Renewable Feedstocks are in the Bag

Chemical firms show growing interest in bio-based production.

By Bill Gerards, Contributing Editor

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Companies in the chemical industry are increasingly using or at least investigating renewable resources such as crops and agricultural residues to replace petroleum-based feedstocks, as we’ve regularly covered (see Related Renewable Energy Content sidebar to the right). This is prompting new, broader thinking about the processes that make polyols, polymers and many other materials.

The price of oil certainly is one major factor driving interest. “It has refocused our thoughts on energy and the need to have alternative feedstocks,” says Katie Hunt, who serves as leader, technology partnerships, at Rohm and Haas Co., Philadelphia, which was recently acquired by Dow Chemical. However, the impetus goes well beyond immediate economic issues.

“Sustainability is the big umbrella under which energy, food and water, and all these global challenges fall,” notes Hunt, who recently received the additional title of corporate sustainability director and is immediate past president of the American Chemical Society. Rohm and Haas wants to help place sustainable development at the forefront of the chemical industry’s thinking, she says, adding that sustainability will be infused throughout the company’s activities. The company is adopting the principles of a non-governmental organization called The Natural Step, which helps companies around the world to integrate  sustainability thinking into the full range of their procedures and policies.

Renewables should be used when they make good environmental sense as well as good business sense, she stresses: “We’re not just looking for a ‘feel-good’ here.”
The potential is luring firms into the chemical industry. For instance, last year corn miller Archer Daniels Midland (ADM), Decatur, Ill., formed an industrial chemicals group. “Renewable, bio-based industrial chemicals fit into two major trends that we’re seeing in the marketplace: the desire to improve a product’s environmental footprint and the desire to reduce the use of petroleum-based products,” ADM said at the time.
However, going green may require companies to critically reevaluate how they operate plants and what kind of expertise is essential. After all, bioprocessing typically involves small-scale low-temperature batch operations rather than large-scale continuous units, notes Ryan Gill, managing director of the Colorado Center for Biorefining and Biofuels (C2B2) at the University of Colorado, Boulder, Colo. (C2B2 gets support from a number of chemical companies). But some firms may find it hard to change from their commodity mindset, believes Oliver Peoples, co-founder and chief scientific officer of bioproducts developer Metabolix, Cambridge, Mass. “The innovation will take place in the small companies,” he predicts.

“You need to be constantly looking for those competencies you’d like to have” and pursuing alliances that make sense, regardless of the partner’s sector or size,” counsels Hunt.

Pursuits of biofeedstock ventures do indeed come in all shapes, sizes, strategies and places. For instance, when DNP Green Technology, Princeton, N.J., wanted to commercialize its fermentation route for making succinic acid from renewable sources, it turned to Agro Industrie Recherches et Developpements (ARD), Pomacle, France, which is owned by a large agricultural group and tries to support the country’s rural economy, to build a demonstration plant, says Dilum Dunuwila, vice president for business development at DNP.

The joint venture, named BioAmber, aims to prove the technology works on an industrial scale at a biorefinery at Pomacle that will be expanding its already diverse mix of products. The biorefinery complex incorporates wheat and sugar-beet processing facilities, a cogeneration unit and an ethanol plant — whose net output of CO2 will go to the succinic acid plant, whose fermentation technology consumes CO2, says Dunuwila. The demonstration plant for succinic acid production is expected to come online in September 2009.

BioAmber’s manufacture of succinic acid from sucrose or glucose fermentation uses patented technology under an exclusive license from the U.S. Department of Energy (DOE) and Michigan State University. The succinic acid can be converted into a number of products including 1,4 butanediol, which is expected to enjoy growing demand.

A Long Journey
Even a true, integrated biorefinery like BioAmber’s represents an early step in a long journey, declares Gill. That journey is towards a second-generation biorefinery that can be large-scale, cost-effective and commercially viable in replacing hydrocarbon feedstocks, he says.

Biofuels face this challenge first. The U.S. government has mandated that 36 billion gallons of fuel used in 2022 must come from renewable sources, with at least 16 billion gallons from cellulosic ethanol — that is, ethanol derived from non-food feedstocks such as cane, grasses, wood and agricultural waste. Gill notes that Democratic presidential candidate Barack Obama wants to raise the renewable fuels requirement to at least 60 billion gallons of advanced biofuels by 2030.

With this mandated expanded level of biofuels production, “it is absolutely critical that we find biomass sources that are scalable” — that is, not limited by constraints that have already shown themselves with corn-based ethanol where “food versus fuel” supply debates arise, notes Gill.

Success in biofuels would be quickly followed by success in biofeedstocks, he expects.
Chemical companies won’t require nearly as vast a quantity of renewables, but Gill still sees them moving to next-generation biofeedstocks. Echoing Hunt, he says the move will occur where it makes sense in terms of cost-savings and compatibility with products and facilities enjoying growing consumer demand. Process integration will be “a real issue” in deciding that compatibility between biofeedstocks and chemical plants, he adds.

