Bio-Based Projects Blossom

Chemical companies nurture efforts to make fuels and feedstocks.

By Seán Ottewell, Editor at Large

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Significant developments in using renewable feedstocks to make fuels and chemicals are blooming. For instance, Shell International, Houston, and Cosan, Sao Paulo, Brazil, in February, signed a memorandum of understanding for a joint venture (jv) worth almost $12 billion to produce ethanol from sugar cane. The deal would create an organization with 2-billion-l./yr. ethanol capacity.

"We see joining with Cosan as a way to grow the role of low-carbon, sustainable biofuels in the global transportation fuel mix. The joint venture would also enable Shell to set up a material and profitable bio-fuels business, with the potential to deploy next generation technologies," notes Mark Williams, downstream director.

The jv includes some of Shell's major interests in next-generation technologies, such as its 50% stake in Iogen, Ottawa, Ont., and its 14.7% interest in Codexis, Redwood City, Calif.

Iogen has been producing cellulosic ethanol at an Ottawa demonstration plant since 2004. Production topped 581,000 liters in 2009, more than double 2008 output. For its part, Codexis focuses on developing highly efficient biocatalysts that replace costly chemical steps in low-carbon manufacturing processes.

Meanwhile, in late January DuPont Danisco Cellulosic Ethanol (DDCE), Itasca, Ill., and it jv partners, the University of Tennessee (UT), Knoxville, Tenn., and Genera Engegy, Knoxville, held a ribbon-cutting ceremony for their cellulosic ethanol demonstration facility in Vonore, Tenn., and hailed it as a world's first. The 250,000-gal./yr. unit relies on agricultural residue such as corncobs and bioenergy crops like switchgrass as feedstocks. So far the partners have invested more than $50 million in the plant (Figure 1).

"The University of Tennessee Biofuels Initiative is the only fully integrated program that is working with farmers and agricultural industry to reliably supply the necessary feedstock so biorefineries can produce plentiful, affordable, renewable and sustainable fuels," notes Kelly Tiller, CEO of Genera Energy and director of external operations for UT's Office of Bioenergy Programs. Plans are in place for Tennessee farmers to devote an additional 4,000 acres to switchgrass this spring, bringing the total to 7,000 acres dedicated to that crop, she adds.

Meanwhile, Dow Chemical, Midand, Mich., which last June announced plans to work with Algenol Biofuels, Bonita Springs, Fla., to build and operate a pilot-scale algae-based integrated biorefinery at Dow's Freeport, Texas, site, has started a major promotion of new biodiesel technologies it has to offer following the acquisition of Rohm & Haas. These include Amberlyst BD20 solid catalyst esterification technology for production of biodiesel from inexpensive low-quality feedstocks and the associated Ambersep BD19WET feedstock purification technology which extends catalyst life time.

More alcohol
This year also is proving to be a busy one for the Energy & Environmental Research Center (EERC), based at the University of North Dakota, Grand Forks, N.D.

The EERC entered into a jv program in January with Syntec Biofuel, Vancouver, B.C., to develop technology to produce butanol from biomass and waste. Syntec already has devised a catalytic thermochemical process that breaks down sustainable low-cost wood and agricultural waste into components that react to form ethanol, methanol, propanol and butanol.

"We have proven our catalyst at the lab scale and so now we need to validate these results in a pilot plant that will be built here [Vancouver]," notes Michael Jackson, Syntec CEO. "It's fairly small, processing 1–3 t./d. of feedstock to give about 300 gal./d. of product. I'd say we have to get six months of results at 24/7 operation before going on to the next level. However, we don't anticipate any unusual scale up problems because the process uses proven gasification and Fischer Tropsch technologies."

Jackson also points to Syntec's work with the University of British Columbia, Vancouver, B.C., to improve catalyst yield. "We are getting 110 gal./t. of product at the moment. About 300 gal./t. is the theoretical maximum but with the University of British Columbia's help we think we can get to about 142 gal./t. That would be incredible."

Glycos Biotechnologies, Houston, is focusing on metabolic engineering and has developed a number of microorganisms that can convert low-value byproducts such as crude glycerin, gums and free fatty acids into higher-value chemicals.

"GlycosBio has a demonstration facility and recently completed a pilot where they proved their proprietary microbial technology to convert glycerin into 13,000 l. of higher-value chemicals and/or advanced ethanol. This success is the precursor to full commercialization which they are working towards in Latin America," says a spokesman.

Accenture, New York City, in a December 2009 report "Betting on Science, Disruptive Technologies in Transport Fuels" cites the company as one of 25 most likely to positively transform the supply-and-demand landscape of sustainable transport fuels and biochemicals within the next five years (see: www.accenture.com/Global/Services/By_Industry/Energy/R_and_I/Betting-on-Science.htm).

Meanwhile, the ChemPro Group, Boonton, N.J., and Mo-Fuel, Sikeston, Miss., have formed an alliance to commercialize a patented process to produce ethanol from cellulosic feedstocks. The route reportedly can handle a full spectrum of such materials, from wood chips and pulp-and-paper-plant byproducts to corn stover, rice straw, grass and even municipal waste. Moreover, its reactor design is said to enable easy addition of extra modular trains to boost capacity.

