From the University of Illinois – Ionic liquid catalyst helps turn emissions into fuel
University of Illinois chemical and biological engineering professor Paul Kenis and his research group joined forces with researchers at Dioxide Materials, a startup company, to produce a catalyst that improves artificial photosynthesis. The company, in the university Research Park, was founded by retired chemical engineering professor Richard Masel. The team reported their results in the journal Science.
Artificial photosynthesis is the process of converting carbon dioxide gas into useful carbon-based chemicals, most notably fuel or other compounds usually derived from petroleum, as an alternative to extracting them from biomass.
In plants, photosynthesis uses solar energy to convert carbon dioxide (CO2) and water to sugars and other hydrocarbons. Biofuels are refined from sugars extracted from crops such as corn. However, in artificial photosynthesis, an electrochemical cell uses energy from a solar collector or a wind turbine to convert CO2 to simple carbon fuels such as formic acid or methanol, which are further refined to make ethanol and other fuels.
“The key advantage is that there is no competition with the food supply,” said Masel, a co-principal investigator of the paper and CEO of Dioxide Materials, “and it is a lot cheaper to transmit electricity than it is to ship biomass to a refinery.”
However, one big hurdle has kept artificial photosynthesis from vaulting into the mainstream: The first step to making fuel, turning carbon dioxide into carbon monoxide, is too energy intensive. It requires so much electricity to drive this first reaction that more energy is used to produce the fuel than can be stored in the fuel.
The Illinois group used a novel approach involving an ionic liquid to catalyze the reaction, greatly reducing the energy required to drive the process. The ionic liquids stabilize the intermediates in the reaction so that less electricity is needed to complete the conversion.
The researchers used an electrochemical cell as a flow reactor, separating the gaseous CO2 input and oxygen output from the liquid electrolyte catalyst with gas-diffusion electrodes. The cell design allowed the researchers to fine-tune the composition of the electrolyte stream to improve reaction kinetics, including adding ionic liquids as a co-catalyst.
“It lowers the overpotential for CO2 reduction tremendously,” said Kenis, who is also a professor of mechanical science and engineering and affiliated with the Beckman Institute for Advanced Science and Technology. “Therefore, a much lower potential has to be applied. Applying a much lower potential corresponds to consuming less energy to drive the process.”
Next, the researchers hope to tackle the problem of throughput. To make their technology useful for commercial applications, they need to speed up the reaction and maximize conversion.
“More work is needed, but this research brings us a significant step closer to reducing our dependence on fossil fuels while simultaneously reducing CO2 emissions that are linked to unwanted climate change,” Kenis said.
Graduate students Brian Rosen, Michael Thorson, Wei Zhu and Devin Whipple and postdoctoral researcher Amin Salehi-Khojin were co-authors of the paper. The U.S. Department of Energy supported this work.
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Don’t forget that when all that synthetic fuel is burned the combustion products consist mostly of CO2 and water, process water can be recycled, and all the hydrogen content of the synthetic fuel returns to water when it is oxidized. It then eventually falls as rain and returns to the earths water cycle where it came from.
The Spanish syn fuel looks to be just a repeat of thermal polymerization which has been available for commercial use since 1996 as developed by Changing World Technologies. The only important difference is that they are using biomass from algae and cyano bacteria rather than plant crops. The technology has been viable at oil prices greater than about $90 / BBL in year 2000 dollars. The only hook has been commercial interest and getting plants approved with NIMBY pressures from green zealots who see it as just another evil oil process. Using that technology we could manufacture essentially unlimited amounts of hydrocarbon base chemicals, limited only by a supply of waste heat sufficient to generate the necessary process temps of between 250 deg C and 500 deg C and some hydrocarbon feed stock.
Any feedstock could be used, that contains both carbon and hydrogen, trash waste plastic, biomass, cultivated feed stocks like grasses, crop waste, or algae all could be used. There is no oil shortage we can make all we need as a convenient energy carrier. We only need the original energy input which could be any source of thermal energy of high enough quality to achieve the required process temps, and secondary energy needs to power pumps etc.
Larry
edit —
change thermal polymerization to thermal de-polymerization
Larry
I think Scott Covert had it right, up top. A really inefficient battery. Like hydrogen.
I think the Invisible Hand’s brass knucks this time round are the proliferating shale gas discoveries. Those who put all their money on NIMBY alternatives are going to end up battered nearly, or entirely, to death.
Kudos to Prof. Kenis & his team for pursuing this research….the sooner that mankind realizes that carbon dioxide is a resource worth capturing & processing, and not just an emissions constituent, the better. There are all sorts of useful products that can be produced from this molecule. My group is working on several competing processes, more to follow.
LarryOldtimer says:
October 7, 2011 at 3:21 pm
How very idiotic. In case no one realized, carbon dioxide is where all of our food comes from. First the total stupidity of turning corn into “fuel”, now this further stupidity.
