The greens worst nightmare? A CO2 to Oil process

Protest signs of the future? /sarc

From the University of Minnesota:

U of M researchers close in on technology for making renewable “petroleum” using bacteria, sunlight and carbon dioxide

MINNEAPOLIS / ST. PAUL (03/23/2011) —University of Minnesota researchers are a key step closer to making renewable petroleum fuels using bacteria, sunlight and carbon dioxide, a goal funded by a $2.2 million United States Department of Energy grant.

Graduate student Janice Frias, who earned her doctorate in January, made the critical step by figuring out how to use a protein to transform fatty acids produced by the bacteria into ketones, which can be cracked to make hydrocarbon fuels. The university is filing patents on the process.

The research is published in the April 1 issue of the Journal of Biological Chemistry. Frias, whose advisor was Larry Wackett, Distinguished McKnight Professor of Biochemistry, is lead author. Other team members include organic chemist Jack Richman, a researcher in the College of Biological Sciences’ Department of Biochemistry, Molecular Biology and Biophysics, and undergraduate Jasmine Erickson, a junior in the College of Biological Sciences. Wackett, who is senior author, is a faculty member in the College of Biological Sciences and the university’s BioTechnology Institute.

“Janice Frias is a very capable and hard-working young scientist,” Wackett says. “She exemplifies the valuable role graduate students play at a public research university.”

Aditya Bhan and Lanny Schmidt, chemical engineering professors in the College of Science and Engineering, are turning the ketones into diesel fuel using catalytic technology they have developed. The ability to produce ketones opens the door to making petroleum-like hydrocarbon fuels using only bacteria, sunlight and carbon dioxide.

“There is enormous interest in using carbon dioxide to make hydrocarbon fuels,” Wackett says. “CO2 is the major greenhouse gas mediating global climate change, so removing it from the atmosphere is good for the environment. It’s also free. And we can use the same infrastructure to process and transport this new hydrocarbon fuel that we use for fossil fuels.”

The research is funded by a $2.2 million grant from the U.S. Department of Energy’s Advanced Research Projects Agency-energy (ARPA-e) program, created to stimulate American leadership in renewable energy technology.

The U of M proposal was one of only 37 selected from 3,700 and one of only three featured in the New York Times when the grants were announced in October 2009. The University of Minnesota’s Initiative for Renewable Energy and the Environment (IREE) and the College of Biological Sciences also provided funding.

Wackett is principal investigator for the ARPA-e grant. His team of co-investigators includes Jeffrey Gralnick, assistant professor of microbiology and Marc von Keitz, chief technical officer of BioCee, as well as Bhan and Schmidt. They are the only group using a photosynthetic bacterium and a hydrocarbon-producing bacterium together to make hydrocarbons from carbon dioxide.

The U of M team is using Synechococcus, a bacterium that fixes carbon dioxide in sunlight and converts CO2 to sugars. Next, they feed the sugars to Shewanella, a bacterium that produces hydrocarbons. This turns CO2, a greenhouse gas produced by combustion of fossil fuel petroleum, into hydrocarbons.

Hydrocarbons (made from carbon and hydrogen) are the main component of fossil fuels. It took hundreds of millions of years of heat and compression to produce fossil fuels, which experts expect to be largely depleted within 50 years.

###

In press at the Journal of Biological Chemistry

Purification and Characterization of OleA from Xanthomonas campestris and Demonstration of a Non-decarboxylative Claisen Condensation Reaction*

  1. Janice A. Frias,
  2. Jack E. Richman,
  3. Jasmine S. Erickson and
  4. Lawrence P. Wackett1

+ Author Affiliations


  1. From the Department of Biochemistry, Molecular Biology, and Biophysics and BioTechnology Institute, University of Minnesota, St. Paul, Minnesota 55108
  1. 1 To whom correspondence should be addressed: Dept. of Biochemistry, Molecular Biology, and Biophysics, 140 Gortner Laboratory, 1479 Gortner Ave., University of Minnesota, St. Paul, MN 55108. Tel.: 612-625-3785; Fax: 612-624-5780; E-mail: wacke003@umn.edu.

