Skip to comments.Startup turns carbon dioxide into fuels
Posted on 06/15/2012 11:16:18 AM PDT by Red Badger
Ask Andrew Bocarsly about the innovation behind Liquid Light, a New Jersey startup company that turns carbon dioxide into fuels and industrial chemicals, and the Princeton University chemistry professor smiles ruefully. "The project goes back to the early '90s," he said. "But nobody cared about carbon dioxide at that time."
Today, carbon dioxide (CO2) is a hot topic. Scientists around the globe are searching for ways to store, dispose of, or prevent the formation of the greenhouse gas, which is a major driver of global climate change. Liquid Light hopes to take this concept one step further and harness waste CO2 as a source of carbon to make industrial chemicals and fuels.
The technology behind the process is simple: Take CO2 and mix it in a water-filled chamber with an electrode and a catalyst. The ensuing chemical reaction converts CO2 into a new molecule, methanol, which can be used as a fuel, an industrial solvent or a starting material for the manufacture of other chemicals.
Liquid Light's founders include Bocarsly and his former graduate student Emily Cole, who earned her Ph.D. from Princeton in 2009. Cole helped revive efforts in Bocarsly's lab to study the conversion of CO2 into usable fuels, which led to the launch of Liquid Light and an ongoing collaboration that Bocarsly said has been extremely positive for his research team at the University.
"We've made some discoveries that wouldn't have been made in a university setting, and this has really accelerated the research," Bocarsly said. "It is a very productive relationship."
Back in the 1990s, a former Ph.D. student of Bocarsly's named Chao Lin conducted some of the earliest experiments on turning CO2 into methanol. He used palladium metal as the electrode and pyridinium, an inexpensive ring-shaped molecule, as the catalyst. By plugging the electrode into an electrical outlet, he could drive an electrochemical reaction that converted CO2 into methanol.
As Bocarsly recalled, Lin was quite excited about his success. However, said Bocarsly, "We published that finding in 1994 and there was approximately zero interest in it."
The work languished until 2005 when Cole, then a new graduate student, told Bocarsly she wanted to work on a clean-energy project. She took up the challenge of reproducing Lin's results, but this time using sunlight instead of electricity to drive the reaction.
Cole set up a flask containing a solution of CO2 and a pyridinium catalyst dissolved in water. In place of sunlight, which emits a broad spectrum of wavelengths of light, she shined on the flask a blue light-emitting diode (LED) because it gives off certain wavelengths that are highly efficient at driving the reaction. In the flask she placed an electrode that is activated by particles of light, or photons. "We used a semiconductor electrode that would allow us to substitute light for electricity," said Cole.
In Cole's setup, photons hit a gallium phosphide semiconductor and excite its electrons to travel to the semiconductor's surface and into the surrounding water. The catalyst then shuttles the electrons to the CO2. Those electrons attract hydrogen from the surrounding water to turn CO2 (one carbon and two oxygens) into methanol (one carbon, one oxygen and four hydrogens) with the release of oxygen.
Bocarsly likes to call the process "reverse combustion" because it is like running a burning reaction backwards. Instead of burning fuel and oxygen to produce CO2, the CO2 converts back into fuel and oxygen. This time, when the team published in May 2008 in the Journal of the American Chemical Society, the results generated a lot of interest.
Taking the idea into industry
One person who read that paper was Kyle Teamey, an entrepreneur who was representing a venture capital firm that wanted to invest in clean-energy technologies. He was attracted to the idea that waste CO2 could be put to use as a starting material for making fuels and industrial chemicals that could be sold at a profit.
"Everyone had been talking about burying CO2 underground," said Teamey. "Why not instead turn carbon dioxide into something valuable?"
After months of talks with Bocarsly and Cole as well as other advisers, Teamey and Cole co-founded Liquid Light. The company licensed the technology from the University. Teamey serves as company president, while Cole and her team of chemists tackle the practical issue of how to scale up a laboratory invention to an industrial scale. Bocarsly serves as chair of the company's scientific advisory board.
The research has received funding from the Air Force Office of Scientific Research (AFSOR), the National Science Foundation and the Department of Energy (DOE). The collaboration between Liquid Light and the University was supported by the DOE Small Business Innovation Research program and the AFOSR Small Business Technology Transfer program.
Princeton's agreement with Liquid Light allowed the company to continue to collaborate with Bocarsly and his research team. Before long, new discoveries were emerging. "They started noticing interesting chemistry that we wouldn't have predicted," said Bocarsly.
The Princeton scientists did some additional studies, and made a surprising discovery: They could turn CO2, which contains only one carbon, into a compound with a carbon-carbon bond, which vastly increases the possibilities for creating commercial applications. This was radical because although the reaction is certainly possible, it is highly unlikely to happen because so many other competing reactions are occurring.
"Everyone who electrochemically reduces CO2 today makes compounds with only one carbon," said Bocarsly. "Nobody makes things with carbon-carbon bonds." He paused. "But we can."
"That was a very 'wow' moment," recalled Cole, "because we thought that our process could only make methanol. But now we were finding that we could make a variety of products, and that is what makes this technology commercially interesting." She said Liquid Light scientists can now make more than 20 different products from CO2.
