materials and
use combinations of both recycled and renewable rawr materials. Envirez™ resins now contain
more types and higher percentages (up to 40 percent) of renewable raw materials. Ashland has
developed formulations for a wide variety of composite fabrication methods including infusion,
pultrusion, casting, and gelcoats. These formulations expand the reach of Envirez1M into an
assortment of products and markets including green buildings and wind energy devices. They
enable composite fabricators to use sustainable components.
EnvirezIM technology leads to reduced dependence on petroleum, lower emissions, energy
savings, and a smaller carbon footprint. In the last three years, Envirez™ resins have incorporated
over 12 million pounds of recycled PET. Using a novel, biobased reactive intermediate, Ashland
has developed EnvirezIM lowstyrcne resins that lower the traditional styrene content by one-third
and reduce both hazardous air pollutants (HAPs) and volatile organic compounds (VOCs). The
Envirez™ product line has experienced double-digit growth in the past several years. Envirez™
low styrene resins have completed review under the Toxic Substances Control Act (TSCA) and
are undergoing field trials at numerous composite fabricators.
Compostable Multilayer Food Packaging
Most conventional food packaging consists of a multilayer film structure comprised of
polyolefin or polyamide resins and adhesives. The layers include barriers, colorful print, and
adhesives to bond all the layers together. Because conventional packaging is neither recyclable nor
compostable, landfills are the only disposal option. When organic material goes into a landfill
it degrades over time, releasing landfill gas (LFG), which is a mixture of the environmental
Ashland Performance
Materials
BASF Corporation
31
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Bayer
MaterialScience
Bayer AG
pollutants methane gas and carbon dioxide (CC>2). Because less than 30 percent of the landfills
in the United States collect LFG, the majority of organic material placed into landfills eventually
releases LFG,
In 2011, BASF's Biodegradable Polymers Group successfully made a completely compostable
multilayer food packaging structure with high barrier properties. The structure consists of six
layers: an Ecoflex'8' and Ecovio'8' outer layer, Joncryl SLX (printing ink layer), Epotal P 100 ECO
(adhesive coating), a metallization layer, Versamid'8' (pre-met primer), and an Ecoflex® and
Ecovio*1 inner layer. Ecoflex'8'is a bioplastic copolyester and Ecovio® is a compound of Ecoflex'*
with polylactic acid (PLA). This packaging structure meets the barrier requirements for a large
number of packaged consumer goods.
For the first time, food packaging wastes can be diverted to industrial composting facilities
that create end-of-life value far beyond putting the packaging in landfills. Composting and the
subsequent use of the finished compost produce beneficial factors for the environment and
resource management. BASF compostable multilayer packaging will allow landfill diversion
for programs throughout the United States that are working toward Zero Waste. One of the
benefits of diverting organic waste from landfills is increasing landfill lifespans. This reduces the
need to build new landfills or expand existing ones, which will save energy, reduce emissions to
water, and reduce air pollutants from building new landfills. BASF is partnering with the Seattle
Mariners in their zero waste initiative through the Green Sports Alliance to replace trash cans
with recycle and compost bins.
One-Component, UV-Curable, Waterborne
Polyuretbane Coatings
In the 198()'s, Bayer MaterialScience (BMS) developed water-based unsaturatcd polyesters
that were UV- or peroxide-curable and reduced volatile organic compounds (VOCs) and
very hazardous air pollutants (VHAPs). Unfortunately, this technology did not displace the
acid-catalyzed nitrocellulose lacquer systems. In 1992, Bayer's two-component (2K) water-based
polyurethane coatings entered the wood coatings market. This technology displaced high-VOC
and high-VHAP coating systems and won the 2000 Presidential Green Chemistry Award, but
it was limited in its user-friendliness and slow drying speeds, especially on automated wood
coating lines.
In 1999, BMS developed a one-component (IK), UV-curable, waterborne polyurethane
with reduced VOCs and VHAPs for wood coatings. In this nominated process, BMS reacts a
polyisocyanate and a polyol in a BMS production facility to create a polyisocyanate prepolymer.
They then react this with a UV-curable polyol through an isocyanate—alcohol reaction to
form IK, UV-curable waterborne polyurethanes. The process develops high-molecular-weight
polymers (over 200,000 g/mol) in water without residual isocyanate monomer or polyisocyanate
prepolymer. The product contains ultra-low VOCs because BMS's proprietary process removes
the acetone carrier after manufacturing.
Renowned manufacturers of office furniture now advertise products made with BMS
coating systems as having low emissions and being environmentally compatible. Large furniture
companies are increasingly specifying coating systems with low or no solvent. BMS coatings cure
in just seconds under UV light and meet low- or no-solvent specifications very cost-effectively.
Between 2007 and 2011, commercial use of this coating system to replace acid-catalyzed
varnishes or nitrocellulose lacquers resulted in reductions of 50—90 percent for VOCs and
50—99 percent for VHAPs, which is equivalent to removing 2.6 million pounds of organic
solvents and 49,000 pounds of formaldehyde from the U.S. environment. Emerging markets
for BMS's IK UV-curable waterborne polyurethane include aerospace and defense, site-applied
UV-cured flooring, sunshine-cured wood decking, special effects coatings, and wet-strength
papers.
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FIREBLOCfC™ Intumescent Resin
Composites used to manufacture interior and exterior parts for applications in trains,
tramways, subways and other rolling stock must meet fire retardant specifications. Traditional
chemicals used in fire retardant composites are decabromodiphenyl ethers and antimony trioxide,
which are carcinogens, mutagens, and reproductive toxins. The manufacturing of these fire
retardant composites requires handling highly toxic substances. In case of accidental combustion,
polybrominated aromatic compounds release free radicals that act in synergy with antimony
trioxide to produce bromide radicals and toxic fumes.
