Biodiesel Magazine, ND
10-17-07
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
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 twodimensionally 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 acidcatalyzed 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.”
Bifunctionality
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 Californiabased 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 nanocatalyst 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.”
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 twodimensionally 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 acidcatalyzed 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.”
Bifunctionality
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 Californiabased 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 nanocatalyst 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
jebert@bbibiofuels.com or (701) 746-8385.