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.
Who in their right mind makes copious quantities of surplus CO and then wants to make ethanol to displace petro-gasoline?
“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.”
Is this not a variant of the perpetual motion machine?
Looks like University of Delaware might be willing to sell them the CO (sometime in the future):
http://wattsupwiththat.com/2014/01/31/better-living-through-carbon-conversion-chemistry/
Latest predictions on the science advances in solar panel and storage solutions in The Telegraph
http://www.telegraph.co.uk/finance/comment/ambroseevans_pritchard/10755598/Global-solar-dominance-in-sight-as-science-trumps-fossil-fuels.html
“Solar power will slowly squeeze the revenues of petro-rentier regimes in Russia, Venezuela and Saudi Arabia. They will have to find a new business model, or fade into decline.
Solar power has won the global argument. Photovoltaic energy is already so cheap that it competes with oil, diesel and liquefied natural gas in much of Asia without subsidies.”
“But growing crops for biofuel requires thousands of acres of land”
Make that millions of acres.
“But we have a lot more work to do to make a device that is practical.”
Translation : ain’t gonna happen, but send funds anyway.
Another Non-Starter
Archer-Daniels Midland will never allow this baby to get out of its crib, too much funding and subsidies to lose.
Interesting from a chemistry standpoint, and likely to be very useful in the future, but not for automobiles.
Ethanol (as noted in a previous post) was introduced to mitigate the emission of VOCs in auto exhaust, although I don’t know if that was ever shown to happen. What has been demonstrated, however, is that it reduces the amount of energy in a gallon of “gasohol” (also known as E-10 where I live- Barackistan, formerly known as Illinois).
Last summer, I drove my 2003 Ford CVPI out west. Stopping for fuel (I think it was in Colorado), I saw that the lower octane fuel (85) was more expensive than the mid-range fuel (87 Octane).
Realizing that the difference in price was the absence of ethanol, I chose to perform an experiment. I always note my gasoline purchases (date, odometer reading, total number of gallons, price per gallon, and total cost for a tankful) and have for a number of years- the impetus for this behavior was the realization that, as engine control systems have improved, the only way to tell that a vehicle needs a tuneup these days is to check the MPG- the car performs pretty much the same, otherwise.
My Police Interceptor normally gets about 18 MPG, city or highway. During the course of this experiment, however, running on the “low-octane” gasoline, my MPG improved to 23.6- almost a 30% increase! And this was driving through the mountains, not on flat ground like in Illinois!
No matter how bad an idea ethanol in gasoline is, it won’t go away. The lobbyists have both political parties bought off, and any non-farm alternative will die a quiet death.
Maybe the Department of Energy will issue a grant. That is where good ideas go to die…
Mark 543 says:
April 9, 2014 at 1:18 pm
“@So? There is a nonzero probability that the world’s leading scientific societies are correct and the politically motivated bloggers are wrong about climate change. Even it is only 20%”
IFF warming and CO2 increase correlate from 1979 to 1997 – 18 years – AND then, warming stops while CO2 continues to increase from 1997 to 2014 – 17 years and counting – AND all climate models failed to predict the latter, insisting on a continuation of the warming trend, we can SAFELY say that attempts at predicting the future climate have completely failed. In fact, a random generator would have beat the climate models.
So, we can say: Climate Science is worse than guessing. It has negative predictive skill. It has a NEGATIVE probability of being right.
the last thing we want to do is pull co-2 out of the air .It is vital for all life on earth less is not better.
I think this is cool. Makes the carbon-nutcases happy, might have commercial value and might get corn being used for what corn should be used for; food!
Perhaps a rare win-win-win. (hence probably highly unlikely!)
why not grow industrial hemp on all the land not suitable for farming over 25 million acres in usa could be used as far as i can find out 1 acre can produce 30 barrells of oil witch can be used to power all manner of things also the seed cake left over is perfect for animal feed and the stalk is brilliant for building houses a win win situation all round me thinks also hemp absorbs huge amounts of co2
@James Baldwin, just think about the math! Do realize how MUCH carbon-dioxide we can pull out of the air and impact the ppm minimally but make LOTS of ethanol!
For the Joule process, it would use CO2 to make ethanol, gasoline, or diesel. Once the fuel is burning, it is CO2 once again! Win win.
we should do every thing possible to increase the co-2 in the air.Plants will do better and increase crop yields.
Storing energy in a liquid fuel is what our transport system is based on – solid state energy storage (batteries) just don’t cut it. Given the acceptance that there is some finite limit to oil (and lpg) a reasonably cost effective method of producing ethanol would be useful at some stage. However, this outcome is still a long way off with this technology – a fact placed front and center by the inventor.
Since cellulosic ethanol is still five years away from commercialization (as it has been for about 15 years now, I think), we are still looking at fermentation of sugars (not starch from corn) as the only viable method. Great if you can grow sugar-cane without displacing food crops, but this is not an option for pretty much anyone except Brazil (and Australia, but I don’t think they have cottoned on yet – don’t anybody tell them!).
Oh well, good job our oil reserves keep growing then I guess…..
rgb wrote, “OTOH, maybe they’ll figure out how to make an integrated nano-material fabric that can be stretched into sheets and laid out in solar cells. As long as the sheet is kept damp and in the sun, it pulls CO_2 from the air, combines it with water on the sheet, and gives off ETOH, which floats up to the top of the panel and into a condenser coil so that all day long, ethanol accumulates at the bottom.”
Kind of an engineer’s/chemist’s/physicist’s version of photosynthesis.