Intumescent coatings swell with heat, offering passive fire protection. Intumescent coatings
have been known for years, but these products were very difficult to formulate and apply. In 2008,
CCP Composites developed a breakthrough product, FIREBLOCK™ intumescent unsaturated
polyester resins (LJPRs), which can be molded with glass fiber to manufacture fire retardant parts.
In the intumescence mechanism, high temperatures cause ammonium polyphosphate to release
an acid that simultaneously reacts with melamine in the resin to liberate a gas. The gas diffuses
into small bubbles and carbonizes the carbon-rich polyalcohol. These actions form foam that
solidifies into a char and shields the underlying material to stop the combustion cycle.
FIREBLOCK™ resin is a commercially viable alternative to bromine-containing fire retardant
LJPRs used in a wide variety of composites. It is completely free of halogens, mutagens, carcinogens,
and reproductive toxins. In addition to meeting the same standards on materials fire behavior as
do traditional fire retardants, FIREBLOCK™ intumescent resin also has a lower density than
standard unsaturated polyester resins. It is environmentally friendly, with a 13 percent reduction
in carbon dioxide (CO2) emissions compared to standard fire retardants in the railway industry.
A significant portion of today's estimated 10 million pounds annual use of brominated LJPRs
could be converted into FIREBLOCK™ technology in the next five years in the United States.
Vegetable Oil Insulating Fluid for Improved High Voltage
Transformer Capability
Fob/chlorinated biphenyls (PCBs) form the basis for traditional dielectric coolant fluids, but
they present 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 an innocuous environmental
and health profile. Envirotemp™ FR3™ fluid contains approximately 97 percent food-grade
soy oil blended with small amounts of additives for long-term performance.
The National Institute of Standards and Technology (NIST) directly compared FR3™ fluid
to mineral oil in its total lifecycle assessment called BEES® 4.0, Building for Environmental and
Economic Sustainability. Using the carbon dioxide equivalent (CO2 eq.) amount of greenhouse
gas (GHG) generated from raw materials through end of life, FR3™ fluid has reduced GHG
emissions by over 98 percent (or over 102,000 tons of CC>2 eq.) to date compared to mineral oil.
This essentially carbon-neutral result assumes that FR3™' fluid or mineral oil would be placed in
equivalent transformers. Roughly 450,000 transformers now contain over 25 million gallons of
Envirotemp™ FR3™ fluid instead of petroleum-based mineral oil.
In 2011, Cooper combined the chemistries of FR3™ fluid and solid insulating paper
with advanced high voltage transformer design to produce a new generation of even greener
biotransformers. The chemical interactions between FR3 ™ fluid and the solid insulating structure
create greater thermal capacity that allows an optimized biotransformcr design. With this increased
capacity, Cooper removed 3—15 percent of the fluid volume and 3 percent of the construction
CCP
Cooper Power
Systems
33
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Cytec Inc.
materials from the biotransformers. Using the BEES analysis on 25 million gallons of FR3™ fluid,
the new generation of biotransformers could save an additional 2,000 tons of GHG emissions.
Other advantages include improved fire safety, remediation of accidental spills, and sustainable
supply benefitting U.S. farmers. New transformer designs with FR3™ fluid will be available
in 2012.
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 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 promulgated
regulations, the elimination of BPA from interior can coating systems is a matter of public and
scientific interest.
Cytec has developed a new generation of BPA-free, saturated polyester resins for the main
binder. These polyester resins, together with phenolic resins, can be used in interior can coatings.
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 the monomers 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 the U.S. Food and Drug Administration's (FDA's)
regulation 21 CFR §175.300 for polyesters. Computer modeling indicates that DUROFTAL
PE 6607/60BGMP docs not have the cstrogenic 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 eliminate BPA completely and perform
comparably to existing systems. Commercial sales began in 2008. In 2010, Cytec began its first
full-scale production of the phenolic part of the system. In 2011, Cytec's first commercial sales of
DUROFTAL PE 6607/60BGMP eliminated about 10 tons of BPA.
The Dowr Chemical
Company
EVOQUE™Pre-Composite Polymers
Titanium dioxide (TiO?) is the primary white pigment in paint; it provides opacity by
scattering visible light. The process that derives TiOi from titanium ore requires large quantities
of energy, complete digestion with excess chlorine or sulfuric acid, and a multistcp purification.
Dow has developed EVOQUE™ Pre-Composite Polymer Technology for making paint
with 10—20 percent less TiO2. Dow controls the interaction between individual pre-composite
polymers and TiO2 pigment particles to achieve a TiO?-centered structure surrounded by
polymer molecules. As the pigment-polymer composites in paint dry to a film, the prc-compositc
polymers keep the individual TiC>2 particles separated so they are evenly distributed. Performance
benefits resulting from improved film formation and reduced photodegradation (due to reduced
TiO2, which promotes photodegradation) are expected to improve exterior durability by
20 percent.
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Third-party validated, lifecycle assessment (LCA) shows that TiC>2 reductions facilitated by
EVOQUE™ Pre-Composite Polymer Technology in exterior house paint reduce the associated
carbon footprint by 22.5 percent, water consumption by 30 percent, NOx and SOx emissions
by 24 percent, potential water eutrophication (algal bloom) by 27 percent, potential chemical
oxygen demand (COD) by 30 percent, and non-methane volatile compounds (NMVOC) by 35
percent. These last two factors impede water quality and air quality, respectively.
EYOQUE1M Pre-Composite Polymer Technology is currently compatible with wrhite and
pastel acrylics, which account for approximately 165 million gallons of U.S. paint produced
annually. Based onTiC>2 removal alone, using EVOQUEIM Pre-Composite Polymer Technology
in half of this paint could reduce associated greenhouse gas (GHG) emissions by approximately
54,000 metric tons of carbon dioxide equivalents (CO? eq.). The enhanced performance and
durability expected from paints with EVOQUE™ Pre-Composite Polymer Technology could
increase this reduction to 123,000 metric tons of CO2 eq., which is comparable to the annual
CO2 emissions generated from the gasoline used by approximately 14,000 cars.
