Green Chemistry: Biofeedstocks Still Grow

Figure 1. Cellulosic Ethanol Catalysts: DuPont scientist
Paul Vitennan developed biocatalysts for DDCE joint venture.
Source: DuPont.

BASF trumpets its resolve to use renewable raw materials. "We place a high priority on selecting the most sustainable resources for each application," states "Report 2008: Economic, Environmental, Social Performance." "We use renewable raw materials when they offer economic or environmental advantages… We are also developing products such as catalysts and process chemicals for the decomposition of biomass to facilitate the use of renewable raw materials." DuPont, Wilmington, Del., also clearly is focusing on renewables. "This country has to lead the way to an energy-secure future," stresses Uma Chowdhry, its senior vice president and chief science and technology officer. The path toward sustainability in energy and chemicals requires expertise in feedstocks, enzymes, genetics, refining and more — generally "leveraging the entire supply chain," she adds. DuPont is committed to a wide range of collaborations for "renewable technologies" research and to moving from cellulosic ethanol to biobutanol as "the next-generation biofuel." A partnership between DuPont Danisco Cellulosic Ethanol (DDCE) and the University of Tennessee, Knoxville, Tenn., expects to begin pilot production of ethanol from cellulosics — corn waste and switchgrass — this year at Vonore, Tenn. (Figure 1). DuPont is partnering with BP for biobutanol; they hope to have a "commercial biotechnology package" ready in 2010, aiming to use non-food feedstocks and produce biobutanol at prices lower than that of ethanol. However, today's economic realities are impacting industry's efforts. In a recent interview, Gill reported that C2B2's momentum toward renewable fuels and feedstocks has decreased. Some chemical companies, including DuPont and Dow, have dropped their membership. There's still plenty going on, but the change in economic conditions constitutes nothing less than "a threat to the industry," he declares. Changing ParadigmThe industry is moving forward, but "the paradigm is changing," notes Dilum Dunuwila, vice president for business development at DNP Green Technology, Princeton, N.J. When oil prices exceeded $100 per barrel last year, a broad switch from petroleum to bio-based feedstocks seemed almost a given, Dunuwila says. Now the transition looks to be more incremental, more pragmatic and complementary, and based on the value of biotechnologies with regard to price, performance, renewable content and CO₂ footprint reduction. The company, which is commercializing a fermentation route to succinic acid from corn, wheat, sugar beet, sugar cane and cellulosics, is persevering. Succinic acid production should start this fall at a 2,000-metric-ton/yr demonstration plant at Pomacle, France, of its joint venture Bioamber. "There's a significant burden on industrial biotech companies to show that fermentation technologies work at a significant scale for long periods of time," says Dunuwila. Besides proving its process reliable and flexible enough for multiple feedstocks, the company must convince potential customers that succinic acid will be available to them in sufficient quantities and at competitive prices. "We have developed technologies with the value chain — renewable feedstock companies to petrochemicals — in mind." One promising target market is the C4 segment, including 1,4 butanediol. Bioamber announced a partnership in December with Basic Solutions, Leeds, U.K., for a "new generation of runway de-icers with a low impact profile." Testing at airports should begin this winter. The paradigm also is changing because oil price spikes aren't the only driver of innovation, Dunuwila adds. Carbon taxes and caps on greenhouse gases emissions are looming. Also, consumer demand for renewables and greener technologies provides an impetus. "Even the big players have accepted that there's a place for biochemicals… The new innovation cycle, particularly for polymers, shows 100% of the effort dedicated to technologies from bio-sources," he says. Another company staking out locations along the renewable resources value chain is Microbia Inc., Lexington, Mass. It aims to leverage its metabolic engineering and bioprocessing expertise to develop and commercialize green processes for specialty and commodity chemicals production. The first specialty chemical products should appear in 2010. "The company's pipeline includes two carotenoid products for use in human and animal nutrition markets that are traditionally manufactured from petrochemical-derived raw materials," Microbia notes. "Currently at the commercialization stage, Microbia believes its natural fermentation-based processes for these products offer significant cost advantages over traditional chemical synthesis methods, with the additional advantage of being based on renewable raw materials." "We're feeling very good about our technology right now," declares Richard Bailey, CEO. While the current economy has complicated raising money, there are interested investors, he says. Prudent use of capital dictates opting for toll manufacturing instead of building a facility. In addition, "we are doing some things sequentially where normally we would have done them as parallel," Bailey notes. Succeeding with commodity chemicals requires large-scale low-cost infrastructure that a small company can't provide. So, Microbia aims to team up with major producers. One such partnership is with Tate & Lyle, London, to pursue unspecified opportunities, says Bailey.