Abstract

OleA catalyzes the condensation of fatty acyl groups in the first step of bacterial long-chain olefin biosynthesis, but the mechanism of the condensation reaction is controversial. In this study, OleA from Xanthomonas campestris was expressed in Escherichia coli and purified to homogeneity. The purified protein was shown to be active with fatty acyl-CoA substrates that ranged from C8 to C16 in length. With limiting myristoyl-CoA (C14), 1 mol of the free coenzyme A was released/mol of myristoyl-CoA consumed. Using [14C]myristoyl-CoA, the other products were identified as myristic acid, 2-myristoylmyristic acid, and 14-heptacosanone. 2-Myristoylmyristic acid was indicated to be the physiologically relevant product of OleA in several ways. First, 2-myristoylmyristic acid was the major condensed product in short incubations, but over time, it decreased with the concomitant increase of 14-heptacosanone. Second, synthetic 2-myristoylmyristic acid showed similar decarboxylation kinetics in the absence of OleA. Third, 2-myristoylmyristic acid was shown to be reactive with purified OleC and OleD to generate the olefin 14-heptacosene, a product seen in previous in vivo studies. The decarboxylation product, 14-heptacosanone, did not react with OleC and OleD to produce any demonstrable product. Substantial hydrolysis of fatty acyl-CoA substrates to the corresponding fatty acids was observed, but it is currently unclear if this occurs in vivo. In total, these data are consistent with OleA catalyzing a non-decarboxylative Claisen condensation reaction in the first step of the olefin biosynthetic pathway previously found to be present in at least 70 different bacterial strains.

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Andrew Girle
March 30, 2011 1:11 pm

This is not a new idea – I have a book on my shelves from 1956 that describes this being done in a US University, a pilot plant was established and produced gasoline at twice the cost of gasoline available at the pump, which meant that it would take a significant rise in fuel prices to make it economical. The author concluded that technology would make it cheaper when the need arose. Looks like that need is approaching!
As for the growing area – use of ponds is highly inefficient, far better is stacked rows of growth media being circulated in clear tubes – the surface area is not just the top few millimeters of the pond but tens of thousands of times that in the network of tubes, and the source of the CO2 was even in 1956 being proposed as the waste gas from coil or oil fired power stations.

Steve R
March 30, 2011 1:13 pm

I’ve often wondered why some smart organic chemist couldn’t figure out a reaction to combine coal and methane (both of which are plentiful) to form a mid-weight hydrocarbon such as iso-octane:
7C (coal) + 9CH4(nat gas) –> 2C8H18 (octane)
note: I’m not talking of the better known Fisher-Tropsch method (which didn’t use natural gas for the source of Hydrogen in the process)

March 30, 2011 1:19 pm

But… if the world gets dependant on using CO2 to generate energy, and the use of energy is ramping up exponentially as more and more countries join modernity…
Oh my god! We might use up all of the CO2 in our atmosphere and kill off all vegetation! This research must be stopped immediately, because one possible outcome is unacceptible!

1DandyTroll
March 30, 2011 1:48 pm

I would imagine the greens worst nightmare begins when the rest of us actually starts, doing what our parents told us to do, before we could leave the table, to eat our greens, and proudly exclaim: Hey, we only eat vegans!

A Lovell
March 30, 2011 2:36 pm

Richard B says:
March 30, 2011 at 7:52 am
http://assassinationscience.com/climategate
Thanks for the website. I read as much as I could find on Climategate 16 months ago when the emails were first released, but that site puts it all in perspective.
I’ve just read the whole lot over the course of several hours, riveting stuff. I still can’t believe that with all that evidence those ‘scientists’ are still spouting the same old stuff.
The edifice is crumbling, but only one slow brick at a time.

Legatus
March 30, 2011 2:39 pm

Petroleum to last 50 years *yawn*.
During WWII, many many moons ago, the Germans had a bit of a feul problem. So, they made artificial oil from coal and even air. Have we de-evolved sooo very much that we are now too stupid to do what they do soooo many decades ago? Look it up.
We could make oil from air now. Stage one, build lots of nuclear power plants, heck, make them good ones, such as breeders, pebble bed ones, even, dare i say it, thorium ones. Thats just stage one, to get the economy booming (ps, you also need to frog march a lot of government regulators out to the parking lot and shoot them, which is the real sticking point). Now that you have lots of power, you can use it to convert electric power to oil from air, more economy booming (as well as the biosphere). Now, with that booming economy, get cheap access to space, or just so much wealth that it doesn’t matter how much it costs. Now, make solar panel space stations, lots of them, that beam microwaves back to collectors on earth. You now have unlimited electric power forever, and all the feul you want, and we don’t even have to trade in our cars.
So, have we de-evolved, or maybe those old Germans were soo much smarter than we are today??