What’s better, using the electricity directly to power an electric motor at 92% efficiency to propel a vehicle, or use the electricity at 57% efficiency to make ethanol which then has a 25% efficiency to run a motor to propel a vehicle.
Mark 543 says:
April 9, 2014 at 1:18 pm
“@So? There is a nonzero probability that the world’s leading scientific societies are correct and the politically motivated bloggers are wrong about climate change. Even it is only 20%”
What about scientifically motivated bloggers & the thousands of scientists in relevant disciplines who agree with them?
The suborned, bought off societies have been 100% wrong so far, ie their hypothesis has been repeatedly falsified & they haven’t even been able to reject the null hypothesis. Why do you suppose there is a 20% chance that they might be right at some point in the future?
As I understand this, it proposes to take electricity (a form of energy) and turn it into ethanol (a form of energy). To produce work one must convert the stored energy into ‘work’ such as heating (cooking) or motion (vehicle fuel). An advantage is that it is relatively energy dense per unit volume compared with batteries or super capacitors which could store the electricity directly and give it back on demand. A disadvantage is that it has to be combusted, or reacted in a fuel cell to get back electricity, meaning it is a battery, and not a very efficient one at that. There are ethanol-powered cell phones – did you know that?
The ‘closed loop’ thing is not really closed – it has a huge input of solar energy. Well there is nothing wrong with that but it has to compete with the other ways one could store solar energy and move it around for sale. I certainly favour ending the subsidies on corn ethanol and putting the money saved into developing this and other technologies like Propanol.
Replacement Fuel Research is vitally important
Despite all the hoopla, “tight oil ” wells deplete at about 20%/year – and require ever increasing drilling. The IEA reports existing oil fields are depleting at about 6%/year.
We are dangerously past the time for major efforts to develop replacement fuels. See Richard L. Hirsch, The Impending World Energy Mess.
Bjorn Lomborg and the Copenhagen Consensus identifies research into replacement fuels as one of the most effective applications of funds – far ahead of subsidies for existing technologies.
Long term energy sources are nuclear fusion – solar energy or artificial fusion; and nuclear fission – such as conventional reactors or Thorium reactors. Hydrogen can be made by electrolysis or solar thermochemical catalytic cycles. For for practicality, dense liquid fuels are required.
Heather Willhauer et al of the US Navy shows how CO2 could be extracted from sea water. H2+CO2 can make Methanol and thence gasoline/diesel/JP5 or JP8 or directly via Fischer Tropsch reaction.
So research such as reported should be encouraged to search for the most economic transition and long term replacement fuels.
@ironargonaut says:
April 9, 2014 at 1:44 pm
You can gasify coal. There is a “water shift” reaction that produces a mixture of H2 and CO, popular in the late 1800’s/early 1900’s as “town gas”.
@David Chapell says:
April 9, 2014 at 2:13 pm
Not really. You still have to supply external energy to drive the reaction.
@upcountrywater says:
April 9, 2014 at 2:12 pm
I don’t think this is about net energy efficiency. It’s really about how you generate a portable energy source when you can’t make a battery big enough or storage density is just too critical. If you use grid energy of whatever stripe (coal, oil, gas, nuclear, hydro, wind, solar, etc) to drive the process, what you are really doing is converting electricity from a use-it-or-lose-it form (the grid) to a use-it-whenever form (liquid fuel). If I could plug a machine into an outlet in my house and get a liquid fuel to burn in my snowblower, lawnmower, or automobile, as long as the final cost was competitive (for me personally, not more that 10-15% over gas station prices), I’d buy that machine, assuming the amortized cost was similarly reasonable. It’s all about economics, not net efficiency.
In it’s current guise it’s just another in a long line of processes that take petroleum and convert it into something else to be used for energy production.(e.g. hydrogen fuel cells)
Why not just mine the huge deposits of methane trapped on the bottom of the ocean, and convert that to methanol; it would be more carbon friendly than ethanol, and you wouldn’t get drunk from it.
Show me a working installation ready for series production, an energy balance that tells me how much power has to go into the process and how much comes out. If the balance is positive I will have a look at it.
But please spare me the the stories. There are over a million most promising stories on the web that never made it. Now we’re shutting down power plants without a reliable base load production.
Very, very dangerous.
Cool. And it sounds way more constructive than tornado walls and hurricane windmills.
Well, you – uhm, appear to have “accidentally skipped” a few “minor” steps there.
You take power station electricity, generated at efficiencies between 38% to 62%, and transmitted across the state at some 98% to 93% efficiency, to go into a battery and get converted into stored chemical energy at about a 72% to 76% efficiency.
So, your initial energy is now only .62 x .96 x .72 of the initial amount. But it is only stored chemical energy – very much less useful than – say, the stored chemical energy in a gallon of gasoline or jet fuel that is ALREADY in chemical form. And, in fact, since the stored chemical energy in a battery is inside a very, very heavy container (the battery itself) you cannot use that chemical energy in anything that flies or drives efficiently. It also takes a very long time to recharge compared to stored chemical fuels that can be refilled in mere moments millions of times every day by unskilled labor safely.
Also, that chemical energy is now only stored for a short time in a very, very, very heavy and very, very very expensive battery using very dirty raw materials and a very large amount of energy to produce that doesn’t last a very long time before it has to be replaced.
Now, you have to re-convert that stored chemical energy in the battery BACK to DC electricity but now at a lower efficiency of 62% to 75% efficiency, control it at a 96% to 90% efficiency, and then drive a motor at the 85% efficiency to the wheels. Some energy you can get back from regenerative braking – a good thing! – but only some.
net? Your battery powered car is no better today than they were in 1900.