From Stanford University
Stanford scientists discover a novel way to make ethanol without corn or other plants
Stanford University scientists have found a new, highly efficient way to produce liquid ethanol from carbon monoxide gas. This promising discovery could provide an eco-friendly alternative to conventional ethanol production from corn and other crops, say the scientists. Their results are published in the April 9 advanced online edition of the journal Nature.
“We have discovered the first metal catalyst that can produce appreciable amounts of ethanol from carbon monoxide at room temperature and pressure – a notoriously difficult electrochemical reaction,” said Matthew Kanan, an assistant professor of chemistry at Stanford and coauthor of the Nature study.
Most ethanol today is produced at high-temperature fermentation facilities that chemically convert corn, sugarcane and other plants into liquid fuel. But growing crops for biofuel requires thousands of acres of land and vast quantities of fertilizer and water. In some parts of the United States, it takes more than 800 gallons of water to grow a bushel of corn, which, in turn, yields about 3 gallons of ethanol.
The new technique developed by Kanan and Stanford graduate student Christina Li requires no fermentation and, if scaled up, could help address many of the land- and water-use issues surrounding ethanol production today. “Our study demonstrates the feasibility of making ethanol by electrocatalysis,” Kanan said. “But we have a lot more work to do to make a device that is practical.”
Novel electrodes
Two years ago, Kanan and Li created a novel electrode made of a material they called oxide-derived copper. They used the term “oxide-derived” because the metallic electrode was produced from copper oxide.
“Conventional copper electrodes consist of individual nanoparticles that just sit on top of each other,” Kanan said. “Oxide-derived copper, on the other hand, is made of copper nanocrystals that are all linked together in a continuous network with well-defined grain boundaries. The process of transforming copper oxide into metallic copper creates the network of nanocrystals.”
For the Nature study, Kanan and Li built an electrochemical cell – a device consisting of two electrodes placed in water saturated with carbon monoxide gas. When a voltage is applied across the electrodes of a conventional cell, a current flows and water is converted to oxygen gas at one electrode (the anode) and hydrogen gas at the other electrode (the cathode). The challenge was to find a cathode that would reduce carbon monoxide to ethanol instead of reducing water to hydrogen.
“Most materials are incapable of reducing carbon monoxide and exclusively react with water,” Kanan said. “Copper is the only exception, but conventional copper is very inefficient.”
In the Nature experiment, Kanan and Li used a cathode made of oxide-derived copper. When a small voltage was applied, the results were dramatic.
“The oxide-derived copper produced ethanol and acetate with 57 percent faradaic efficiency,” Kanan said. “That means 57 percent of the electric current went into producing these two compounds from carbon monoxide. We’re excited because this represents a more than 10-fold increase in efficiency over conventional copper catalysts. Our models suggest that the nanocrystalline network in the oxide-derived copper was critical for achieving these results.”
Carbon neutral
The Stanford team has begun looking for ways to create other fuels and improve the overall efficiency of the process. “In this experiment, ethanol was the major product,” Kanan said. “Propanol would actually be a higher energy-density fuel than ethanol, but right now there is no efficient way to produce it.”
In the experiment, Kanan and Li found that a slightly altered oxide-derived copper catalyst produced propanol with 10 percent efficiency. The team is working to improve the yield for propanol by further tuning the catalyst’s structure.
Ultimately, Kanan would like to see a scaled-up version of the catalytic cell powered by electricity from the sun, wind or other renewable resource.
For the process to be carbon neutral, scientists will have to find a new way to make carbon monoxide from renewable energy instead of fossil fuel, the primary source today. Kanan envisions taking carbon dioxide (CO2) from the atmosphere to produce carbon monoxide, which, in turn, would be fed to a copper catalyst to make liquid fuel. The CO2 that is released into the atmosphere during fuel combustion would be re-used to make more carbon monoxide and more fuel – a closed-loop, emissions-free process.