Just speaking to my wife’s cousin in Kansas today . . . the farmers are all out picking corn. Yield looks to be about 40 to 45 bushels per acre . . . as against 145 bushels per acre about 3 to 4 years ago. And she said that the stored reserves farmers store were already running out.
But if it is famine that is wanted, this is another good way of bringing it on.
____________________________________________________________________
Unfortunately that seems to be what is planned for us. With the 2008 food crisis Monsanto, Cargill, ADM, Goldman Sachs made record profits. Now with the mid west flooding this spring, Soros & Rothschild and others are snapping up farmland as farmers bankrupt. Over 90% of American farmers work outside their home to support their farms so the over 20% unemployment rate is not helping.
BTW for farmers the price of grain never went back down after 2008 when feed prices more than doubled, putting the local chicken plants out of business and likely the 400 area chicken farms that supplied them. If we do not have another food crisis by spring I will be very very surprised.
This gives a pretty factual account of what is going on: https://projectpangaia.wordpress.com/category/bio-fuel/
Oh and around my area we had over a month of drought so the corn is knee high, brown with no ears – GRIM
This is the report from before our local corn crop died:
Thursday, June 30, 2011: USDA: Corn Stocks Down 15 Percent from June 2010 Soybean Stocks Up 8 Percent All Wheat Stocks Down 12 Percent: http://climateerinvest.blogspot.com/2011/06/usda-corn-stocks-down-15-percent-from.html
This sounds more like people searching for a problem then a solution. Nothing all that wrong with the concept. Like all these apparently simple things honorably complex with the details are examined.
The Science abstract page is here. I’ve read the paper, and the authors are properly modest in their claims. Unlike the UI press release.
The press release has a few objective errors. For example, it says that, “The ionic liquids stabilize the intermediates in the reaction so that less electricity is needed to complete the conversion.” In fact, the ionic liquids lower the overpotential of the reaction, meaning the reaction goes at a lower driving Voltage. It still requires exactly the same amount of electricity — meaning the number of electrons required to produce CO from CO2 (two electrons).
It’s possible that the ionic liquid suppressed side reactions — which would use excess electrons (more electricity) — but the paper doesn’t say that.
The press release also says, “The first step to making fuel, turning carbon dioxide into carbon monoxide, is too energy intensive. It requires so much electricity to drive this first reaction that more energy is used to produce the fuel than can be stored in the fuel.”
This is pretty muddled. The same amount of electricity is always required to produce the CO (fuel) itself. If the process is inefficient, i.e., if there are side reactions, then some of the electrons (electricity) are diverted into side products. But side-products is not what they’re talking about. They’re talking about catalysis, which lowers the activation barrier and makes a reaction faster or more efficient (or both), but doesn’t change the electron count. The two PR sentences are confused about the difference between energy and electricity.
Not only that, but Thermodynamics tells us that no process is ever 100% efficient. Therefore, it will always require more energy to produce CO from CO2 than the CO is worth itself.
Photosynthesis works because the energy is free to plants. Using electricity generated elsewhere — even through solar power — to reduce CO2 to CO for fuels will always be a net energy loss. Presently, the reported process is at 87% efficiency but that’s only at the lowest Voltage. At higher driving Voltages, which should increase the rate of CO production, energy is lost to resistive heating and the efficiency decreases.
The scientists involved did a nice piece of work, and made a nice discovery. They hypothesized a more efficient reaction, did the experimental test, and found a positive outcome. They were properly diffident in their peer-reviewed report. It’s a fine example of productive science and congratulations are in order.
The problem comes because the successful experiment has been over-sold in the inflamed context of AGW. It’s about PR people at universities, and universities looking for the fashionable limelight that can be touted in DC during the budget process. The technical process is about a million miles away from commercial reality. Entropy says it will probably never be suitable to produce liquid fuels in a commercially viable way in competition with fossil fuels or nuclear (fission or fusion).
“hotrod (Larry L) says:
October 7, 2011 at 3:40 pm
[…]
Don’t forget that when all that synthetic fuel is burned the combustion products consist mostly of CO2 and water, process water can be recycled, and all the hydrogen content of the synthetic fuel returns to water when it is oxidized. It then eventually falls as rain and returns to the earths water cycle where it came from.”
Sure, I did not suggest water would vanish from the planet. The whole point of synthetic fuels however is to use them in transportation, an open system, so one does not get closed loop, process water back directly as might possible if burned at power plant. If the proposed system was tapping an aquifer for the water in, say, the US southwest to take advantage of the of sun there they won’t get the water back “as rain”.
Pat Franks, well said. My remnant physical organic chemistry was telling me the same things.
“Pat Frank says:
October 7, 2011 at 4:34 pm
Not only that, but Thermodynamics tells us that no process is ever 100% efficient. …
Yes it does. So then what are you getting at in the following?
Photosynthesis works because the energy is free to plants. Using electricity generated elsewhere — even through solar power — to reduce CO2 to CO for fuels will always be a net energy loss.
