Biofeedstocks see real growth

Figure 1. Plant at Loudon, Tenn., makes two product lines based on corn fermentation.

“We have two generic products,” explains the joint venture’s presi-dent Steve Mirshak; their different characteristics suit them for specific ap-plications (Figure 2). Zemea propanediol finds use in personal-care and liq-uid-detergent consumer goods. Susterra propanediol finds use in industrial applications such as de-icing fluids, antifreeze and heat-transfer fluids.

Figure 2. Corn-based propanediol goes into products ranging from cosmetics to industrial heat-transfer fluids.

To get the right bug to transform corn’s sugar into Bio-PD, DuPont worked with Genencor, a Rochester, N.Y.-based division of Danisco A/S, Copenhagen. Then, DuPont allied itself with Tate & Lyle. They began de-velopment in 2000 at a pilot plant at Tate & Lyle’s research center and North American headquarters in Decatur, Ill., and in May 2004, created the joint venture. The 100-million-lb/yr plant went onstream in November 2006. The Loudon facility features nine-story fermentation vessels, the world’s largest, says Mirshak, who expects output to reach full capacity by 2009.

The plant also boasts a positive environmental impact. “We use 40% less energy to produce Bio-PD than a petroleum-based [glycol] product,” he says. “We recently revised our lifecycle estimates and found that cradle-to-gate, from the cornfield to the exit of our plant, reduces greenhouse-gases emissions by 56%.”

The development is already garnering accolades. The research teams from DuPont, Tate & Lyle and Genencor received a 2007 “Heroes of Chem-istry” Award from the American Chemical Society.

Bio-based polyethylene

Instead of corn, Dow Chemical, Midland, Mich., is relying on sugar cane as a feedstock. This summer Dow and Crystalsev, a Brazilian sugar-cane grower and ethanol producer, set up a 50/50 joint venture to build the first world-scale integrated facility to convert cane sugar into polyethylene.

“The joint venture’s product will have the same functionality, look and feel of Dowlex resins manufactured at other Dow facilities,” notes Jim Fitterling, president of Dow Basic Plastics. The Brazilian site will include 120,000 hectares, or approximately 250,000 acres, of sugar-cane production. “We’ll crush about 8 million tons of sugar to produce 700,000 liters [184,000 gallons] of ethanol.” The polyethylene facility will consume about 350,000 liters or 92,200 gallons, he adds.

The still-unnamed joint venture already has already started a year –long study that will get into the engineering design, location, infrastructure needs, supply-chain logistics, energy and economics. Fitterling predicts ethanol production from the plant’s first unit in 2009 and its second in 2010. “Full production’s expected in 2011, when we can go ethanol-to-polyethylene.”

The prime motivation for Dow, which has an established position in the Brazilian polyethylene market, is to insulate itself from high and volatile costs of conventional feedstock. A positive impact on climate change wasn’t an initial driver, “but as we developed the project, interesting things arose regarding sustainability and renewable resources,” Fitterling adds, noting the project will have about one-seventh of the CO₂ footprint of traditional poly-ethylene production.

Another project benefit will come through co-generation of energy by combustion of bagasse or residue cane fiber. Sugar cane produces six-to-eight times the energy required for its conversion to ethanol, Fitterling ex-plains. Beyond using recovered energy in ethylene/polyethylene production, the joint venture will sell some to the electrical grid.

Corn-to-ethanol technology, which is popular in North America, was a nonstarter for this project. One limitation was its slower reaction kinetics, Fitterling notes. “That makes it very uncompetitive compared to sugar cane in Brazil.”

Polyol progress

Meanwhile, in the U.S., Dow is making headway in natural-oil polyols (NOP), which it began investigating in the late 1990s. “We moved ahead in earnest after the [2001] purchase of Union Carbide,” recalls Erin O’Driscoll, Dow Polyurethanes business development manager.

Using Dow-developed process equipment and Carbide-based hydro-formulation technology, Dow ran a full-scale production campaign for soy-based polyol at a contract manufacturer in 2005, she notes, making hundreds of thousands of pounds of NOP for commercial trials by end-users (Figure 3).

Figure 3. Full-scale production campaign for natural-oil polyols allowed trial manufacturing of foam.