“Technology already exists for converting CO2 to carbon monoxide, but the missing piece was the efficient conversion of carbon monoxide to a useful fuel that’s liquid, easy to store and nontoxic,” Kanan said. “Prior to our study, there was a sense that no catalyst could efficiently reduce carbon monoxide to a liquid. We have a solution to this problem that’s made of copper, which is cheap and abundant. We hope our results inspire other people to work on our system or develop a new catalyst that converts carbon monoxide to fuel.”
The Nature study was coauthored by Jim Ciston, a senior staff scientist with the National Center for Electron Microscopy at Lawrence Berkeley National Laboratory.
The research was supported by Stanford University, the National Science Foundation and the U.S. Department of Energy.
This article was written by Mark Shwartz, Precourt Institute for Energy at Stanford University.
As long as it doesn’t ruin my small gas engines. I am in.
Did I mention that it has to provide more energy than it takes to make it in net total?
Catherine, you write “Doesn’t the cellulose feedstock require fossil fuel fertilizers & pesticides to grow? Or more chemicals for the soil to replace the nutrients not plowed back in?”
Corn is grown for the food it produces. So, in principle, the fuel, fertilizers and pesticides are being used for the food. The corn stover is used to plough back into the land for future years. However, POET and the farmers have worked out that of the 4 tons per acre of corn stover that is produced, only 3 tons per acre is required for future years. So there is 1 ton per acre, which is waste, and this is what is used to produced the ethanol.
@ur momisugly bhiggum says:
April 9, 2014 at 5:15 pm
*****
Looks like you’ve found a whole lotta nothin there for tax breaks. States give all kinds of companies tax breaks, so those aren’t anything specific to refineries. The New York Times hit piece does not name the laws, just hints at them.
Finally, tax breaks just allow a business to keep some money. Subsidies are tax payer monies given to favored businesses. Big difference.
Jim Cripwell,
I have heard the same stories for 10 years now about cellulosic ethanol plants being “nearly there”. I am happy to hear someone else is still going on this, but these reports are no different than ones I have read before from at least three different companies that no longer exist. They have made it work for short runs, but cannot cope with the variation in input material and still get efficient production such that it is a commercial process.
Forgive me if I want to wait until they actually start producing commercially before I believe it.
9 April: Reuters: By Barbara Lewis and Foo Yun Chee: New EU rules on energy funding phase out subsidies for renewables
Funding green energy will become harder under EU rules published on Wednesday designed to replace subsidies with market-based schemes, just when the Ukraine crisis has heightened the need for alternatives to imported fossil fuel.
The executive European Commission said the guidelines, which will be gradually phased in, strike a necessary balance after fierce political debate about the cost of green subsidies.
“Politically, it’s the best balance possible. We were obliged to establish a lot of trade-offs,” the Commission’s competition chief, Joaquin Almunia, told reporters.
But green energy campaigners, who protested outside the Commission headquarters in Brussels, said the rules were a victory for industry and a blow to the renewables sector as well as ordinary consumers.
The rules take effect from July 1 this year and from 2017 all member states will have to hold tenders to support new green power facilities following a pilot phase from 2015-16.
The idea is to replace feed-in tariffs, which have little or no relation to market reality but have spurred renewable development, with auctions or bidding processes open to all green energy generators competing equally for government funds…
Following extensive lobbying from companies, the new rules allow for exemptions in special circumstances, including sparing energy-intensive industries such as chemicals, metals, paper and ceramics from helping to pay for renewable power. That leaves ordinary household consumers to pick up the bill…
CITIZENS ‘LOSE TWICE’
Environmental groups and the renewables lobby are concerned the EU’s renewed emphasis on increasing energy security and weaning itself off Russian gas because of instability in transit nation Ukraine will lead only to more use of coal and efforts to develop shale gas, not more green power.
“It’s the whole contradiction of the Commission, which asks that we learn from the Ukraine-Russia crisis and then gives in to corporate lobbies,” Claude Turmes, a member of the European Parliament representing the Green Party, told Reuters.
