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.
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Carbon neutral
————
So?
Way cool. Further evidence that within the next few decades, we’ll be able to cheaply synthesize all sorts of things that are currently very expensive to either mine or derive in other ways from natural resources. Research and technology are going to solve the many technical challenges of the century, not carbon trading.
rgb
This is very good news.
There are however useful ways we could use plants in this regard. Mesquite is an example, it can grow on very poor land non irrigated, and produce year after year. This could be done on land not otherwise useful today. If set up ideally you might even bolster local water tables long term as the organic matter slowly builds up on the surface and allows for better water retention. We certainly couldn’t grow all our fuels like this, but there is a potential niche there to be sure.
I always knew corn based ethanol would fail. I truly cannot understand why anyone would ever push for it, it is a horribly inefficient way to have thrown around resources. Dont dismiss plants entirely though!!!
This will go over like a cement cloud here in Wisconsin, and the rest of the corn belt, where the farmers tenaciously hold on to their corn subsidies.
I would not invest in this process until I could see a complete energy, energy cost, and mass balance including the electrical energy required to process this uphill reaction and including an estimate of the CO2 generated from the required electricity.and including the enrgy required to concentrate the ethanol/water solution.
@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%, finding a cheap way to make fuel without causing CO2 emissions is to be welcomed. That it would not compete with food crops and reduce dependence of oil from hostile countries is all the better.
Ok, let me get this straight. I take the output of a power plant, and then in order to remove the oxygen atoms from the carbon I need the output of about 5 power plants of the same size (coal plants are about 40% efficient, heat to electricity and the CO to ethanol process is 57% efficient). So in order to remove the carbon dioxide exhaust from one plant, it takes the electrical output of roughly 5. Does this make sense to anyone out there?
The energy in a coal plant comes from adding the two oxygen atoms to one of carbon (a process we call burning). The energy required to separate the oxygen from CO2 is roughly the same as you get from burning carbon. Actually it is worse than that because the separation processes are inefficient and making electricity is inefficient (2nd law).
No process that involves the decomposition of CO2 can make any sense from a conservation of energy standpoint.
So making ethanol from carbon monoxide…. does this mean the cars can just have a fuel line from the muffler to the gas tank and fuel themselves??? Count me in!!
Now CO IS a deadly gas. Any productive use of excesses would be beneficial. But that begs another question. Where are they going to get all the CO from? If they eliminate the production of Ethanol from plants, there goes a significant source of the CO.
Some I forgot … on what tree does carbon monoxide grow?
Randy,
“I always knew corn based ethanol would fail. I truly cannot understand why anyone would ever push for it, it is a horribly inefficient way to have thrown around resources.”
1. Ethanol was first added to gasoline in the US not for reducing gas consumption or for reducing CO2 emissions, but to reduce VOC(volatile organic compounds) emissions. VOCs tend to be very toxic and were at the time the big problem in tailpipe emissions. Ethanol does a very good job of this, but it only takes around 5% ethenol.
2. At the time we first started adding ethanol to gas, corn was the crop in which we had the highest surplus. That surplus was so large, we were running out of places to store it effectively. At the time, it made sense to use corn for ethanol production.
This is really interesting science. Too bad they have to dress it up as a global warming mitigation scheme to maintain their funding.
The flaw in their carbon neutral plan is that you still need energy input to make it work. I suppose if efficient enough it could become a way of storing energy from windmills and solar farms that are currently impractical due to being intermittent and expensive, and it provides a potential liquid fuel source for vehicles instead of trying to store electricity in batteries, BUT, it still comes down to economics. The advantage that fossil fuels have is that the energy input process has already been done when we dig the stuff out of the ground. Can the cost of generating ethanol this way compete with the cost of refining oil? I seriously doubt it.
But the science itself is truly interesting.
http://www.geek.com/science/game-changing-navy-technology-can-turn-seawater-into-jet-fuel-1590495/
US Navy creates fuel from seawater. A nuclear aircraft carrier could [use] this process to create fuel for its aircraft and lower the need for tanker replenishment
Sandi: April 9, 2014 at 1:15 pm
“This will go over like a cement cloud here in Wisconsin, and the rest of the corn belt, where the farmers tenaciously hold on to their corn subsidies.”
Well they could try another novel market and try selling their corn for, oh I dunno…. Food?
“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,…”
Perhaps using either solar or wind power would make sense here?
There is already a company with a process to convert CO2 to ethanol, gasoline, and diesel. They are building a commercial plant.
From the article:
Joule’s process produces fuels from specially engineered photosynthetic bacteria, waste carbon dioxide, sunlight and water. The production method involves erecting solar converter systems across unused land.
Joule says the technology has the potential to decentralize the fuel industry, allowing fuel to be produced wherever the necessary elements are available.
Joule was founded in 2007 by Flagship Ventures, and has raised at $110 million in funding to date from Flagship and unnamed investors.
