The 2011 award winners are:

Greener synthetic pathways: Genomatica, San Diego, Calif. Genomatica is developing and commercializing sustainable basic and intermediate chemicals made from renewable feedstocks including readily available sugars, biomass, and syngas. The company aims to transform the chemical industry through the cost-advantaged, smaller-footprint production of bio-based chemicals as direct replacements for major industrial chemicals that are currently petroleum-based in a trillion-dollar global market.

The first target molecule for Genomatica is 1,4-butanediol (BDO). BDO is used to make spandex, automotive plastics, running shoes, and many other products; it has an approximately 2.8 billion pound, $3-billion worldwide market. Genomatica has been producing BDO at pilot scale in 3,000 liter fermentations since the first half of 2010, and is moving to production at demonstration scale in 2011.

Initial lifecycle analyses show that Genomatica’s Bio-BDO will require about 60% less energy than acetylene-based BDO. Also, the biobased BDO pathway consumes carbon dioxide (CO₂), resulting in a reduction of 70% in CO₂ emissions. Fermentation requires no organic solvent, and the water used is recycled. Furthermore, the Bio-BDO fermentation process operates near ambient pressure and temperature, thus providing a safer working environment. These advantages lead to reduced costs: production facilities should cost significantly less, and production expenses for Bio-BDO should be 15–30% less than petroleum-based BDO. Genomatica expects Bio-BDO to be competitive at oil prices of $45 per barrel or at natural gas prices of $3.50 per million Btu.

Genomatica’s integrated bioprocess engineering and extensive intellectual property allow it to develop organisms and processes rapidly for many other basic chemicals. Because the chemical industry uses approximately 8% of the world’s fossil fuels, Genomatica’s technology has the potential to reduce carbon emissions by hundreds of millions of tons percent annually.

Genomatica has entered into partnerships with several major companies including Tate & Lyle, M & G (a major European chemicals producer), Waste Management, and Mitsubishi Chemical to implement their technology at a commercial scale. Genomatica expects to begin commercial production of Bio-BDO in 2012. They plan to roll out plants in the United States, Europe, and Asia over time.

Greener reaction conditions: Kraton Performance Polymers, LLC, Houston, Texas. Kraton has developed a family of halogen-free, high-flow, polymer membranes made using less solvent. Polymer membranes are used in a variety of purification processes including reverse osmosis water desalination; water ultra-purification; salt recovery, and waste acid recovery. Membrane efficiency is limited by the rate at which water (or another molecule) crosses the membrane (the flux). Increasing the pressure of the “dirty” side of the membrane can increase the flux, but a higher pressure requires a stronger membrane.

Kraton Performance Polymers developed NEXAR polymer membrane technology for applications requiring high water or ion flux. Kraton’s NEXAR polymers are block copolymers with separate regions that provide strength (poly(t-butyl styrene)), toughness and flexibility (poly(ethylene–propylene)), and water or ion transport (styrene–sulfonated styrene). These A-B-C-B-A pentablock copolymers exhibit strength and toughness in dry and wet conditions. Kraton’s production process for NEXAR polymers uses up to 50% less hydrocarbon solvent and completely eliminates halogenated cosolvents.

The biggest benefits are during use. NEXARTM polymers have an exceptionally high water flux of up to 400 times higher than current reverse osmosis membranes. This could translate into significant reductions in energy and materials use. Modeling shows that a medium-sized reverse osmosis (RO) plant could save, conservatively, more than 70% of its membrane costs and approximately 50% of its energy costs. For applications in electrodialysis reversal (EDR), the higher mechanical strength of NEXAR polymers makes it possible to use thinner membranes, which reduces material use by up to 50% and reduces energy loss due to membrane resistance.

More important, NEXAR polymers eliminate the current use of PVC (poly(vinyl chloride)) in electrodialysis membranes. The outstanding water transport rate of NEXARTM membranes also significantly improves energy recovery ventilation (ERV), by which exhausted indoor air conditions incoming fresh air. For other humidity regulation applications, including high-performance textiles and clothing, NEXARTM polymers offer environmental benefits by completely eliminating halogenated products such as Nafion polymers and PTFE (poly(tetrafluoroethylene)) that may require hazardous halogenated processing aids.