“
Plants also lose energy in converting from light to chemical energy, and the solar energy from PV is ‘free’ in the sense that the light is free, even if the PV panels are not. The point seems to be to discover the most efficient way to make syn fuel.
George (Jim) Hebbard PE says:
October 7, 2011 at 12:16 pm
“……Fortunately Andrea Rossi’s October 6 E-Cat test was a major success, and energy efficiency will never need concern us again.
Q.E.D.”
______________________________________________________________________
Since no one else followed up on this I will.
Here is the link for the guy who asked: http://freeenergytruth.blogspot.com/2011/10/ecat-test-mainstream-finally-break-9.html
It is a blog because the “Official Media” has not yet reported it.
Whether it is the truth I have no idea but it seems reall.
RE: Rossi’s ECat – still looks like pseudo science. http://www.peswiki.com/index.php/News:Real-Time_Updates_on_the_October_6,_2011_E-Cat_Test
So, can I eat the corn now?
d(^_^)b
http://libertyatstake.blogspot.com/
“Because the Only Good Progressive is a Failed Progressive”
Crazy schemes always get a “That’s Hot” from me.
Josualdo – thanks for the link. Certainly that process will produce the desired end, but the means (solar energy, photosynthesis, electromagnetic fields) to the end do not justice the high cost of the product.
I predict it will require more energy into the process then it gennerates just as the U.S. ethanol scam does.
The process is called “Photosynthesis in a Lipid Aqueous Nutrient Target” AKA PLANT
Falstaff, even if the light on a PV cell is free, one is using the electricity it generates to produce a synfuel — say CO — from CO2. The energy in the produced CO will be less than the energy in the electricity that was used to produce it. Therefore, one is always better off using the PV current to power things directly.
Even at low efficiency, plants make out because they contribute nothing to building and maintaining the sun. The light is free all the way back through the source.
Even at an electrolysis conversion efficiency of 100%, one is only at break-even with respect to the delivered energy. Transmission losses and the cost of the PV production and maintenance is extra, so the total process still amounts to a net loss.
The only way to make the CO2 to CO process economically viable is if the electrolysis efficiency is greater than 100%, to pay for the upstream costs. That is physically impossible unless one has a supernatural source of electrons. Or the process would pay off if CO becomes so precious that its market value is more than the production costs. But that will never happen.
OK, it could happen in the event of a draconian green tyranny that forbade the use of any and all fossil fuels or fission power. In that event electrical power of any sort would become extremely expensive and precious, and the means of exchange would be measurable in units of triple-A flashlight batteries. Batteries themselves would be available only to the very rich. And then, of course, no one would have the available power to electrolyze CO2 into CO anyway.
So, we cut down all plant life in an area, build solar power plants to do what plants do. Great, sign me up.
Thanks, Alan, science shows us the way. 🙂
They’re stealing food from plants?!
/sarc
Okay, joking aside, I can see potential applications in scrubbing CO2 from the air of enclosed environments, like in submarines. However, if the first step is the conversion of CO2 to carbon monoxide, just imagine the result if that carbon monoxide leaks.
How many square miles need to be covered per gigawatt?
What land can be utilised to site these systems?
How will the electricity be stored for when people actually want to use it?
How much maintenance is required?
What is the lifespan of the equipment?
What is the cost of the electrical grid needed to support it?
Is it economically feasible?
Pat Frank and Astoneril,
The idea that might be economically feasible is to put the solar farms in deserts and transport the fuel to the people who live a ways away. Say in S. E. California, in Arizona or New Mexico, and transport the fuel to Los Angeles, Phoenix, Tucson or Albuquerque. It really is not dumber (should the process be made cheap) than carrying petroleum by tanker from Indonesia to the Port of Los Angeles, and then hauling gasoline to Las Vegas. It just depends on how cheaply (all costs considered) it can be done.
to others: There is no risk of reducing the CO2 too much — the fuel will be burned and the CO2 returned to the atmosphere.
Gail Combs, thanks for the link to the ECAT. It still looks like a scam to me, albeit a very elaborate scam.
It isn’t hard to show that the thing works. It’s hot! Hook the sucker up to a Stirling engine, drive an electrical generator, feed the power back into it, detach the external electricity supply, and see how much electricity it supplies to an external machine, and for how long. Rossi et al. have done everything else these last 6 months except show that it works.
The most useful solar/wind device I can think of is one that concentrates atmospheric CO2 to 1,000 ppm to feed greenhouses.
Currently they burn fossil fuels to get the CO2.
Such a device would reduce CO2 emissions AND reduce atmospheric CO2 AND produce more food.
I’ll speculate that such a device hasn’t been developed because the CAGW crowd don’t want to highlight the fact that more atmospheric CO2 means more food thru higher crop yields.
Solar powered fractional distillation of air appears feasible, but then I’m not an engineer.