SED Olefin Block Copolymers
INFUSE™ Olefin Block Copolymers (OBCs) are produced with a patent-pending shuttling
process that represents an innovation in catalyst technology and that delivers breakthrough
performance using 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 polyolefins.
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. The OBC manufacturing process fits into existing facilities with only limited
changes to equipment, leading to significant resource savings. 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 1NSITE™ Technology. From 2008 to 2011, Dow
OBCs replaced a number of existing polymers including styrene— ethylene— butylene— styrene
(SEBS), thermoplastic vulcanizatcs (TPV), and flexible poly(vinyl chlorine) (f-PVC) for
85 customers worldwide.
Chlorantraniliprole: Increased Food Production, Reduced
Risks, More Sustainable Agriculture
The caterpillar larvae of many lepidopteran species are major agricultural pests, defoliating
plants and attacking fruit and root systems. Lepidopteran pests are likely responsible for
30—40 percent of insect damage to crops; they consume 50 percent of all crops in many developing
countries. Although insecticides arc available to control these pests, many present significant risks
to humans or the environment.
The Dow Chemical
Company
DyPont Company
35
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DuPont redesigned its discovery process for new pesticides by integrating chemistry and
biology with lexicological, environmental, and site-of-action studies to optimize safety and
product performance simultaneously. 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. Because
it selectively targets insects, chlorantraniliprole is inherently safer to people and other nontarget
organisms. EPA classifies chlorantraniliprole as a reduced risk pesticide. It may be the safest of
all lepidopteran insecticides, including those derived from natural sources. Chlorantraniliprole
is usually one to two orders of magnitude more potent against target pests than are pyrethroids,
carbamates, and organophosphates. Its lower use rates mean less pesticide gets into the environment
with a corresponding reduction in the exposure of workers and the public. ChlorantraniHprole'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. In 2011 alone, more than
20 million farmers and 400 crops benefitted from insect control by chlorantraniliprole.
I Development of a Commercially Viable, Integrated,
Cellulosic Ethanol Production Process
Traditional production of ethanol from starches, such as corn grain, diverts resources from
food production. DuPont has developed a biochemical technology that produces ethanol from
non-food lignocellulosic bio mass such as corn stover. DuPont's process is an integrated pathway
with sufficiently high yields and liters of ethanol to be commercially viable.
It integrates three components: First, dilute ammonia pretreatment decouples the carbohydrate
polymers from the lignin matrix 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 and liters of fermentable 6-carbon
and 5-carbon sugars. Third, the optimized metabolic pathways of a recombinant ethanologen
(Zymomonas mobilis) produce ethanol efficiently by simultaneously metabolizing both the
6-carbon and 5-carbon sugars. Integrating and optimizing these three components enables a very
efficient process, a green footprint, and lower costs, including less capital investment than other
known cellulosic ethanol processes. If corncob feedstocks cost $50 per dry ton, the ethanol from
DuPont's process could cost less than $2 per gallon.
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 DuPont's process
could potentially reduce greenhouse gas (GHG) emissions by over 100 percent compared to
gasoline, which is substantially larger than GHG reductions from other grain-based ethanol
processes.
A flexible-feedstock, 250,000 gallon-per-year demonstration facility in Vonore, TN is currently
yielding over 70 gallons per U.S. ton of biomass and ethanol titers in excess of 70 grams per liter.
In 2014, the first commercial-size facility to convert corn stover to over 25 million gallons of
ethanol annually is expected to start up in Nevada, IA.
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Production of Isobutanol from the Synergy between
Metabolic and Process Engineering
Isobutanol, an advanced biofuel, offers significant technical and commercial 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 toxidty, and the
ability to reach targeted production economics,
DuPont was the first to create and develop integrated biological and process technologies
that use microbes to produce isobutanol from renewable resources. DuPont's strategy for low-
cost commercialization includes retrofitting existing ethanol plants to produce isobutanol from
current ethanol-industry feedstocks (i.e., corn grain and sugarcane), lignocellulosic biomass, and
macroalgae (seaweed). A proprietary yeast strain engineered with a novel biosynthetic pathway
ferments sugars from these feedstocks to isobutanol. DuPont selected key enzymes based on their
isobutanol specificity and cofactor requirements, then maintained flux through to isobutanol by
eliminating byproduct reactions that could compete with the chosen pathway. This yeast-based
isobutanologen is a drop-in biocatalyst suitable for retrofitted ethanol plants.
A major challenge in commercial isobutanol production by microbes is the intolerance of the
microbes to commercially relevant aqueous liters of isobutanol. DuPont met this challenge by
reducing the aqueous concentration of isobutanol in fermentations, thereby avoiding enzyme
inhibition by its product while minimizing production cost and environmental footprint.
The fermentation rate, titer, and yield are significantly superior to those of traditional
acetone—butanol—ethanol (ABE) fermentations. This performance demonstrates cost-effective
biological production of isobutanol for chemicals and fuels. DuPont's technology can displace
petroleum-based syntheses for isobutanol and directly replace refined gasoline from crude oil
with a greener, biobased product. Further, its advantages over incumbent technologies include
reducing greenhouse gas (GHG) emissions by 40—70 percent, local and national economic
benefits, and increased national security through domestic fuel supplies. During 2011, DuPont
began operating a large-scale demonstration plant for isobutanol in the United Kingdom in a
joint venture with Butamax™ Advanced BioFuels.