Kraton introduced NEXARTM polymers in the United States, China, and Germany during 2010. In the third quarter of 2010, Kraton completed its first successful large-scale production of NEXARTM of about 10 metric tons.

Designing greener chemicals: The Sherwin-Williams Company, Cleveland, Ohio. Oil-based alkyd paints have high levels of volatile organic compounds (VOCs) that become air pollutants as the paint dries. Previous acrylic paints contained lower VOCs, but could not match the performance of alkyds. Sherwin-Williams developed water-based acrylic alkyd paints with low VOCs that can be made from recycled soda bottle plastic (PET), acrylics, and soybean oil. These paints combine the performance benefits of alkyds and low VOC content of acrylics. In 2010, Sherwin-Williams manufactured enough of these new paints to eliminate more than 800,000 pounds of VOCs.

Small business: BioAmber, Inc., Plymouth, Minn. BioAmber is producing succinic acid that is both renewable and lower cost by combining an E. coli biocatalyst licensed from the Department of Energy with a novel purification process. BioAmber’s process uses 60% less energy than succinic acid made from fossil fuels, offers a smaller carbon footprint, and costs 40% less.

Succinic acid has traditionally been produced from petroleum-based feedstocks. In addition to its current use in food, drug, and cosmetic applications, succinic acid is a platform molecule that can be used to make a wide range of chemicals and polymers. BioAmber has developed an integrated technology that produces large, commercial quantities of succinic acid by fermentation rather than from petroleum feedstocks. Since early 2010, BioAmber has been producing succinic acid by bacterial fermentation of glucose in the world's only large-scale, dedicated, biobased succinic acid plant.

This $30-million plant includes an integrated, continuous downstream process. BioAmber believes its renewable succinic acid is the first direct substitution of a fermentation-derived chemical for a petroleum-derived chemical.

BioAmber’s economic advantage has given a number of chemical markets the confidence both to use succinic acid as a substitute for existing petrochemicals and to develop new applications for succinic acid. Succinic acid can replace some chemicals directly, including adipic acid for polyurethane applications and highly corrosive acetate salts for deicing applications. BioAmber has also made it economically feasible to (1) transform biobased succinic acid into renewable 1,4 butanediol and other four-carbon chemicals; (2) produce succinate esters for use as nontoxic solvents and substitutes for phthalate-based plasticizers in PVC (poly(vinyl chloride)) and other polymers; and (3) produce biodegradable, renewable performance plastics. BioAmber is leading the development of modified polybutylene succinate (mPBS), a polyester that is over 50 percent biobased and offers good heat-resistance (above 100 °C) and biodegradability (ASTM D6400 compliant).

In 2011, BioAmber plans to begin constructing a 20,000 metric ton facility in North America that will sequester more than 8,000 tons of CO₂ per year, an amount equal to the emissions of 8,000 cross-country airplane flights or 2,300 compact cars annually. BioAmber has also signed partnership agreements with several major companies, including Cargill, DuPont, Mitsubishi Chemical, and Mitsui & Co.

Academic: Bruce H. Lipshutz, PhD, University of California, Santa Barbara. Organic solvents are routinely used as the medium for organic reactions and constitute a large percentage of the world’s chemical production waste. Most organic solvents are derived from petroleum and are volatile, flammable, and toxic. Typically, organic reactions cannot be done in water because the reactants themselves are insoluble. Surfactants can be used to increase the solubility of organic reactants in water, but they often disperse the reactants, slowing the reactions.