One of the chemicals Liquid Light can make is isopropanol, commonly known as rubbing alcohol and an important industrial chemical. Another is butanol, which could be commercially important as a fuel. Liquid Light's technology offers the potential to make these chemicals at lower cost than today's methods, which involve starting with fossil fuels such as petroleum and natural gas.
Back in the Princeton lab
While Liquid Light is developing the technology commercially, back in the chemistry department at Princeton, Bocarsly and his team are tackling a question that has puzzled the chemist since the 1990s: Why does pyridinium work so well as a catalyst for the reaction? Based on its structure, the ring-shaped molecule is an unlikely catalyst for this reaction because it shuttles just one electron at a time. But to convert CO2 to methanol requires six electrons, and to make higher-carbon molecules takes even more electrons.
Bocarsly and his team in collaboration with Steven Bernasek, professor of chemistry are doing studies to understand the steps in the chemical reaction, and they are making rapid progress. "There are clearly some intermediate products formed during the reaction that do not sit around for a long time and are not there in very high concentrations," said Bocarsly.
The Princeton team also is studying the factors that determine which products can be made from CO2. The researchers have found that very subtle changes in the electrode surface can lead to production of different chemicals. For example, CO2 plus a pyridinium catalyst and a platinum electrode make methanol. However, the same catalyst and a different electrode give a different product. The team published its findings on how the reaction is affected by catalyst concentration, temperature and pressure in the journal ChemSusChem last year.
Meanwhile, scientists at Liquid Light are overcoming the practical hurdles inherent in converting laboratory findings to commercial technologies. One finding is that using sunlight to drive the reaction is not as efficient as using standard electricity from a wall outlet, so the researchers are exploring ways to harness electrical power generated from green technologies such as wind or hydroelectric power.
Citing government statistics that the United States generates about 5.5 billion metric tons of CO2 per year, Teamey said it will not be hard to obtain the starting materials for this new industry. However, the CO2 needs to be relatively pure, a requirement that rules out gasoline tailpipes and coal-fired power plants. Instead, said Teamey, the CO2 could come from manufacturing facilities, such as fertilizer manufacturers and cement plants, which according to Teamey emit some 100 million tons of high-purity CO2 each year.
Cole said her transition from Princeton Ph.D. graduate to startup employee has been a smooth one. "Startups can be very exciting because you are taking work from the academic setting and trying to make it work economically in the marketplace," she said. "It is rewarding because you can see your project from graduate school become an actual technology that impacts people."
Journal reference: Journal of the American Chemical Society
Provided by Princeton University.
Liquid Light licensed its technology from Princeton. Cole leads a team of chemists who tackle the practical issue of how to scale up a laboratory invention to an industrial scale, while Bocarsly chairs the company's scientific advisory board. Credit: Denise Applewhite
This photoelectrochemical cell contains a solution of carbon dioxide and pyridinium as a catalyst dissolved in water. A low-power blue light-emitting diode (LED) provides light, which activates the semiconductor, causing the conversion of the CO2 and water to methanol and oxygen with the help of the pyridine catalyst. This cell is highly efficient, with greater than 95 percent of the electrons generated by the illumination going into the formation of methanol. Credit: Andrew Bocarsly
Doing technically at great effort and expense what God’s green trees and plants do now? (Well, almost.)
Exactly! NET negative calories.
WHY is this a good idea??????
Great idea. His weak point is that we already have an almost limitless supply of fuel, and it’s just sitting there in the ground waiting to be harvested.
If you create easily used hydrocarbons during the low power usage times at power plants for use in auxillary generators or portable engines like cars, you can come out ahead of where you are today. Coal plants are difficult to turn on and off, so if you run them at constant output and run the excess into one of these for later use you can make the whole process more efficient. Is it a net energy loss? Yes, but less that the alternative of just making steam without turning a turbine to keep the plant running.
And when back when in organic chemistry III, all of our tests involved manufacturing a desired complex organic molecule from methanol or methane, and catalysts. Point being, the chemistry to go from methanol to most any other organic molecule is well defined.
I would love to know the longevity of the electrodes and catalyst along with their cost.
Even at somewhat low efficiencies, the ability to create a combustible gas from an intermittent source such as wind or solar and a plentiful byproduct would allow for that energy to be consumed and made productive when needed.
This is no silver bullet but we do not need a silver bullet just many bullets of all types for a variety of needs.
Step that up to butanol and you will have a decent replacement for gasoline.
What we need is more coal fired electrical power to drive the blue LEDs that convert CO2 to hydrocarbons!!
They’re proposing to drive the reaction with sunlight, not blue LEDs.
Yep, just like ethanol.
Unless the energy comes from some source that doesn't itself release CO2 (nuclear, hydropower, etc.), you're right back where you started.
In one way, this product (method) is just like ethanol -- without raping the taxpayer, neither would ever come to market.
We have thousands of years of cheap, abundant energy sources. Let the market decide, not leftist or RINO politicians.