The company’s first “SunSprings” demonstration plant is located in Hobbs, N.M., and was commissioned last September and funded by Joule’s $70 million round of funding from early 2012.
http://www.bizjournals.com/boston/blog/startups/2013/04/joule-renewable-gasoline-jet-fuel.html
http://www.jouleunlimited.com/
Mark 543 says:
April 9, 2014 at 1:18 pm
There’s nothing new about making fuel from nuclear energy with no CO2 output. Hydrogen gas can be produced from (waste)water. Liquefied H2 can be supplied by pipeline.
And don’t go off on a Fukushima rant. That’s like making decisions based on a black and white 60s TV versus a modern flat screen TV. Nuclear technology has changed. Modern modular reactors can’t melt down.
http://www.nei.org/Issues-Policy/New-Nuclear-Energy-Facilities/Small-Reactor-Designs
http://www.gen4energy.com/
http://www.nuscalepower.com/
http://news.nationalgeographic.com/news/energy/2013/06/130605-small-modular-nuclear-reactors-tennessee/
Fukushima v modular Gen4 technology comparison
http://www.gen4energy.com/technology/safety-security/ (scroll to bottom)
Where do you get a significantly pure source of co to make this work?
unless I’m missing something energy in will exceed energy out. Without cheap electric power this is worthless.
The joule process will get concentrated CO2 from a cement plant or fossil fuel electricity plant.
This Company makes Ethanol from natural gas but the EPA wont let them use it with gasoline even though it is exactly the same as grain ethanol.
http://www.chron.com/business/energy/article/Incentives-sought-for-ethanol-made-from-natural-1597659.php
From the article:
Joule’s hydrocarbon fuels have the additional benefit of being inherently sulfur-free. For the diesel and gasoline markets, this gives refiners the ability to meet sulfur content requirements without raising production costs or fuel prices. As just announced on March 29, 2013, the US Environmental Protection Agency is seeking to further reduce the sulfur content of gasoline by more than 60% beginning in 2017.
Joule is now commercializing its first product, Sunflow-E, for global availability in early 2015. Construction of the company’s first commercial plants is planned to begin in 2014 in multiple locations worldwide.
To support its progress towards commercialization, the company has launched Joule Fuels, a global subsidiary formed to capitalize on the $1+ trillion fuels market with exclusive access to Joule’s revolutionary technology, IP and know-how.
“Joule’s production platform is well suited to many regions around the world, where improving local energy security and environmental performance are critical goals,” said Peter Erich, President of Joule Fuels. “We are actively seeking sites and partners to deploy Joule Fuels plants in these regions, enabling localized production of high-volume, cost-competitive fuels in a sustainable process. This includes unique opportunities for off-take partners and input providers, including industrial CO2 emitters who can meet sustainability goals by directly converting their emissions into clean, renewable fuels.”
http://www.biofuelsdigest.com/bdigest/2014/03/13/joule-unlimited-biofuels-digests-5-minute-guide-2/
Wow! That is environmentally friendly?
IF this new technique can be scaled up and is commercially viable then this must be a nightmare for many greens. It would once again show that all the panic over co2 is similar to the horse manure panic of the late 19th century. We always seem to get ourselves out of a ‘fix’. At the end of the day crude oil will not last forever, but suck it out while it’s there I say.
The advantage that fossil fuels have is that the energy input process has already been done when we dig the stuff out of the ground. Can the cost of generating ethanol this way compete with the cost of refining oil? I seriously doubt it.
At the conversion efficiencies they suggest in the top article, possibly. All it appears to require as input is electricity (plus water, catalysts, and sources of CO and/or CO_2 gas. One could indeed imagine setting up closed-system loops where the source of the CO/CO_2 is the burning of the ethanol produced, so that one is basically using the ethanol only as a means of energy storage.
But the beauty of research is that nobody will implement this as production technology unless it IS able to find some economic niche where it is cost-advantageous. It might not be advantageous now, but in fifty years it might be. It’s just like our ability to synthesize gasoline or diesel out of coal — marginally unprofitable by design as long as it is cheaper to directly mine oil than to mine coal and convert it into oil, but as the relative scarcity of one rises compared to the other, that could change.
The real problem with the process is that I’ll wager it doesn’t work very well given only the CO or CO_2 levels available in the atmosphere. I’m guessing that it works with a basically saturated CO level in the water. Concentrating the gas in the water to make a suitable catalytic feedstock (and then distilling out the resulting ethanol) are both going to substantially add cost.
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. Once again, rates and efficiencies are key, but a passive pay-once-use-forever catalytic sheet that produced liters of ethanol per square meter of collector per suitable time unit with nothing added but water, that would be an attractive thing.
rgb
There are two commercial plants about to go into production, producing ethanol from waste agricultural products; POET/DSM and Dupont. The feedstock is corn stover, and POET has worked out with farmers that 1 ton per acre of the corn stover produced is, in fact, waste.
Don’t get me wrong. I am in favor of any commercially viable way of turning waste products into useful fuel. Will the two plants I mentioned be commercially viable? We wont know until at least the end of this year, but both are being financed mainly with private money.
No one notices it’s another net energy loss, really just a nice science experiment…