Professor Lipshutz has designed a novel, second-generation surfactant called TPGS-750-M. It is a designer surfactant composed of safe, inexpensive ingredients: tocopherol (vitamin E), succinic acid (an intermediate in cellular respiration), and methoxy poly(ethylene glycol) (a common, degradable hydrophilic group also called MPEG-750). TPGS-750-M forms nanomicelles in water that are lipophilic on the inside and hydrophilic on the outside. A small amount of TPGS-750-M is all that is required to spontaneously form 50–100 nm diameter micelles in water to serve as nanoreactors.

TPGS-750-M is engineered to be the right size to facilitate broadly used organic reactions, such as cross-couplings. Reactants and catalysts dissolve in the micelles, resulting in high concentrations that lead to dramatically increased reaction rates at ambient temperature. No additional energy is required.

Several very common organic reactions that are catalyzed by transition metals can take place within TPGS-750-M micelles in water at room temperature and in high isolated yields. These reactions include ruthenium-catalyzed olefin metatheses (Grubbs); palladium-catalyzed cross-couplings (Suzuki, Heck, and Sonogashira); unsymmetrical aminations; allylic aminations and silylations; and aryl borylations. Even palladium-catalyzed aromatic carbon–hydrogen bond activation to make new carbon–carbon bonds can be done at room temperature, an extraordinary achievement.

Product isolation is straightforward; complications such as frothing and foaming associated with other surfactants are not observed. Recycling the surfactant after use is also very efficient: the insoluble product can be recovered by extraction, and the aqueous surfactant is simply reused with negligible loss of activity. Future generations of surfactants may include a catalyst tethered to a surfactant to provide both the reaction vessel (the inside of the micelle) and the catalyst to enable the reaction. Tethering catalysts in this way may reduce one-time use of rare-earth minerals as catalysts.

In all, this technology offers opportunities for industrial processes to replace large amounts of organic solvents with very small amounts of a benign surfactant nanodispersed in water only. High-quality water is not needed: these reactions can even be run in seawater. Sigma-Aldrich is currently offering TPGS-750-M for sale, making it broadly available to research laboratories.

Awards Methodology. An independent panel of technical experts convened by the American Chemical Society Green Chemistry Institute selected the 2011 winners from among scores of nominated technologies. During the program’s life, EPA has received more than 1,400 nominations and presented awards to 82 winners. Winning technologies alone are responsible for reducing the use or generation of more than 199 million pounds of hazardous chemicals, saving 21 billion gallons of water, and eliminating 57 million pounds of carbon dioxide releases to the air. These benefits are in addition to significant energy and cost savings by the winners and their customers.

Green Chemistry market opportunity of $98.5B in 2020

A new report from Pike Research concludes that green chemistry represents a market opportunity that will grow from $2.8 billion in 2011 to $98.5 billion by 2020. The definition of “green chemistry” is broad, Pike notes, and is evolving to meet a wide array of challenges ranging from dangerous and wasteful production processes and a heavy reliance on increasingly expensive petroleum to the persistence in the environment of toxic substances with far-reaching (and increasingly well-understood) effects on human and animal growth.

Green chemistry markets are currently nascent, with many technologies still at laboratory or pilot scale, and many production-scale green chemical plants are not expected to be running at capacity for several more years. However, most green chemical companies are targeting large, existing chemical markets, so adoption of these products is limited less by market development issues than by the ability to feed extant markets at required levels of cost and performance.

—Pike Research president Clint Wheelock

Wheelock adds that, while Pike Research anticipates dramatic growth rates for green chemicals during the coming decade, these emerging markets represent a drop in the bucket compared to the $4 trillion global chemical industry. By 2020, the firm expects that the total chemical industry will expand to $5.3 trillion in annual revenues, making green chemistry an approximately 2% component of that.

Pike Research forecasts that green alternatives in the polymer sector will represent the highest penetration level (5.7%) within the total chemical market, as it is somewhat more developed than the other key sectors. The special, fine, and commodity chemical sectors are more nascent and will enjoy somewhat lower penetration rates during the forecast period. The three major themes driving the green chemistry movement forward are:

• Waste minimization in the chemical production process;
• Replacement of existing products with less toxic alternatives; and
• A shift to renewable (non-petroleum) feedstocks.