Dow’s multi-step process decomposes the vegetable oil into essential components and functionalizes the molecules to create diols, triols, etc., O’Driscoll explains, adding that the process suits many natural oil feed-stocks besides soy. She says the NOP renewable content depends on cus-tomer-application-specific design requirements for the final polyol. Initial NOP offerings will be for conventional bedding-and-furniture slab foam; memory or viscoelastic foams; flame-laminate foams for the automotive in-dustry; and coatings, adhesives, sealants and elastomers.

Initially the company’s Dow Haltermann Custom Processing (DHCP) unit in Houston will manufacture the NOP. “We’ve had our first commercial sale to a domestic company,” O’Driscoll says, forecasting fully commercial production by the end of 2007.

A new industry?

While DuPont and Dow employ materials traditionally grown mainly for food use, researchers are sowing other types of biofeedstocks. “We’re on the verge of the beginning of a new industry producing fuels and chemicals from biomass — non-food — feedstocks,” believes Jonathan R. Mielenz, leader of the bioconversion-science-and-technology group at the U.S. De-partment of Energy‘s (DOE’s) Oak Ridge National Laboratory (ORNL), Oak Ridge, Tenn.

Mielenz thinks that food-crop/starch-based feedstocks work better than biomass-based ones for monomers and polymers, though. That’s pri-marily because biomass-based chemicals require more purification, he ex-plains.

However, that doesn’t limit the use of biomass for other chemicals. For example, he suggests biomass is preferred for ethanol and butanol “in part, because they can easily be separated from the fermentation liquor by distillation.” These biomass-derived alcohols also have the same properties as ones produced from conventional feedstocks, he says.

Fermentation of biomass can readily produce chemicals such as fur-furals, levulinic acid and other materials. Ongoing work at ORNL involves cellulose-to-ethanol fermentation at high temperature, Mielenz notes. This yields not only ethanol but byproducts such as lactic and acetic acids. De-veloping new processes like these and making them available to companies for commercialization remains an ORNL goal, he stresses.

One company taking advantage of DOE fermentation technology is Diversified Natural Products Inc. (DNP), New York, N.Y. “DNP has exclusive rights to the succinic-acid-fermentation technology developed at DOE and patented by it and Michigan State University,” says Dilum Dunu-wila, the company’s vice president of business development.

DNP has allied itself with France’s Agro Industries Recherche et Developpement (ARD) to create joint venture BioAmber. “ARD has extensive experience in developing and commercializing fermentation-based products,” notes Dunuwila.

Funded by the Champagne Cereales cereal, Crystal Union sugar-beet and Chamtor alfalfa cooperatives, ARD will provide direct access to wheat- and sugar-beet-derived glucose through an 80-million-gal/yr ethanol facility the cooperatives are constructing at Bazancourt-Pomacle, France. Phase I of the Cristanol ethanol plant began operation this June. Phase II, which will about double capacity, is under construction and should come online in late 2008. It also will yield byproduct CO₂, a raw material for BioAmber’s succinic acid, to be produced at an adjacent bio-refinery.

Currently, BioAmber is moving ahead with a 5,000-metric-ton/yr succinic-acid demonstration facility near the ethanol plant. Dunuwila expects start up in the first quarter of 2009. Then, the joint venture plans to construct a 50,000-metric-ton/yr unit that integrates with the ethanol plant. “DNP will build a similar-sized facility in North America,” he predicts.

Fueling additional demand

Meanwhile, the use of biofeedstocks to make fuels continues to grow. For instance, palm oil is winning a notable role as a feedstock. Facilities based on it are “becoming very large” says Peter Faessler, lead application engi-neer with Sulzer Chemtech, Winterthur, Switzerland. He adds that the un-wanted, higher-melting solid fraction in crude-palm-oil-based biodiesel is an important raw material for oleochemicals. That particular fraction can be further purified by distillation or hydrogenation to produce fatty alcohols.

Soy serves as a principal feedstock in biodiesel production at Future-Fuel Chemical, Batesville, Ark., which got into biofuels in late 2005. Be-sides biodiesel, the company has been making premium fuel pellets with North Arkansas hardwoods since last March.