Grignard Reactions Go Greener with Continuous
Processing
The synthetic pathways of numerous intermediates tor food additives, industrial chemicals, and
pharmaccuticals have included the Grignard reaction since the start of the 20th century. 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 has developed inherently safer Grignard chemistry using a continuous
stirred tank reactor (CSTR) that allows continuous formation of Grignard reagents with
continuous coupling and quenching operations. This strategy minimizes hazards by operating
at a small reaction volume, performing metal activation only once for each campaign and using
2-methyltetrahydrofuran (2-MeTHF), as a Grignard reagent and reaction solvent that may be
derived from renewable resources. Grignard reactions using 2-MeTHF also result in products with
enhanced chemo- and stereoselectivity. Relative to batch processing, the continuous approach
allows rapid, steady-state control and overall reductions up to 43 percent in magnesium, 10
percent in Grignard reagent stoichiometry, and 30 percent in process mass intensity (PMI). The
DuPont Company
Bytamax™
LLC
Eli Lilly and
Company
37
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Corporation
Corporation
continuous approach reduces reaction impurities substantially. In addition, small-scale operation
at end-of-reaction dilution allows all ambient processing conditions.
Lilly is using its CSTR Grignard approach to produce three pharmaceutical intermediates. One
of these is the penultimate intermediate of LY2216684. HC1, a norepinephrine reuptake inhibitor
that is under phase 3 clinical investigation for treatment of depression. Lilly uses a similar approach
to synthesize an intermediate for LY500307, an investigational new drug candidate under clinical
evaluation to treat benign prostatic hyperplasia. Lilly anticipates commercial production on
22 liter scales that will replace the 2,000 liter reactors used in batch processes.
Catalytic Treatment of Hydrogen Peroxide in IBM
Semiconductor Wastewater
Semiconductor manufacturing produces a large ammonia and hydrogen peroxide wastewater
stream that requires treatment. Through 2009, the industry standard for treating this wastewater
stream was to reduce the hydrogen peroxide with sodium bisulfate then to neutralize it with
sodium hydroxide. The next step was separating ammonia by distilling the wastewater to remove
ammonium hydroxide. The added sodium bisulfite and sodium hydroxide contributed high
levels of total dissolved solids (TDS) to IBM's wastewaters and final effluent discharge, and both
were also becoming increasingly expensive.
In 2003, IBM's East Fishkill plant (EFK) began an initiative with the New York State
Department of Environmental Conservation to reduce the TDS in the site's effluent discharge to a
small receiving stream. Over the next six years, IBM EFK investigated alternative technologies to
remove sources of TDS from its manufacturing wastewaters and wastewater treatment processes.
In early 2009, IBM qualified a catalytic enzyme process to replace the existing sodium bisulfate
process for removing hydrogen peroxide from the ammonia wastewater. This process uses a small
quantity of a catalase derived from Aspergillus niger fermentation to decompose peroxide into
water and oxygen. It does not contribute TDS to the site's effluent discharge and costs a fraction
of the previous treatment. The new process incorporates existing building equipment as much as
possible and integrates flawlessly into the existing treatment system.
IBM started and completed design and construction of the full-scale peroxide treatment
system in 2009, with startup continuing through March 2010. Annually, this new process
eliminates the use of 510,000 gallons of 38 percent sodium bisulfite and 135,000 gallons of
50 percent sodium hydroxide for acid neutralization. It reduces chemical costs by $675,000 per
year. The catalytic reduction of hydrogen peroxide process has been online continuously since
the beginning of 2010 and is currently patent-pending.
Elimination ofPFOSandPFOA in IBM Semiconductor
Manufacturing Processes Development ofPhotoacid
Generators Free of Perfluoroalkyl Sulfonates
In 2002, EPA restricted new applications of perfluorooctane sulfonate (PFOS) compounds
because scientific evidence showed that PFOS persists and bioaccumulatcs 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."
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Voluntarily, IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA). In
2006, IBM issued a Corporate Directive to eliminate PFOS and PFOA from all manufacturing
processes by 2010. IBM worked with chemical suppliers to identify and qualify a non-PFOS
replacement tor the PFOS surfactant in buffered oxide etch (BOE) chemicals. In 2008, after a
multiyear investigation and extensive qualifications, both IBM fabrication plants finished replacing
the PFOS surfactant in all BOE chemicals with perfluorobutane sulfonate (PFBS), for which EPA
has fewer environmental concerns.
IBM also sought replacements for specific photoresists and antireflective coatings (ARCs) that
contained PFOS or PFOA as a surfactant or photoadd 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, non-PFOA lithographic
chemicals. This change eliminates approximately 140 kilograms of PFOS and PFOA annually.
Total annual PFOS consumption by the semiconductor industry worldwide is estimated at 8,000
kilograms. IBM believes it is the only company in the world to eliminate PFOS and PFOA compounds
completely from semiconductor manufacturing. IBM has also developed PAGs free of perfluoroalkyl
sulfonates (PFAS) for both dry and immersion 193-nm semiconductor photolithography processes,
with equivalent performance in 45-nm and 32-nm semiconductor technology. IBM is pursuing
technology transfer opportunities to commercialize its PFAS-free PAGs for a wider range of
applications.
NATRASURFIM PS-Ill Polymeric Surfactant: Achieving
Next Generation Mildness in Personal Care Products with
a Reduced Environmental Footprint
The production of personal cleansing products, such as shampoos, body washes, and facial
cleansers, consumes sizable, ever-increasing volumes of surfactants. Traditionally, the industry
used largely nonrenewable, petroleum-derived synthetic detergents to achieve mildness in personal
cleansers. Although these well-established surfactants are safe and cost-effective, they could be
improved in their mildness, renewability, manufacturing processes, and biodegradability.
Johnson & Johnson and AkzoNobel have collaborated to develop NATRASURF™
PS-Ill, an innovative, starch-based polymeric surfactant (PS) for formulating mild personal
care products. PS-Ill is based on the patented discovery that PSs overcome the problem of
surfactant-induced irritation because they cannot penetrate living tissue. NATRASURF1M
PS-111, the first personal care ingredient of its kind, delivers the cleaning and foaming performance
of traditional surfactants and. has virtually no irritation potential.
NATRASURF1M PS-Ill minimizes environmental impacts throughout its lifecycle.