Figure 2. Demonstration Plant: Facility in Jennings, La.,
uses bagasse and sugar waste to produce ethanol.
Source: Verenium.

Expanding the ChoicesThe number and variety of project and product announcements suggest a fast pace of activity in the biofeedstocks and renewables arena. The movement from food-based ethanol to cellulosic ethanol is brisk. Besides the DDCE/University of Tennessee demonstration plant, BP, London, and Verenium, Cambridge, Mass., announced in February a 50/50 joint venture for a commercial-scale plant in Highlands County, Fla., with ground breaking planned in 2010. Ethanol now is being produced from bagasse and sugar waste by Verenium in Jennings, La. (Figure 2), from woody biomass by Range Fuels, in Denver, Colo., and from wheat straw by Iogen in Ottawa, Canada, according to the annual report posted at the RFA website, http://www.ethanolrfa.org. Other feedstocks attract chemical experts and corporate investors, too. Algae promises high supply scale-up potential because of its prolific growth. OriginOil, Los Angeles, says its bioreactor technology speeds algae development; the company hopes to license that technology to customers including chemical and oil companies, and to enter into partnerships with biofuels producers. Archer Daniels Midland (ADM), Decatur, Ill., is collaborating with ConocoPhillips, Houston, to turn corn stover, switchgrass and wood waste into biocrude that can be processed in traditional refineries. In addition, ADM is operating biodiesel production plants in North Dakota and Brazil. There's also plenty of action in products and services to support bio-based production or reduce its cost. For instance, Verenium announced in March a partnership with Alfa Laval, Lund, Sweden, to offer enzymatic degumming services that increase the yields of biodiesel — using Verenium's Purifine PLC enzyme and Alfa Laval's engineering services and equipment. Meanwhile, Rohm and Haas, Philadelphia, (now part of Dow) has introduced a feedstock purification technology that is said to allow biodiesel makers to efficiently convert alternative feedstocks like crude vegetable oils and animal fats. Akzo Nobel Polymer Chemicals, Chicago, and lactic-acid-derivatives supplier Purac, Gorinchem, the Netherlands, reported in January that they've developed additives that will broaden the applications for polylactic acid (PLA) in the growing biopolymer market. The new additives help make PLA more stable and amenable to various processing equipment. Altering its ApproachDuPont's primary goal only a few years ago was to not add bio-components to its existing portfolio but to find "transformative new products that could only be brought to market using the new biotechnology tools." Biobutanol, now in development with partner BP, reflects that goal — "a new product with superior performance that just happened to be biologically derived and renewably sourced," notes Jan Koninckx, global business director for DuPont BioFuels, a part of DuPont Applied BioSciences. He tells Chemical Processing DuPont remains interested in biofeedstocks that entail a different approach but is also willing to invest in biofeedstocks that promise to fit well into existing processes. Biobutanol "will likely fit into the existing grain ethanol process infrastructure," he expects; the DDCE joint venture will seek to bolt its technology onto existing grain ethanol assets or will develop new stand-alone facilities. One thing is for sure, says Koninckx: "The development of new biomaterials, biofuels and other Applied BioSciences products and technologies requires an integration of disciplines." DuPont's broad toolkit doesn't negate the need for partnerships with other companies "in this day and age where speed to market is so critical." Koninckx points to Bio-PDO — 1,3 propanediol derived from corn and considered an important building block for bioproducts including polymers. The company partnered with Genencor, Rochester, N.Y., (now a division of Danisco) to develop the catalyst; Bio-PDO is manufactured in the Loudon, Tenn., plant of joint venture DuPont Tate & Lyle Bio Products. DuPont "will always have a door open to potential partnerships that help us move our technologies from lab to market in the most sustainable and cost-effective way," declares Konnickx. Working Along a Broad FrontDow Chemical also is striving to broadly use renewable resources. The Midland, Mich.