Nano-Style Biodiesel Production

A new company is gearing up to galvanize the biodiesel industry with microscopic catalysts that could lower the cost of biodiesel production by up to 25 cents a gallon.
By Jessica Ebert | October 16, 2007
It's hard for most people to imagine a gram of material made up of tiny spheres no larger than the period at the end of this sentence that when stretched out two-dimensionally would cover the surface of a football field. Perhaps harder to imagine is a solid bead that size serving as a pivotal instrument in biodiesel production. Biodiesel producers around the globe, however, have vivid imaginations when it comes to more efficient production methods and are clamoring for more information about the technology. "People representing over 30 percent of the worldwide biodiesel capacity have contacted us about the technology," says Larry Lenhart, CEO of Catilin Inc., the startup created to commercialize the technology. "It's reassuring and highlights the need for new biodiesel technologies."

The nano-sized spheres, invented by Victor Lin, a chemistry professor at Iowa State University in Ames and a scientist for the U.S. DOE Ames Laboratory, weren't originally designed for biodiesel production. "Our expertise is in catalysis and material synthesis," Lin explains. "We initially wanted to explore this class of materials because we were interested in their structure."

It turns out this structure, a honeycomb of channels that run through the sphere, serves as a foundation for the development of tiny porous materials useful for a range of catalysis and biotechnological applications. Biodiesel production happens to be one of these applications, and the implementation of these tiny tools has been proven in the lab to alleviate several sticky points in the process.

Homogeneous Versus Heterogeneous
In simple terms, the production of biodiesel involves a chemical reaction between a vegetable oil or animal fat and methanol that creates a mixture of methyl esters and glycerol. The latter is a byproduct that can be turned into value-added chemicals while the former is purified to make biodiesel. In order to reduce the energy needed for the reaction to proceed, a basic catalyst is added. Today, that chemical of choice is sodium methoxide, a potentially explosive but inexpensive option.

Sodium methoxide, as well as other commonly used catalysts for biodiesel production are known as homogeneous catalysts because they dissolve in the reaction solution. The rub is that these chemicals become trapped in glycerin, and sometimes in the biodiesel itself, and must be removed. To do this, acid is added to neutralize the base and water is used to wash it from the products. Besides adding a layer of cost to biodiesel production, adding water shortens the lifetime of the biodiesel, Lin explains.

The new honeycomb spheres, however, are heterogeneous catalysts that don't break down in solution. "Our catalyst is a solid," Lin says. "We don't have anything leaching into the solution so when the reaction is finished we simply do a filtration to recover the spheres." In a bench-top reaction, the nano-particles are simply added to an oil and methanol mix forming a milky suspension. The reaction is run to completion and the entire mixture filtered to capture the catalytic spheres, which can be recycled and used again and again.

In addition, these new catalysts allow for the processing of numerous feedstocks, a feature expected to improve the economy of biodiesel production. At this time, sodium methoxide tends to be most effective in reactions involving soybean oil because this feedstock contains few of the impurities called free fatty acids (FFAs) that react with the catalyst to form soaps or salts. But the cost of this feedstock is on the rise and producers are looking to cheaper, albeit not as clean, options including animal fats such as beef tallow and chicken fat. When these cheaper feedstocks are used, however, they must first be pretreated in an acid-catalyzed reaction that converts the FFAs into esters. "It's like a catch-22," Lin says. "You want to use a cheaper feedstock but in order to use the cheaper feedstock you have to add another reaction and use another catalyst. All this defeats the purpose of switching the feedstock. Our catalyst will have the ability to contain both acidic and basic functionalities."

This kind of bifunctionality is abundant in nature, Lin says. Enzymes, for example, contain both acidic and basic residues. These residues are spatially separated yet work together to catalyze reactions. But how do you make a solid sphere act like an enzyme? "Our initial thinking was that if we could load the surface of these spheres with catalytically active functionalities we could enhance the kinetics and throughput of a reaction," Lin explains.