PS-Ill is sodium hydrolyzed potato starch dodecenylsucdnate, a 90 percent renewable material
derived by reacting hydrolyzed potato starch with an alkenylsucdnic anhydride. This low-
temperature, aqueous esterification offers many advantages over traditional esterifications, including
energy efficiency and atom economy. The starch ester used for PS-111 is nonirritating to skin and
eyes, nonallergenic, nontoxic to humans and aquatic organisms, nonbioaccumulative, and readily
biodegradable. PS-Ill is supplied to manufacturers as a self-preserving, spray-dried powder;
this eliminates the need for chemical preservatives and reduces the energy used to store and ship
conventional aqueous surfactant solutions.
PS-Ill has the potential to replace millions of pounds per year of nonrenewable, poorly
biodegradable surfactants and emulsifiers. Further, this technology can be readily leveraged for use
&
Johnson Consumer
Companies, Inc.
AkzoNobel Surface
Chemistry LLC
39
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Kop-Coat, Inc.
in agricultural, household, and industrial applications. NATRASURF™ PS-111 exemplifies how
green chemistry can enable cost-effective, sustainable materials that benefit both consumers and
the environment without sacrificing performance or efficacy. In December 2011, Johnson &C
Johnson launched the AVEENO® Pure Renewal line of shampoos, the first products containing
NATRASURF™ PS-111.
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. Preservatives and insecticides can improve the
durability of wood significantly, but methods to deliver these protectants into wood are largely
based on old, environmentally damaging technologies.
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 at a cost that is less than one quarter the cost of the closest competing
treatment technology.
In 2010, EPA registered the patented Tru-Core'*1 technology as a wood preservative. In 2011,
Tru-Core® technology was used in the dual treatment process for approximately two million
railroad ties. Tru-Core® Type 1 is currently undergoing evaluation by ICC-ES (International
Code Council Evaluation Service) for acceptance into the 2012 International Building Code.
Oil-Based Performance in a Water-Based Formula with Less
Environmental Impact
Solvent- and shellac-based stain-blocking primers typically include resins that require petroleum-
based solvents such as mineral spirits or ethanol. These solvents are not only combustible (and
in some cases flammable); they also release significant amounts of volatile organic compounds
(VOCs) during application and drying. Water-based primers made with a variety of acrylic and
styrene—acrylic resins are available, but they have extended dry times and cannot approach the
stain-blocking properties of solvent-based primers.
Masterchem Brands has developed KILZ MAX™ primer, using specialized epoxy-
based resin technology to provide heavy stain-blocking and odor blocking in a more
eco-friendly, water-based formula. This product has the benefits of solvent- or shellac-based
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primers including the ability to block severe stains and odors, resist tannin stains, and more. It
does not have the associated drawbacks of high odor, high VOCs, or clean up that requires
mineral spirits. Independent testing confirms that KILZ MAX™ performs as well or better than
oil- and shellac-based primers on virtually all problem stains, odors, and other surface imperfections.
It also meets or exceeds the performance of many products marketed as having similar technology.
KILZ MAXIM primer has a VOC level near 75 grams per liter; this is over seven-fold lower
than competitive shellac-based primers and six-fold lower than typical competitive specialty primers.
Replacing the solvent with water in KILZ MAX™ primer eliminates approximately 3 pounds
of VOCs per gallon compared to KILZ'8' Original solvent-based primer. In 2007, Masterchem
Brands sold over 3-3 million gallons of KILZ® Original primer. Replacing the higher-VOC
version with KILZ MAX™ primer would reduce airborne VOCs by as much as 9 million pounds
annually. Another benefit is the ability to sell high-performance stain-blockers in areas regulated
by the South Coast Air Quality Management District (SCAQMD), the California Air Resources
Board (CARB), and others. KILZ MAX™ primer was first produced and launched in retail
markets in 2011.
Revolutionizing Insect Control: Bt Technology
Crop insect pests have limited food production tor centuries. Although chemical insecticides
were the most advanced tools for insect control until the 1990s, they had undesirable environmental
effects, were toxic to some nontarget organisms, and required repeated applications to crops.
Unlike traditional pesticides, Monsanto's recently patented technology uses insect control present
in nature. Bacillus thuringiensis (Bt, a ubiquitous soil microbe) produces Cry (crystal) proteins,
which are insectiddal toxins. Using biotechnology, Monsanto combined its knowledge of Cry
proteins with pioneering plant molecular genetics to create crop plants that express synthetic Bt
Cry proteins engineered to be highly specific toxins against insect pests. In addition to reducing
the use of pesticides, the specificity of Cry proteins ensures only target organisms are affected and
not humans, animals, or nontarget, beneficial insects. Monsanto's application of biotechnology
to controlling pests makes both pesticide manufacturing and chemical pesticide applications less
necessary.
Farmers planting insect-resistant crops experience improved safety and health because of reduced
handling and use of pesticides. They spend less time applying insecticides. Reduced applications
mean fewer containers, less fuel, and less aerial spraying: all factors that benefit the environment
while increasing yields and enhancing farmers' lives.
Bt technology continues to be applied across many plant varieties, increasing yields and
reducing the need for chemical pesticides. All Bt traits in commercial use have been created with
Monsanto's patented synthetic Bt gene technology; traits Monsanto developed have been licensed
to and sold by numerous seed companies, as well as by Monsanto itself. Some companies have
developed their own insect resistance traits, but all of these traits have used Monsanto's synthetic
gene technology covered by a recently issued patent (U.S. patent 7,741,118 Bl). In 2010,
65 percent of all corn grown in the United States and 75 percent of all cotton grown in the United
States included one or more Bt traits.
Monsanto Company
41
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NALCO
Pacific Northwest
Archer Daniels
Company
NALCO s APEX™ Program: Sustainable Technology for
Paint Detackification
For decades, manufacturers have used hazardous melamine—formaldehyde—acid colloids to
detackify paint overspray in spray booths. Melamine is an irritant, however, and chronic exposure
may cause cancer or reproductive damage. Formaldehyde is a known carcinogen according to
the Occupational Safety and Health Administration (OSHA). Further, the colloid is derived
from feedstocks based on nonrenewable petroleum or natural gas. In searching for an alternative,
U.S.-based manufacturing companies established an initiative to create a green method for paint
detackification using innovative chemistry.