Near-Term Progress
Much of the focus for the foreseeable future will center on cellulosic ethanol. Once production technology for cellulosic ethanol matures, the cost should run about $0.75/gal., including feedstock and capital recovery, predicts “The Role of Biomass in America’s Energy Future,” a project jointly headed by Dartmouth and the Natural Resources Defense Council, New York City, and sponsored by the DOE, among others. This reflects a representative price for cellulosic biomass of $60/dry ton, notes Lee R. Lynd, a professor of environmental engineering design at Dartmouth and co-leader of the project, which corresponds to oil at $22/bbl. (Lynd has developed a bacterium to enhance production of cellulosic ethanol, see In Process: Bacterium Boosts Ethanol Prospects:

This potentially low-cost alternative is attracting a number of companies. For instance, DuPont, Wilmington, Del., announced in July a partnership between DuPont Danisco Cellulosic Ethanol (DDCE) and the University of Tennessee Research Foundation to build “an innovative pilot-scale biorefinery” to “develop the commercial package for DDCE’s leading cellulosic ethanol technology.” Important elements include working with Tennessee farmers “to develop the first dedicated cellulosic energy crop supply chain for cellulosic biorefineries utilizing switchgrass” plus the design of a facility flexible enough to operate on either switchgrass or corn waste — stover, cobs and fiber.

DuPont already markets products based on renewables. For instance, the company told Chemical Processing that next year it will complete an expansion of its Sorona polymer plant in Lenoir County, N.C. A key ingredient in the polymer is so-called Bio-PDO — 1,3 propoanediol derived from corn and considered an important building block for bioproducts.

The Bio-PDO is manufactured in the Loudon, Tenn., plant of DuPont Tate & Lyle Bio Products, a partnership with sugar-maker Tate & Lyle, London, U.K. The joint venture recently announced that its Zemea brand of propanediol, developed for use in cosmetics and personal care products, has received certification as a natural product by Ecocert, L’Isle Jourdain, France, an international certification group.

Zemea and another branded grade of Bio-PDO, as well as Sorona and a renewably sourced polyol branded Cerenol are among the offerings of DuPont BioMaterials, one of the businesses in the DuPont Applied BioSciences technology platform for high-performance renewable-sourced materials. Another Applied Biosciences business, DuPont Bio Fuels, last year entered a partnership with BP to construct a demonstration facility for biobutanol, an advanced biofuel that might compete with ethanol in the future.

Another company that has formed a partnership with BP — this time to accelerate the development and commercialization of cellulosic ethanol — is Verenium, Cambridge, Mass., which has proprietary technology for producing ethanol from such feedstocks as sugar-cane bagasse, wood products, agricultural waste and dedicated energy crops.  A first-phase agreement between BP and Verenium announced in August aims to invest $90 million in technology development over the next 18 months. A second-phase agreement, now in discussions, could yield a joint venture set to develop projects in the U.S. and potentially to license the technology overseas. Verenium foresees the  first commercial-scale facility starting production of cellulosic ethanol by 2012. At this time, a plant capacity of 30 million gallons per year is envisioned, using sugar-cane bagasse, energy cane (similar to sugar cane but high in fiber and closer to the predecessors of today’s high-sucrose canes), high-biomass grain sorghum, and similar grassy crops.

Verenium also has recently won a DOE grant that it expects to use to support operations at a demonstration-scale cellulosic ethanol biorefinery in Jennings, La. DOE has committed nearly $2 billion, over more than a decade, to support cellulosic energy technology, notes John Howe, vice president for public affairs at Verenium. Much of DOE’s money has gone toward use of corn stover and switchgrass as feedstocks, although Verenium’s own part of the research has centered on faster-growing canes, yielding more biomass per acre. Nevertheless, the company’s technology is adaptable to a broad range of feedstocks, Howe stresses.
“This is part of a historic shift,” he adds, reflecting that the energy and chemical industries’ stepped-up focus on renewable carbohydrate sources of energy is actually a reversal of the shift toward fossil hydrocarbons that started with coal-burning industries of the 18th century. The quest isn’t only for cheaper power but also for finding the most efficient, practicable ways to produce sugars as chemical building blocks, says Howe. No one company can do it alone: “Alliances are going to be a key part of making this technology commercial.”

More Direct Route  
Production of bio-based chemicals typically requires fermentation, e.g., to make ethanol or another building block. However, Metabolix is working on a shortcut. In August the company revealed that it had bioengineered switchgrass plants to produce significant amounts of polyhydroxyalkanoate (PHA) bioplastics in their leaf tissues. “This result is the first successful expression of a new functional multi-gene pathway in switchgrass,” demonstrating “a powerful tool for maximizing the potential of biomass crops for both bioplastics and biofuels production,” Metabolix declared.
“We’re looking at this whole bioenergy space not because we want to be a biofuels company but because, by adding value to those crops, we can facilitate low-cost bioplastic or biofeedstock production,” says Peoples. Biotechnology can add value by giving a crop like switchgrass multiple desirable traits such as drought tolerance, high yield and high degradability, he adds.