And that's just what they did. Leo Manzer, a retiree who directed DuPont's corporate catalysis center, visualizes the nano-catalysts as a bundle of straws. "You can vary the diameter of the straw very precisely to modify the surfaces in a very controlled fashion so that the acidic reactions take place on the outside of the straw and the triglycerides go down through the channel," he explains. "Basic catalysts decorate the inside of the straw and cause transesterification to take place. The methyl esters then exit the bottom of the straw," says Manzer, who developed catalysts for DuPont for 32 years before founding his own consulting company, Catalytic Insights LLC. "This is a pretty slick technology," he says. "It's a nice example of designing a catalyst to do a specific job."

That's what representatives of Mohr Davidow Ventures (MDV), a California-based investment firm concluded when they attended one of Lin's presentations. "We saw Dr. Lin making a presentation and thought about the applicability of this technology in the biodiesel market given the growth of the industry," explains Lenhart, who also serves as an executive-in-residence at MDV. "We saw this as a great opportunity to get in on the ground floor of a game-changing technology."

To that end, MDV started working with Lin to create a business around the technology. MDV invested $3 million into the business dubbed Catilin Inc. ("cat" for catalysis and "lin" for Lin) and pulled it out of Iowa State University, although the college still owns a portion of the business and continues to be a contributor of the technology, Lenhart says.

Catilin has been operating since the end of May and at this time the company has three objectives: "First and foremost we want to make sure this technology that we've proven in the lab works at a biodiesel pilot plant," he says. "We want to make sure we can produce our catalyst at a production level that makes sense and we want to make sure that the technology not only works economically but that it also works to produce the appropriate standards of biodiesel, the right ASTM levels."

To meet these objectives, the company is currently refurbishing a pilot plant at the Iowa Energy Center's Biomass Energy Conversion (BECON) facility. BECON, which is near Iowa State University, serves as a bioenergy plant for scaling-up promising laboratory research in biofuels. "We're breaking down and changing out some of the equipment because our process doesn't need as much equipment as the existing biodiesel plant needed," Lenhart explains. He expects that Catilin will be producing biodiesel and collecting results by the end of the year. "When you take something from bench to pilot-plant scale you get nervous if you're introducing a lot of new variables to the process like heat and pressure," he says. "We're really not introducing a lot of new things. Our process is not high heat, it's not high temperature, we're not mixing four or five things together so it's not as risky as you might find at another scale-up facility." The biggest challenge the company may face in scale-up is optimizing the rate of biodiesel produced with the heterogeneous catalyst. The advantage of a homogenous catalyst is that it tends to be reactive because it is in phase with the reactants. With the new heterogeneous catalyst, however, the reactants have to come into contact with the spheres and move through the pores. This could potentially slow down the reaction. That's where the BECON facility will come in handy. The pilot plant will house a 100-gallon reactor and could produce up to 1 MMgy, Lin explains. The modular nature of BECON makes it ideal for Catilin's scale-up because the company will be able to showcase the various options for incorporating the nano-catalyst technology into new and existing facilities. "BECON provides a unique flexibility that allows us to go in and play around with different ideas," Lin says. One of these is engineering a filtration system for the recycling of the beads. Another is designing a catalyst column where reactants would flow in and products out. "Right now we're working hard to figure out what is the best and most economical design," Lin says. "We want to be able to show people, this is how it works and these are the options so that they can decide what will work best for their operation."

The potential of the technology is great: a more economical biodiesel production process, a recyclable catalyst, and a cleaner biodiesel and glycerol byproduct. And the timing for these new catalysts might be right. "Some of the problems that didn't exist 20 or 30 years ago will now be a grand challenge," Lin says. "I think people are now starting to realize the importance of this kind of research."

"This is a really attractive technology that we're bringing to the table at the right time," Lenhart adds. "We're getting a good sense of the economic and environmental value of biodiesel but as a country we're trying to figure out how much to invest in biodiesel infrastructure. We help produce biodiesel on a more economic basis with less waste, requiring fewer government subsidies. That's a very attractive technology for people who might be interested in renewable fuels, which happens to be everybody."

Jessica Ebert is a Biodiesel Magazine staff writer. She can be reached at [email protected] or (701) 746-8385.
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