NALCO developed the APEX™ program to support this initiative. The APEX™ program
consists of an etherified, cationically modified corn starch mixed with a small amount of
a proprietary amphoteric polymer and a polybasic aluminum salt. It is formulated from over
99 percent sustainable resources. When added to a paint system at a pH above 7-0, APEX™
generates a highly cross-linked "sweep floe" that rapidly coagulates and completely detackifies
paint solids, creating an easily dcwaterable sludge. The APEX™ program completely eliminates
formaldehyde and other harmful, nonrenewable raw materials in these applications.
The APEX™ program benefits every manufacturing company that adopts it by: (1) reducing
total costs of operation (typically over 30 percent); (2) reducing chemical use (typically over
80 percent); (3) reducing the generation and transportation of wastes (typically over 50 percent);
(4) reducing water use; and (5) reducing emissions of volatile organic compounds (VOCs).
A large automotive plant in Alabama first implemented APEX™, where it reduced solid
waste generation by 267,000 pounds and saved $90,000 in disposal costs. It reduced VOC
generation by over 3,000 pounds (an 80% reduction). It also reduced the frequency of booth
cleaning from weekly to once per quarter, saving an additional $160,000 in operating costs and
significantly reducing use of cleaning chemicals. NALCO's APEX™'program is currently used in
85 assembly plants.
Propylene Glycolfrom Renewable Sources
Propylene glycol (PG) is a commodity chemical used in everyday consumer products such as
liquid detergents, hand sanitizers, pharmaceuticals, and cosmetics, as well as in industrial products
such as plastics, paint, antifreeze, and aircraft deicer. The largest use of PG is as a monomer in
plastics, especially fiberglass resins. Until recently, PG has been produced almost entirely from
petroleum resources. Each year, worldwide PG production consumes more than two billion
pounds of petroleum.
To eliminate this use of petroleum and to replace the toxic feedstocks involved, Battelle
scientists at Pacific Northwest National Laboratory (PNNL) developed a catalytic process for
producing PG from renewable sources. The propylene glycol from renewable sources (PGRS)
process relies on a carbon-supported bifunctional metal catalyst in combination with a soluble
base co-catalyst. The multistep process proceeds in a single reactor to produce PG in high
selectivity and at high conversion. This safe, sustainable, cost-competitive, and commercially
viable alternative converts plant-based, seed-oil-derived glycerol or plant sugar alcohols into PG,
which can then be purified to meet a variety of market specifications. The glycerol can come from
a variety of sources, including the crude glycerol byproduct of biodiesel production. The PGRS
process currently produces propylene glycol for the first time on a commercial scale entirely from
renewable resources. A lifecyde analysis shows that the PGRS process eliminates up to 61 percent
of the greenhouse gas (GHG) produced by the traditional propylene oxide route to PG.
42
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Archer Daniels Midland (ADM) commissioned and is now operating a new 100,000 metric ton
per year PG facility using Battelle's technology. This represents the first of its kind in the world:
an operational, commercial-scale facility producing PG that meets U.S. Pharmacopeia (LISP)
specifications entirely from renewable resources. Other competing technologies have been unable to
produce PG from renewable materials of this high-quality material at full scale.
New Green Commercial Biocatalytic Route to
Atorvastatin Calcium, the Lipitor API
Atorvastatin is the active pharmaceutical ingredient (API) in Lipitor. Since its launch in 1997,
Lipitor has been the most-prescribed branded cholesterol-lowering medication in the world. This
success, together with Pfizer's commitment to continuous improvement, made the production
of atorvastatin an obvious target for improvement. Pfizer challenged itself to make dramatic
improvements in both the efficiency and environmental performance of the manufacturing route
to atorvastatin.
The original manufacturing process required a chiral starting material. Because optimizing this
process would not achieve the transformational changes that Pfizer sought, the company developed
a completely new, more efficient, commercial route to atorvastatin calcium using a biocatalytic
process.
The new green process incorporates a water-based 2-deoxyribose-5-phosphate aldolase
(DERA) enzyme at the beginning of the route to make a lactol from an amino aldehyde
(i.e., 3-phthalimidopropionaldehyde; PPA) and acetaldehyde. The synthesis eliminates the use of
cyanide or azide moieties to introduce nitrogen because it is already present in the lactol. In contrast
to the original synthesis, the DERA enzyme sets both stereocenters with high selectivity in water
at room temperature. Converting the resulting lactol into isopropyl acetonide atorvastatin (IAA) is
extremely efficient: it involves four high-yield chemical steps (oxidation, esterification, deprotection,
Paal Knorr) with only the IAA product being isolated as a solid. Finally, IAA is converted to
atorvastatin calcium, the API product.
Pfizer's green process substantially reduces the environmental impact by eliminating hazardous
steps and reducing or eliminating required chemicals. For example, the new synthesis eliminates the
previous high-pressure hydrogenation step with its associated metal catalysts. It also avoids pyrophoric
K-butyl lithium and its associated butane waste gas. The need for significant other reagents and
solvents has either been eliminated or dramatically reduced. The U.S. Food and Drug Administration
(FDA) approved the new manufacturing process in April 2010. Pfizer manufactured commercial
scale validation batches in 2011 and is currently transitioning to full-scale commercial manufacture.
Ethos™ Modular Commercial Floor Coverings
Polymeric poly(vinyl butyral) (PVB) is a thermoplastic terpolymer of vinyl acetate, vinyl alcohol,
and vinyl butyral that provides shatterproof properties to windshields and other safety glass. Although
rccyclcrs have recovered the glass from safety glass and sold it into other markets for years, most of
the PVB film has been sent to landfills or burned for energy.