I am mentally imagining
a strange rube goldberg type device
installed at a factory
with windmill blades mounted over the smokestack
that spin from the heat rising from the stack
that send electrical power to the electrodes
that convert the CO2 in the stack emissions
into fuel that runs the factory
but, what do we do when we run out of CO2? We will be right back where we started from and the we will be required to use fossil fuels so as to supply the green energy jobs at the CO2 convering industry.
Let’s see, based on projected increases, we have in excess of 500 years of known reserves for natural gas;m more than 500 years of coal; more known reserves of oil than anyone else on the planet and finding more all of the time, and virtually untapped nuclear power (except in the Navy).
When you burn the fuel produced from CO2, it turns back into CO2........
Only one aspect of this really intrigues me. That’s the idea that maybe something can come along to take the wind out of the carbon dioxide Nazi’s sails. That would be a beautiful thing.
Thanks! I figured as much. Key here is how much electricity does it take to convert CO2 into useful fuels?
Methanol is also called wood alcohol. It’s obvious why they didn’t mention that. They are re-inventing the tree, something that took billions of years of massively parallel natural computation to develop. Good luck with that.
Thanks for the interesting post Red Badger but looking at some of the replies it would seem we have some of the same mentality we decry from the left.
There is no perfect energy source for every application. A country like the USA needs every possible source imaginable as our energy requirements are so diverse.
What works good in a car may not work in the center of an explosives factory or what works to heat domestic hot water may not work in an airplane. So what? Give us as many possible sources of energy and the market place will figure out the winners for each application and there might be multiple winners for a single application.
I am disappointed so many shots taken at this and numerous other ideas by fellow Freepers. I almost had to look at the URL to make sure I had not been hijacked to the DU.
On a large scale, I foresee this technology being utilized to reclaim CO2 from power plants and factories to recover some of the fuel costs. On a small scale, it could also be used for home heating or small business CO2 reclamation.
With the CO2 factor being removed from the objections to coal fired power plants, there is no longer any bluster about greenhouse gases and global warming...............
Nuclear power plants are reallly difficult............
"... searching for ways to store, dispose of, or prevent the formation of the greenhouse gas, which is a major driver of global climate change."
The only problem with that is people don't enjoy drinking butanol. As others have pointed out the energy required to make methanol, ethanol or butanol would be more than returned through combustion. Therefore using this as a fuel isn't practical, so we might as well enjoy it!
Why not just use the fossil fuels that come naturally out of the ground// This is silly.
Thanks Red Badger.
sorry, but that was supposed to be taken as sarcasm directed to the liberal left.
” Understand your point about the shots, but most new “breakthroughs” never mature to viability. It’s very easy to remain sceptical, particularly when the article contains:”
As a corporate engineer for over 26 years I can attest to the value of “breakthroughs” which never reach maturity.
If ideas are allowed to be brought forth without all the chicken little, back biting, Monday morning quarterbacking it is amazing how the initial spark can create an entirely new concept even if the the actual spark ultimately is never used.
In fact it is unrealistic to believe the initial idea will remain unchanged after it is evaluated. I’d gladly take 100 failed ideas vs no ideas any day of the week as I have seen how failed ideas lead to a new path.
Leave all the negativity to the DU as that is all they have. They never create anything just destroy or steal the work of others.
During past years I'm aware of many phenomonal breakthroughs; not all of them matured but provided another rung on the ladder to reach something that did.
By the way, I just noticed that you and I have the same FR sign-up date: 1999-07-21. Welcome to FR. :)
Yes Ken, the glow-bull warming crapola was expected given the source. They will never learn.
Butanol can also be dehydrated using standard petchem catalysts to butane and then dimerized or trimerized or oligomerized to any other straight chain alkane, or isomerized to any of the branched chain aromatics this is standard petroleum refinery tech that is done on the level of millions of tons per day using crude oil and NG liquid feeds. Butanol is also an industrial solvent / base chemical that is currently worth more per gallon than gasoline on the wholesale market if they make butanol it will not end up as motor fuel it is too valuable a chemical commodity for that currently.
Methanol can be turned directly into isooctane using the MTG process at high commercially viable yields ask the South Africans they do the MTG process by the millions of tons commercially already. the MTG process yields isocatane and propane in an 3:1 ratio with no side reactions over a zeolite catalyst.
If the catalyst are cheap enough and blue light is all you need plus CO2 there are plenty of compounds that florescence in full sunlight one could be tuned to take in broad spectrum sunlight and florescence out blue light directly to one of these catalitic cells, but if you can go directly from electrons to chemical energy at 95% efficency skip the solar photon to semicondutor electron step and just use off peak power from wind, hydro, and nukes.
Texas has installed over 5 gigawatts of wind power that peaks out in the middle of the night while we all sleep and during the heat of the day anyone who has lived in west Texas will tell you there is no wind to be had it's just hot and dry till sun down then bam out of no where the wind starts to howl again it has to do with the advection of unequal cooling of the different land use types to the cloud less night sky. All that power at night mostly goes to waste as we Texans are off work and going to sleep right as the wind really peaks out all the way till the sun comes up and heats the ground up again the mid-mornings.
At which point, the complaint will become something else.
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