“Citizens will lose twice: they will pay for industries’ new free ride and will continue to suffer from an outdated energy system.”…
However, the latest guidelines do not include rules on aid for nuclear energy. This means if member states want to fund such projects, they need to notify the Commission, which will assess requests on a case-by-case basis.
The omission was a blow to Britain, which wants to use state guarantees to help finance a nuclear plant to be built by France’s EDF…
***The industry exemptions cover 68 sectors in all.
As European energy costs exceed those in the United States, where shale gas has reduced prices, Eurofer, the European Steel Association, complained that even with the waivers it faced a competitive disadvantage.
(Additional reporting by Ben Garside in London; Editing by Dale Hudson)
http://news.yahoo.com/eu-rules-energy-funding-phase-subsidies-renewables-134639321–finance.html
I hope they remembered to weigh BOTH electrodes before and after the experiment.
bhiggum says:
April 9, 2014 at 4:48 pm
It’s not a perfect fuel, but it’s far better than depending on other countries for petroleum.
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Not a perfect fuel? It’s an inert filler, i.e., NO FUEL AT ALL. When they put 10% ethanol in gasoline, my mileage went down 10%.
BTW . . . we’re still importing petroleum.
In fact, the U.S. uses 365.65 million gallons of gasoline a DAY. DD making 30 millions gallons a year in Iowa is spit in the ocean. To make enough alcohol agriculturally to replace gasoline in the U.S. alone, you would need 600,000,000 acres of land. Nearly a million square miles. How is plowing up the country “far better than depending on other countries for petroleum?” It’s not desirable, looking beyond it’s not even possible.
“Ethanol? Who needs it?” I do, for one. In Australia E10 is 95 octane and cheaper than 91, 95 and 98 octane “normal” unleaded petrol. I get better economy from E10 than the other fuels, and save up to 20 cents per litre. Considering that I cover 900km in a day sometimes, that’s a considerable saving. E10 fuel is uncommon in my part of Oz, however, in part because it’s not state-mandated (state as in NSW, WA etc) and ethanol is not produced, at least in any quantity, in my state of residence. Australia has a good number of in particular, turbocharged European cars, which require at least 95 octane petrol, E10 is a cheaper way of obtaining 95 octane fuel without the incurring sting of 95 or 98 octane unleaded, which can be 10-20 cents per litre dearer depending on location.
‘Oxide-derived copper, on the other hand, is made of copper nanocrystals that are all linked together in a continuous network with well-defined grain boundaries’
What is the cost of producing the anode, on top of the copper cost?
Very nice, but pointless research at this time. Unless CO2 is a pollutant and we are out of inexpensive liquid transportation fuels, this is and will always be a horrible idea. Even with their high efficiency reaction, it will take almost twice as much energy to PRODUCE the ethanol than you will get out of it. So, it only makes sense if the energy source for this comes from nuclear or hydro and there are no cheap sources of hydrocarbon fuels available (as in we have already pumped it all out of the ground).
Thus to reiterate, since at 400ppm CO2 is NOT a pollutant and we are not out of inexpensive hydrocarbon fuels…..
RIF
“Ultimately, Kanan would like to see a scaled-up version of the catalytic cell powered by electricity from the sun, wind or other renewable resource.”
I think this has real potential.
If we make the aim to stabilise CO2 levels, then the doomsday scenarios no longer apply. We would then be able to continue to use fossil fuels (discarding the finite resource arguments). The annual increase in global CO2 concentration is approximately 2ppm at this time. That’s the amount that needs to be sucked back out. No doubt that’s gigatonnes of ethanol, so it will be difficult (understatement).
You use the unreliable (i.e. intermittent, unpredictable) power created by renewable sources, and dedicate them to this conversion of CO2 to ethanol. This ethanol is the ‘battery’ that stores the power from the renewables.