Figure 1
Pioneer Plant: First fullscale production plant for Mirel biopolymer is taking shape in Clinton, Iowa.
Source: Metabolix.

Metabolix, like other companies, isn’t restricting itself to a single feedstock; it may work with crops other than switchgrass — oil seeds and sugar cane, for example. And it’s also partnering. It formed a joint venture with ADM called Telles, which is commercializing “sustainable and biodegradable” bioplastics trademarked Mirel. The first commercial-scale Mirel production plant is under construction adjacent to ADM’s Clinton, Iowa, wet corn mill (Figure 1). The Mirel plant is expected to be online in the second quarter of 2009 with a capacity of 110 million lb/yr of Mirel resin, in pellet form destined for converters and end-use products.

Other firms also see promise in biopolymers and “green” feedstocks for plastics.” For instance, Braskem, Sao Paolo, Brazil, announced this year a linear polyethylene made from biobutene and intended for markets such as packaging, automotive and hygiene. Also this year, NatureWorks, Minnetonka, Minn., a joint venture of Cargill, Minneapolis, Minn., and Teijin Ltd., Osaka, Japan, launched Ingeo biopolymer fibers for apparel, furnishing and other textile applications. Ingeo is an extruded form of the company’s namesake biopolymer, which already has won acceptance, e.g., for films, containers and coatings.

Meanwhile, Cargill revealed in July that it had begun construction of what it calls the first “world scale” bio-based polyols plant. The $22-million soybean-based facility in Chicago will make so-called BiOH polyols for producing polyurethane for furniture, automotive and other markets. Cargill introduced the polyols in 2005, using a toll processor, but added its own production facilities in Brazil in 2007.

Dow, which began research on bio-based polyols in the early 1990s, markets its Natural-Oil Polyols (NOP) derived from soybeans. Last year the company introduced Renuva brand Renewable Resource Technology for making soybean oil-based polyols.
Dow has been active in biofeedstocks and bioproducts on several fronts. Most recently, in July, it announced a program with the DOE’s National Renewable Energy Laboratory, Golden, Colo., to jointly develop and evaluate a process to convert biomass to ethanol and other chemical building blocks. A “mixed alcohol catalyst” from Dow will be used to convert nonfood materials like wood wastes and corn leaves to synthesis gas. The gas will be converted into a mixture of alcohols including ethanol for use as transportation fuel or chemical building blocks.

Figure 2
Epichlorohydrin Pilot Plant: Dow developed its glycerin-to-epichlorohydrin process at this pilot plant in Germany.
Source: Dow Epoxy.

A joint venture of Dow and Crystalserv in Brazil produces Dowlex brand polyethylene resins through a process that converts sugar to ethanol and then into ethylene.
Other Dow activities include the manufacture of Propylene Glycol Renewable (PGR) from the glycerin byproduct of biodiesel making. Dow Epoxy has developed a process to produce epichlorohydrin from glycerin and is building a world-scale plant in Shanghai (Figure 2).

The company is aggressively pursuing bio-based products , says Erin O’Driscoll, director of Dow’s Biosciences team. The pieces are fitting together, but Dow isn’t rushing headlong into any and every opportunity with renewables, she adds.
Opportunities may lead to new products, but these still should fit with the company’s existing businesses; they also should offer differentiated value propositions and must make sense in terms of expected market growth. Other factors include the raw material supply in the place where a project is being considered and the suitability of the conversion technology. Replacement of petroleum-based feedstocks with bio-based feedstocks is more likely to occur at new plants being planned to meet growing demand and less likely if retrofitting is involved. “Every project has to compete” on the basis of good business sense, O’Driscoll stresses.

The Business Case
More and more companies are confronting decisions about biofeedstock projects and the role that renewables will play in their business planning, notes Mike Mendez, business consultant with AspenTech, Burlington, Mass., a supplier of software and services to process industries. The equations for determining the business sense of a given project can get very complicated. Perspectives differ on where in the pipeline — with the feedstock itself, in the fermentation step or in other steps in the pathways toward intermediates and final products — renewables make the most sense. There have been questions about food supply versus fuel supply, governmental policies, socioeconomic trends, and about whether the “green” technologies really use less energy or have a smaller environmental footprint. But the answers are emerging, at least on the macro scale, he says.

“I’m confident we will make fuels from biomass,” declares Mendez. Breakthroughs in fuels will unleash even more breakthroughs in chemical feedstocks. “There are brand new industries being created,” he says. “There’s a lot of momentum being generated.”
In such an environment of change, chemists and engineers today need to be both reflective and responsive, says Hunt. The reflection can come through various channels, including the principles of green chemistry — one of which is the use of renewable feedstocks. But responsiveness is important, too, she stresses. Companies have to “think, plan, and do” despite the complexity and uncertainty, acting in the context of the unique circumstances of each site and project but also in the light of general principles of good business sense.

“What’s different now is the traction,” she concludes. Companies are “taking it to the next level.” She refers to the pointillistic style of painting where countless dots of different colors appear as a picture when viewed as a whole. “The difference is not doing it in a pointillist way, but rather doing it in a strategic way,” says Hunt.


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