-based firm in January announced its latest collaborative agreement to help reduce dependence on traditional oil and gas sources. It aims to jointly develop technology with specialty chemicals company Sud-Chemie, Munich, Germany, to more efficiently and economically convert synthesis gas, derived from biomass as well as coal, into "building block" chemicals. Efforts will focus on catalysts to produce chemicals including alcohols and olefins, the companies say. Dow adds that its enthusiasm for syngas conversion, which is largely understood to yield chemicals and fuels using existing (albeit expensive) technology, is "a promising route for the scale that Dow needs to have an impact." Dow is involved in many other renewables-focused partnerships. For instance, the firm says it's finalizing an agreement with DOE's National Renewable Energy Laboratory, Golden, Colo., to jointly develop and evaluate a biomass conversion process using a "mixed alcohol catalyst" from Dow. The aim is to transform materials like wood wastes and corn leaves into syngas for further conversion into ethanol and other alcohols. Dow is moving ahead on a number of other fronts, including its Renuva brand technology for making soybean-based polyols and its use of glycerin byproduct from biodiesel manufacture for producing Propylene Glycol Renewable and epichlorhydrin. The company is teaming up with Crystalsev/Santelisa Vale in Brazil to make polyethylene from sugar cane. Plans call for a 350,000-metric-ton/yr facility; startup date isn't firm. The worldwide economic situation isn't calling into question the company's push into renewables but does affect "how fast you can move," says Steve Tuttle, global business director for Dow BioSciences. Today's tough climate actually proves the value of partnerships that "help leverage external expertise," he adds. Dow, like other companies, says it continues to scrutinize each renewable-resources business prospect from a number of perspectives, including the availability and scale-up potential of appropriate feedstocks, the market for intermediate and end products, and compatibility of feedstocks and products with infrastructure and processes. Prospects generally keep improving. Innovation "continues to expand, not just in a linear fashion, because as you learn and advance technology, it becomes exponential," explains Tuttle. Coming TogetherAs knowledge deepens, the distinctions between work on biofuels and biofeedstocks are becoming less sharp, Tuttle says. "A molecule doesn't know whether it's going to be used for fuel or chemicals." A well-positioned company understands "the fuel/chemistry interface." Research and development that benefits both the fuel and chemistry sides "has dual market opportunities." Dow also gains from its expertise in catalysis because it's "a big enabler" for work in such high-priority areas as algae, biocrude, cellulosics and syngas, notes Bob Maughon, senior R&D director for the hydrocarbons and energy business. The potential to integrate diverse bio-focused technologies also captures the imagination at DuPont, and undoubtedly at other chemical companies. The collection of operations within DuPont's Applied BioSciences business and its Bio Materials group presents such opportunities for convergence, notes Koninckx. "You never know if these two businesses may connect at some point in the future," he says. "Our lead scientist often talks about an integrated biorefinery that produces cellulosic ethanol, grain ethanol, biobutanol and biomaterials. It is possible in the future." Sidebar: Mandate Promises Economic Boost The U.S. Renewable Fuels Standard (RFS) sets requirements for blending advanced biofuels — not ethanol derived from corn starch — into gasoline and other transportation fuels. The RFS begins at 0.6 billion gal/yr in 2009 and reaches 21 billion gal/yr in 2022. Such advanced biofuels are expected to reduce lifecycle greenhouse-gas emissions by at least 50% from baseline levels. They also promise to spur significant investments and new jobs, according to "U.S. Economic Impact of Advanced Biofuels Production: Perspectives to 2030" by Bio Economic Research Associates, Cambridge, Mass. That report, released in February 2009 by the Biotechnology Industry Organization, predicts: • Investments in advanced biofuels processing plants will reach $3.2 billion in 2012 and $12.2 billion by 2022.• Direct economic output from the advanced biofuels industry, including capital investments, R&D, technology royalties, processing operations, feedstock production, and biofuels distribution will rise from $5.5 billion in 2012 to $37 billion by 2022. • Direct job creation from advanced biofuels production could reach 29,000 by 2012 and 190,000 by 2022. This will include jobs for operators and technicians.