David L
March 30, 2011 2:54 pm

Wow! Exploiting the carbon cycle to harness the sun’s energy into a useable form for current technologies (I.e petroleum). What a cool idea. But the EPA won’t allow it because CO2 is a known toxic environmental pollutant that should be completely banned! /sarc

Colin
March 30, 2011 3:40 pm

No, philincalifornia, I don’t think it’s harsh at all. There is no more cruel delusion in the energy business than the slogan “sunlight is free”. It’s a delusion because harnessing such a diffuse energy source is always hideously expensive. It’s an inevitable consequence of low energy density.

Mark Role
March 30, 2011 3:44 pm

I’m a green, and I think this is a good thing. The issue with CO2 is that we shouldn’t be taking more of it out of the ground, but if we can take it from the atmosphere and reuse it as liquid fuel, essentially gathering energy from sunlight and storing it as a petro product, this won’t make our planet any worse off than it is.

Laurie Williams
March 30, 2011 3:55 pm

Anthony your statement about the greens hating this is a good one, but apart from that I don’t see any of this as good news.
The statement “CO2 is the major greenhouse gas mediating global climate change, so removing it from the atmosphere is good for the environment.” demonstrates these people’s willingness to continue to profit from the several related hoaxes that global warming is happening, global warming is bad, CO2 is a pollutant and removing it from the atmosphere is a good thing.
One commenter here who said something about “CO2 neutral” does not seem to get it either. More CO2 in the atmosphere would be a bonus in every way, including human health I suspect (more on that later).
And on top of all that these guys are not talking about producing fuels that burn cleanly but about more trendy stinking Diesel.

George E. Smith
March 30, 2011 4:00 pm

“”””” citizenschallenge says:
March 29, 2011 at 11:09 pm
“The greens worst nightmare: A CO2 to Oil process”
Do you WUWT folks listen to yourselves?
What’s up with the totally demonizing of “greens” ?
And the disgusting fantastical twisting of other’s motives?
You folks have actually convinced yourselves that greens don’t want solutions.
It’s sad and helps explain my sense of hopelessness everything I try to reason with Global Warming “skeptics” “””””
Well citizenschallenge (shouldn’t there be an apostrophe in there ?). some of us have been busilyy working each and every day on those very solutions that you still just talk about. In my case for more than half of a century. So I was actually developing solutions long before there even were greens; and long before you were even wet behind the ears.
Do you realize that we used to recycle stuff even 3/4 of a century ago. We used glass bottles for milk, and we put them out for recycling every night, so they took them back, and washed them, and refilled them. How cool is that to actually use something over again. Why we even used our baby’s diapers over again, after washing them.
You of the texting and twittering generation think you invented the idea of conservation and waste reduction and efficient use of resources. Well get in line; you and your parents discarded the solutions that we had long before your time; blame your parents for the mess you have gotten yourselves into now.

JRR Canada
March 30, 2011 4:05 pm

Or using pressure and subsurface heat, oops maybe those russians are right.Seems odd that they find oil where there theory predicts it. Yes there are some good greens, lightly steamed or chopped on my dinner plate, the rest seem to be two legged mental midgets that wallow in their self loathing and self righteousness.

George E. Smith
March 30, 2011 4:13 pm

“”””” David L says:
March 30, 2011 at 2:54 pm
Wow! Exploiting the carbon cycle to harness the sun’s energy into a useable form for current technologies (I.e petroleum). What a cool idea. But the EPA won’t allow it because CO2 is a known toxic environmental pollutant that should be completely banned! /sarc “””””
Well David; don’t laugh, but that actually happened as recently as the great gulf oil well blowout. That oil well spewed out millions of gallons of oil into the water, where it gathered in huge pools. Oil Industry workers, wanted to go out with a fleet of oil tankers, and actually pump that valuable oil out og the ocean into the tankers; after all the idea of drilling that well was to get the oil.
Well the oil would have floated on top of the sea water, that slowly accumulated in the bottoms of those tanker’s tanks, and they would have to periodically pump all that salty water back overboard to where it came from; but most of the oil could have been thusly recovered, therby removing it from the gulf, as a potential hazard to marine life, and delicate coastlines.
The EPA nixed the plan saying that they could not pump the water overboard again as it was contaminated with oil. So instead, they dumped millions of gallons of toxic dispersants into the ocean to break up all those oil pools so you couldn’t recover the oil. So now you had both oil pollution and chemical dispersant pollution as well, and no oil production from the well.
As I have often said, Ignorance is NOT a disease; we are all born with it. But Stupidity has to be taught, and there are plenty who are willing and able to teach it; and most of them work at the taxpayer’s expense, on the “public service” rolls.