You use existing power plants to provide reliable (i.e. constant, predictable) baseline power as at present. Maybe supplement their fuel with this ethanol (I’m not a chemist / chemical engineer – clever people may know / can figure out how to do this) or use the ethanol in cars.
Bottom line – the fossil-sourced carbon is recycled, preserving existing reserves. Power generation is stabilised.
No doubt many of us here will dismiss the need to do any of this to counteract AGW issues, but it does present many useful benefits that provide reasons to pursue the technology.
/dream
Read the text: It’s not CO2 they convert, but CO and that is not the same. There are allready many way’s to convert CO to fuel.
TAG says:
April 9, 2014 at 1:32 pm
US Navy creates fuel from seawater.
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Mother nature has been doing this for hundreds of millions of years. Turning limestone and seawater into “fossil” fuels using iron as a catalyst and the heat of the earth’s interior as the energy source. The result is methane.
1- Where do we get the CO without combustion?
2- If CO2 is so bad, then perhaps it should be recalled that ethanol produces CO2 when it burns?
3-Can this be run on a net positive energy basis at all?
Reblogged this on YFN Georgia LLC and commented:
A very interesting breakthrough. If commercialised, it may dramatically reduce the acreage occupied by grain crops grown for ethanol, and consequently enhance global food security.
Kjetil Nesheim says:
April 9, 2014 at 8:45 pm
‘Kanan envisions taking carbon dioxide (CO2) from the atmosphere to produce carbon monoxide, ‘
Carbon dioxide is not a pollutant, but Carbon Monoxide certainly is! If any of you are thinking about doing this at home, Carbon Monoxide is deadly.
The field corn used in ethanol production is already not a food crop for humans. The spent malt can be used as high-grade livestock feed, though.
A solution looking for a problem.
“””””…..Gamecock says:
April 9, 2014 at 6:28 pm
bhiggum says:
April 9, 2014 at 4:48 pm
It’s not a perfect fuel, but it’s far better than depending on other countries for petroleum.
================
Not a perfect fuel? It’s an inert filler, i.e., NO FUEL AT ALL. When they put 10% ethanol in gasoline, my mileage went down 10%……”””””
Well what did you expect.
Ethanol is Ethyl alcohol C2H6O often written C2H5OH but its just Ethane C2H6 + O or you can write it as 2(CH2)+H2O.
Any alcohol is just n(CH2) +H2O
So it contains water, which is about as low as you can get on the stored chemical energy scale. Well you can get a bit lower by adding salt; AKA seawater.
And yes Ethanol gives you less energy than burning Ethane and by just the amount you get when you burn hydrogen to get water.
So they literally are just adding water to the gasoline when they add any “oxygenate” to the fuel.
And that is superfluous, because any ordinary automobile already contains a device for oxygenating the fuel.
In most of these vehicles, the oxygenator apparatus is usually called an “engine”, or maybe a “motor”. Its sole purpose is to oxygenate fuel to create heat, which heats the working fluid often called “air” to produce rotary motion of some of the oxygenator parts.
Ethers do the same thing as alcohols, but they don’t taste as good as ethanol.
You can actually add your own water to the gasoline, without any ethanol or ether; and it actually works much better. You need to buy a water injector to fit on your rotary oxygenator to then add your own ordinary tap water, which is cheaper than ethanol.
Scientists ‘doing science’ how refreshing and novel.
If stored in oak barrels for more than 3 years.
Would it be Whisky or Whiskey?
Distributing carbon monoxide directly to homes while people are fast asleep is a more efficient way to reduce their carbon footprint. Still, converting a small amount of it to ethanol in advance and feed it to the general populace may prevent public disturbance over the process by making them unaware of the treatment, otherwise it might be considered inconvenient by some, inducing violent behavior.
Where is their computer model and why aren’t we doomed?
Rob, you write “Forgive me if I want to wait until they actually start producing commercially before I believe it.”
Fair enough. There have, indeed, been too many failures. Let us wait until the end of this year, and then take a look at what has happened.