Tandus Flooring is the first manufacturer to use the abundant PVB waste stream and recycle it into
high-performance carpet backing. Ethos™ secondary backing, made from PVB film reclaimed from
windshields and other safety glass, can replace other structured carpet backings such as poly(vinyl
chloride) (PVC), ethylene—vinyl acetate (EVA), polyurcthane, polyolcfin, and bitumen. Producing
ethos1M backing from recycled material reduces the energy and environmental impacts associated
with extracting, harvesting, and transporting virgin raw materials.
Pfizer
Tandus Flooring
43
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Verenium
Corporation
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, recyclabiliry, 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, ethosIM backing has extremely low environmental
lifecycle impacts compared to other products. Tandus's patented, closed-loop process can also
recycle postconsumer carpet with ethos1M backing and other manufacturing waste into new
floor coverings.
Initially, Tandus successfully introduced a six-foot-wide ethos™ cushion backing, Powerbond,
to meet the needs of Kaiser Permanente for high-performance, PVC-free, soft-surface flooring.
In November 2009, the company introduced ethos™ modular. Its production has increased
18-fold in the last two years. Every square yard of ethos1M modular replaces approximately
5.25 pounds of PVC in carpet backing. To date, Tandus has recycled more than 10 million
pounds of PVB into flooring products, keeping PVB from landfills, and potentially replacing
52 million pounds of PVC.
Pyrolase® Cellulase Enzyme Breaker as a Biodegradable
Replacement for Corrosive Adds Oxidizers in
Hydraulic Fracturing Operations
Hydraulic fracturing (fracking) is an advanced drilling technique used to unlock vast stores of
oil and shale gas across the country. It involves pumping pressurized water, sand, and chemicals
underground to open fissures in oil- and gas-containing formations such as shale and improve
the flow to the surface. Fracturing uses a host of corrosive acids and oxidizers to degrade and
remove fracturing fluid residues from formation pores. The fracturing process has drawn harsh
criticism from environmentalists claiming that potential contamination of underground water by
fracturing poses a significant environmental risk. In December 2011, EPA first stated publicly
that fracturing might be to blame for groundwater pollution in Wyoming.
Verenium has developed Pyrolase'5' cellulase to replace the corrosive acids and hazardous
oxidizers used in fracturing. Verenium discovered and isolated the gene for Pyrolase* cellulase, a
thermostable enzyme from the eubacterium Thermotoga maritime, found in geothermally heated
sediment on the ocean floor. Pyrolasc® cellulase is a broad-spectrum p-glycosidase with both
endo- and exo-glucanase activities that provides a complete viscosity break on fracturing fluids
across a broader range of temperatures, wider pH ranges, and higher salinity than other commercial
enzymes. Pyrolase'*1 cellulase is also useful in a wider variety of down-hole conditions. It excels in
hydrolyzing linear and cross-linked fluids, such as guar gum, derivati/ed guar, and carboxymethyl
cellulose, at speeds easily controlled by varying the enzyme loading. It offers superior performance
with zero environmental impact.
Pyrolase'8'cellulase is an easy-to-use liquid. One pound of biodegradable Pyrolase* cellulase can
replace more than 20 pounds of hazardous chemicals, some of which are implicated in soil and
water contamination. Pyrolase*' cellulase is a significant step toward addressing the environmental
and health concerns over hydraulic fracturing both for workers and for those living near fracturing
operations. Verenium launched a campaign in 2011 to commercialize Pyrolase® cellulase to the
oil and gas services industry.
44
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are
ACTA Inc.
Geo'thermal Heat Pumps: A Greener and More Energy-Efficient Renewable
Energy Resource [[[ 15
Chemistry LLC &
Inc.
NATRASURF™ PS-Ill Polymeric Surfactant: Achieving Next Generation Mildness in
Personal Care Products with a Reduced Environmental Footprint ................ .39
Concrete-Friendly™ Powdered Active Carbon (C-PAC™) to Remove Mercury from Flue
Gas Safely 29
Pacific
Laboratory
Propylene Gly col from Renewable Sources.................................. .42
Upcycling Waste Plastic Bags into Valuable Carbon Nanotubes and Carbon Spheres . ... 29
Inc.
BioBased Tile9: A Non-PVC Flooring Made with Rapidly Renewable Resources....... 30
Breakthrough Formaldehyde-Free Coating for Ceiling Tiles 30
Envirez^Technology: Incorporating Renewable and Recycled Feedstocks into Unsaturated
Polyester Resins 31
Compostable Multilayer Food Packaging ................................... 31
AG
One-Component, UV-Curable, Waterborne Polyurethane Coatings 32
AG
One-Component, UV-Curable, Waterborne Polyurethane Coatings ............... .32
Inc.
Producing Chemicals and Carbon fi'om Waste Tires, Plastics, Carpet, and Biomass 15
of &
University of York SUMY
Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis ofDiarylAldimines 9
-------
LLC
Greening the Design of Chemical Production with Microbes ..................... 16
Elimination ofPFOSandPFOA in IBM Semiconductor Manufacturing Processes and
Development ofPhotoacid Generators Free ofPerfluoroalkyl Sulfonates 39
Enzymes Reduce the Energy and Wood Fiber Required to Manufacture High-Quality Paper
LLC
Production ofIsobutanolfrom the Synergy between Metabolic and Process Engineering. . 37
CCP
FIREBLOCK^* Intumescent Resin 33
The City of City of York,
of Chemistry,
Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for
Safe Oil-Thickening Agents (Amphiphiles) 9
W.f
Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon Monoxide . .... 3
*Codexis, Inc. Yi Tang, of California, Los
An Efficient Biocatalytic Process to Manufacture Simvastatin 6
Colonial Chemical, Inc.
Sugd*Nate: A Safer, Milder, Greener Surfactant. ............................. 16
of of Chemistry,
Inc.
EA Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections . .... 13
Vegetable OH Insulating Fluid for Improved High Voltage Transformer Capability 33
* Cornel I Uniwersity, W.
Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon Monoxide 3
Inc.