“We’re a multifeedstock biodiesel producer,” explains biofuels man-ager Rich Byers. The company’s continuous biodiesel process can accom-modate refined soybean oil and cottonseed, canola, corn and palm oils, as well as pork lard, beef tallow and poultry fat. “What comes out is ASTM D6751 biodiesel, made predominantly from soybean and cottonseed oils and probably some pork lard,” he notes. The Batesville facility is a BQ-9000 producer, meaning it satisfies the requirements of the National Biodiesel Ac-creditation Commission. Annual production is 24 million gallons, but the company in April announced plans to boost output to 196 million gal/yr. within 18 months.

For every gallon of biodiesel, FutureFuel produces a pound of glyc-erin. The company currently is investigating methods to use that byproduct in antifreeze and animal-food additives, Byers notes.

Another BQ-9000 producer is Dow. DHCP makes biodiesel in Hous-ton, Texas; Kallo, Belgium; and Middlesbrough, U.K. “For every 10 million gallons of biodiesel, we get 1 million gallons of glycerin,” explains Simon Upfill-Brown, DHCP’s general manager. This has led to another Dow initia-tive, to deal with glycerin byproduct — which is becoming a major issue for biodiesel makers (see www.ChemicalProcessing.com/industrynews/2007/020.html and www.ChemicalProcessing.com/articles/2007/099.html). The company now is converting that glycerin into polyethylene glycol renewable or PGR. In March Dow started what it terms a pilot-scale unit to produce PGR at an an-nual rate of 10 million to 20 million pounds.

“The purity of our product coming out of pilot scale is very close to PGI [propylene glycol industrial grade],” notes Mady Brico, global products director of propylene oxide/propylene glycol for Dow’s Polyurethanes unit. PGR is compatible with many industrial PG applications, such as for unsatu-rated polyester resins for boat hulls and bathroom fixtures, aircraft de-icers, antifreezes as well as heavy-duty liquid laundry detergents. “You have to absorb carbon to grow renewables,” adds Upfill-Brown, pointing out PGR’s potential positive climate-change impact.

Brico expects full-scale commercial availability in 2008–2009, with estimated annual output then of 50 million to 60 million pounds. “We’re waiting to see where glycerin and biodiesel continue to move.” The com-pany is looking at a variety of glycerin supplies, from crude to refined. “Our [current] customer is World Energy, and they actually own the glycerin,” Upfill-Brown says.

Ethanol initiatives

Like biodiesel’s, cellulosic ethanol’s popularity continues to increase. For instance, FutureFuel has been investigating it since this spring. Meanwhile, at the National Corn-to-Ethanol Research Center in Edwardsville, Ill., re-searchers are working on converting corn-kernel fiber into ethanol, explains director John Caupert. “It is conceivable that theoretical ethanol yields will increase by 7% to10%.”

In June, Mendel Biotechnology Inc., Hayward, Calif., and BP, Lon-don, U.K. announced an alliance to develop feedstocks for cellulosic biofu-els. Under the agreement, BP will fund a five-year research program through Mendel.

Research began in June on producing mischanthus, a hardy grass. “It’s the most productive perennial grass in the world — it can be grown in many places,” notes James Zhang, Mendel’s vice president of business develop-ment. Europeans have studied the grass for a decade, he says, and “identified it as promising for cellulosic feedstock.”

Breeding the grass using conventional methods is the team’s initial goal, Zhang says. Each ton of grass now produces about 80 gallons of etha-nol, he explains. “We envision that in a few years, we will be able to get about 100 gallons per ton of grass.” He projects about 10 tons to 15 tons of dried grass per acre and a spring-to-winter growing season. He also foresees creation of grass farms, which Zhang calls dedicated bioenergy farms, and output from them within five years. DOE, the U.S. Department of Agricul-ture and Mendel researched available lands and found “as much as 50 mil-lion acres could be dedicated,” he notes.

In addition, collaborating with BP, Mendel will accelerate an already started breeding program to improve the grass. It plans breeding stations in Champaign-Urbana, Ill. and Auburn, Ala. The company also will step up breeding collaborations with Tinplant Biotechnik und Pflanzenvermehrung GmbH, a breeding-and-plant-science company located in Small Wanzleben, Germany, and Hunan Technical University in China.

Zhang predicts that producing molecules from the entire carbohydrate portion of the crop will require new varieties of grass. “To ensure a consis-tent supply of feedstocks to refineries, a new seed industry is needed to pro-vide farmers with high-yielding varieties.”

One seed that’s already been planted is the idea of using biofeed-stocks, and the chemical industry seems ready to reap the rewards.