"The demonstration unit is in final assembly at our shop here in New Jersey and should be available for Mo-Fuel in the next 2–3 weeks. It's a self-contained cellulose hydrolysis unit running a continuous process that converts cellulose into sugars which can be fermented into ethanol. It demonstrates to potential users that we have the ability to make ethanol from their cellulose materials," said Steve Lavorerio, ChemPro's president, in late January. "The process is also economical as an add-on to existing corn ethanol plants. It can process the low-value waste product with the potential to increase yields of ethanol by 15% and improve the value of byproducts by 50%," he adds.

At least a dozen potential customers are lined up to trial the process, says Ted Lewis, Mo-Fuel president and chief R&D scientist. "Today it is more competitive than existing ethanol plants. But with our reduced construction and operating cost initiatives we should be able to knock the door wide open to production of biofuel that is competitive with petroleum products as well."

Diesel and jet fuels
Also in January DOE awarded UOP, Des Plaines, Ill., a unit of Honeywell, $25 million to build a demonstration unit in Hawaii to convert cellulosic biomass. The facility will use feedstocks such as forestry, agricultural and algae residues to produce pyrolysis oil (Figure 2) that then will be upgraded to transportation fuels. The plant, which will be built at the Tesoro refinery in Kapolei, should start up in 2014.

The unit will employ rapid thermal processing (RTP) technology developed by Ensyn, Ottawa, Ont. UOP and Ensyn in 2008 formed a jv, Envergent Technologies, Des Plaines, Ill., to offer RTP (Figure 3) and further develop technology for upgrading pyrolysis oil to transportation fuels. Earlier this year an Italian power company selected RTP for a facility to convert biomass into pyrolysis oil for power generation. The plant is slated for 2012 start up.

At the same time UOP continues to develop its Ecofining technology for producing diesel fuel. The route uses hydroprocessing to convert triglycerides from natural oils and wastes into high-quality diesels — essentially isomerized paraffins in the diesel range.

"Existing technologies create a methyl ester — but this gives rise to a number of technical issues including blending and the ability of existing pipelines to handle the product," says Graham Ellis, business manager for biorenewable energy. "The big difference between this and other renewable diesel technologies like co-processing is that we have separated the isomerization unit. So we can take any feed and produce exactly what is required in a client's spec. We are on the Mark II version of the process now and are producing Honeywell Green Diesel at about a 20¢/gallon saving over methyl ester production. And this includes capital depreciation," he adds.

The company also has just launched a process that takes the same feeds as Ecofining but uses selective hydrocracking to produce C10–C14 materials comparable to typical jet fuels. With help from Boeing, UOP has worked with a number of airlines including New Zealand Airways, JAL, KLM and Continental to test the product in real situations.

"We have generated 50,000–60,000 gal. from our own toll processing unit which is being used by the U.S. Navy and Air Force for testing and certification. Continental has reported slightly better fuel efficiency than with the usual jet fuel. So there is a lot of push to get swift certification of the fuel and we hope that this will happen this year. We are hoping that our process will lead to the beginning of a renewable jet fuel industry and this is a significant step," says Ellis.

The same process also has served to convert tallow into jet fuel for the U.S. Air Force and algae into jet fuel for the Navy. "We expect to deliver 1,500 gal. to the Navy this summer; there is a huge interest worldwide in algae but there are only a small number of companies that can produce in any quantity from it. We are trying to give them a route to fuel by ensuring that the oils produced are proven to be compatible with Ecofining and renewable jet processes," he notes.

Meanwhile, the EERC is teaming up with Whole Energy Fuels Corp., Bellingham, Wash., to develop cellulosic-based fuel additives to improve engine performance. "This technology will ultimately be used to improve engine performance using a renewable product, both in gasoline and diesel engines. In the case of diesel fuel, our additives will boost the cetane levels, improve flow properties and, most importantly, reduce particulate emissions," explains Ed Olson, EERC senior research advisor. A new company, Mercurius Biofuels, Ferndale, Wash., has been set up to help develop and commercializee the technology.

Mixed messages on algae
The Accenture report notes that continued evolution of first-generation feedstocks such as sugar cane, corn and rapeseed for ethanol, butanol and biodiesel is limited by available biomass. Algae, says Accenture, have the potential to produce 1,200 gal./acre compared to just 48 gal./acre for soybean. However, it adds, this will take significant long-term commitment to reduce costs, which currently run in the range of $2–8/l. ($8–30/gal.).

Even so, the report points to recent algae-based tie-ups between ExxonMobil/Synthetic Genomics, Chevron/Solazyme, Valero/Solix, Shell/Cellana and BP/Martek that might well cut the 10 years it estimates for algae-derived fuels to reach commercial production.

However, researchers from the Department of Civil and Environmental Engineering at the University of Virginia, Charlottesville, Va., caution that significant environmental hurdles must be overcome before fuel production ramps up. Their work indicates that algae production consumes more energy, has higher greenhouse gas emissions and uses more water than other biofuel sources such as switchgrass, canola and corn (See: Environmental Science & Technology, http://pubs.acs.org/doi/abs/10.1021/es902838n).

As an environmentally sustainable alternative to current algae production methods, the researchers propose situating algae production ponds behind wastewater treatment facilities to capture phosphorous and nitrogen — essential nutrients for growing algae that otherwise would need to be produced from petroleum. They also are pursuing complementary research on the economic lifecycle of algae compared to other bionenergy feedstocks.


Seán Ottewell is Chemical Processing's Editor at Large. You can e-mail him at sottewell@putman.net.

 

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