Glycerol tert-Butyl Ether (GTBE): A Biofitel Additive for Today 17
*Cytec Inc.
*MAXHT* Bayer Sodalite Scale Inhibitor .................................. 7
Saturated Polyester-Phenolic Resin Systems for Bisphenol A-Free Interior Can Coatings for
Food Packaging. 34
48
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The
EVOQUE™ Pre-Composite Polymers 34
INFUSE^Olefin Block Copolymers ..................................... .55
of Civil
L.
Improved Resource Use in Carbon Nanotube Synthesis via
Mechanistic Understanding. ............................................ 11
Chlorantraniliprole: Increased Food Production, Reduced Risks, More
Sustainable Agriculture 35
Development of a Commercially Viable, Integrated, Cellulosic
Ethanol Production Process ............................................. 36
DuPont Bulamax™ LLC
Production of Isobutanolfrom the Synergy between Metabolic and Process Engineering. . 37
Inc.
Formaldehyde-Free, High-Strength Biocomposites from Sustainable Resources 17
Generally Recognized as Safe (GRAS) Coatings 18
Inc.
Zero-Emission Production of the Green Lithium Ion SuperPolymef3 Battery 15
*EIevance Inc.
Using Metathesis Catalysis to Produce High-Performing, Green Specialty Chemicals at
Advantageous Costs 5
Eli Lilly
Grignard Reactions Go Greener with Continuous Processing 37
FRX Inc.
Polymeric, Nonhalogenated Flame Retardants with Broad Applicability in
Multiple Industries 19
*Hedrick, L.f M.
of
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 4
H-O-H Technology, Inc.
Conserving Water and Eliminating Chemical Treatment in Cooling Towers 20
o o o
*IBM L. M.
of
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 4
49
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Catalytic Treatment of Hydrogen Peroxide in IBM Semiconductor Wastewater 38
Elimination ofPFOSandPFOA in IBM Semiconductor Manufacturing Processes and
Development ofPhotoacid Generators Free ofPerfluoroalkyl Sulfonates 38
Polymers, LLC
InfiGreen Polyols 20
of The City of
City of
Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for
Safe Oil-Thickening Agents (Amphiphiles) 9
& Inc.
LLC
NATRASURF'[M PS-111 Polymeric Surfactant: Achieving Next Generation Mildness in
Personal Care Products with a Reduced Environmental Footprint ................. 39
Kop-Coat, Inc.
Tm-Core* Protection System for Wood 40
Development and Commercialization of Okie Estolide Esters .................... 21
of of
California,
Chemical Conversion of Biomass into New Generations of Renewable Fuels, Polymers, and
Value-Added Products 10
MAX™PRIMER-SEALER-STAINBLOCKER: Oil-Based Performance in a
Water-Based Formula with Less Environmental Impact. 40
Inc. of
of
A Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections 13
Revolutionizing Insect Control: Bt Technology 41
Bio based Chemicals from Low-Cost Lignocellulosic Sugars. ..................... .21
NALCO's APEX™ Program: Sustainable Technology for Paint Detackification 42
of
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters to Half-Esters ....... 10
SO
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Inc.
High-Performance Polyols from CO'2 at Low Cost 22
Inc.
ElectJ'odialysis and Chromatographic Separation Technology for Chlorine-Free Production
of Potassium Hydroxide and Hydrochloric Acid, 23
The Uniwersity, of Chemistry,
T.¥.
Ethylene: A. Feedstock for Fine Chemical Synthesis 12
Inc.
Producing Industrial Chemicals by Fermenting Renewable Feedstocks at a Lower Cost . ,23
Propylene Glycolfrom Renewable Sources 42
Chemicals, LLC
BURN-OUT™ Durable, Green, Nontoxic Flame Retardant 24
New Green Commercial Biocatalytic Route to Atorvastatin Calcium, the Lipitor API . .43
L., of Civil
Improved Resource Use in Carbon Nanotube Synthesis via Mechanistic Understanding. .11
T.V. of The
Ethylene: A Feedstock for Fine Chemical Synthesis. ........................... .12
LP
Zero-VOC Cleaning and Remediation Technology 24
of
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters.................. 10
Inc.
Sodium Silicide: A. New Alkali Metal Derivative for Safe, Sustainable, and On-Demand
Generation of Hydrogen ............................................... 25
* Stanford University, of M.
L.
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 4
of York SUMY
of &
Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of Diary I Aldimines 9
51
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of
University of
y4 Trw/y Green Process for Converting Ethylene to Ethylene Oxide 12
SUNY of
of &
Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of DiarylAMimines 9
Ethos™-Modular Commercial Floor Coverings 43
*Tang, Yi, of California, Inc.
ylw Efficient Biocatalytic Process to Manufacture Simvastatin 6
Uniwersity, of
Highly Efficient, Practical Monohydrolysis of Symmetric Diesters 10
of California, of
Chemical Conversion ofBiomass into New Generations of Renewable Fuels, Polymers, and
Value-Added Products. ................................................ 10
*Uni¥ersity of California, Yi Tang Inc.
An Efficient Biocatalytic Process to Manufacture Simvastatin 6
of
(ACRES) for
P.
Biobased Polymers and Composites. ...................................... 13
of of
/I 7n//y Green Process for Converting Ethylene to Ethylene Oxide. ................. 12
Inc.
Biobased Adipic Acid for Renewable Nylon and Polyurethane Resins .............. .26
Pyrolase® Cellulose Enzyme Breaker as a Biodegradable Replacement for Corrosive Acids
and Oxidizers in Hydraulic Fracturing Operations........................... 44
VH Inc.
Bacteriocins: A Green, Antimicrobial Pesticide 26
of
of Mines, MicroPhage, Inc.
A Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections 13
52
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*¥tfay mouth, M.f L.
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry 4
Wool, P.,
(ACRES) for
of
Biobased Polymers and Composites 13
53
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Office of Pollution 744K12001
Prevention and June 2012
Toxics (7406M) www.epa.gov
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