Bruce Cobb
March 30, 2011 4:15 pm

Andrew Girle says:
March 30, 2011 at 1:11 pm
This is not a new idea – I have a book on my shelves from 1956 that describes this being done in a US University, a pilot plant was established and produced gasoline at twice the cost of gasoline available at the pump, which meant that it would take a significant rise in fuel prices to make it economical. The author concluded that technology would make it cheaper when the need arose. Looks like that need is approaching!
Gas appears to have been around $.25 a gallon then, which would be about $2.00 or so in todays’ dollars, making the biofuel roughly $4.00. Somehow though, I doubt it could be made at that price, once all costs were factored in (including “free” C02). It would certainly be wonderful if it could.

bill fish
March 30, 2011 4:44 pm

Work on Biofuels should continue if for the only reason to further knowledge on enzymes, biochemistry, and overall science.
As a viable commercial venture, there is one problem: a lot of effort is put in to produce a substance which is then lit with a match.
Enzymes get denatured. Biologicals are fastidious. Monoculture has drawbacks and against the environmental ideal of biological diversity.
Variants of the Fischer-Tropsch process are better commercial candidates. There is much more leeway in terms of input feedstock and the output is a mixture of hydrocarbons usable as fuel. Adding hydrogen (produced by nuclear, wind, solar) to the feedstock increases the percentage of methane and ethane produced.
Fire is the great equalizer: 99.9% of the output is carbon dioxide and water. As far as internal combustion goes, the higher the combustion, the greater the overall thermodynamic efficiency. At high combustion temperatures all fuels are broken down to similar organic fragments.

philincalifornia
March 30, 2011 4:51 pm

Colin says:
March 30, 2011 at 3:40 pm
No, philincalifornia, I don’t think it’s harsh at all. There is no more cruel delusion in the energy business than the slogan “sunlight is free”. It’s a delusion because harnessing such a diffuse energy source is always hideously expensive. It’s an inevitable consequence of low energy density.
——————————————————
I’m finding the price of petroleum-based gasoline to be hideously expensive these days too. Brazil’s sustainable biofuel economy, derived mainly from free sunlight, is not a delusion.
By the way, I know exactly what you are saying and I still think you’re language is harsh. I would make an educated guess that the molecules that are the topic of this post can be made more inexpensively by free sunlight and the X million years of evolution of the bug than by Du Pont chemists, petroleum-based starting materials and (even nuclear) electricity.
There are just some structures that are like that. Ethanol, crap though it is as a product because of its properties, is even on the cusp of profitability.
We can agree to disagree for now, but there are real scientists in this field, so don’t be surprised to see some game-changers, especially as diffuse energy collection infrastructure is already in place.

Richard S Courtney
March 30, 2011 5:07 pm

Colin says, at March 30, 2011 at 3:40 pm,
“There is no more cruel delusion in the energy business than the slogan “sunlight is free”. It’s a delusion because harnessing such a diffuse energy source is always hideously expensive. It’s an inevitable consequence of low energy density.”
Yes! And it needs to be said often because – with the exception of hydro electricity – it is the reason why all the so-called renewables are an expensive and useless waste.
All energy is “free” because it all derives from the “big bang” which initiated the universe. All energy flows capable of conducting work are stages in the process from that event to the heat death of the universe.
But, although energy is “free”, collecting energy and concentrating it to provide useful work in useful amounts is expensive.
Only three processes provide energy flows which can be sampled by humanity. They are
• the residual energy which was concentrated in ancient – now dead – stars,
• the residual energy from the formation of the solar system, and
• the energy flowing from the sun.
Nature has collected and concentrated the energy of some of these flows for us.
Processes which initiated during the lives of ancient stars have generated radioactive substances notably uranium. The stars concentrated that energy so it is in high energy density in those substances. And amounts of these substances were part of the material which accreted to form the Earth, and they may be utilised as fuel in nuclear power plants.
Residual energy from the formation of the solar system is observed in the power of the tides and geothermal forces. Indeed, it can be argued that the Earth and Moon system is still forming because these processes still continue. Like sunlight, there is a lot of tidal and geothermal energy flowing around the Earth but it is spread over the globe so there is little at any one place unless nature stores it before releasing it explosively (as an earthquake and/or tsunami).
Energy flowing from the sun consists of radiations and particles. To date, only sunlight and solar heat have been utilised as solar energy sources by humans. The most useful form of solar energy is fossil fuels which contain solar energy collected by photosynthesis over long times (geological ages) and large areas.
Fuels are stores of energy. Thus they have high concentrations of energy. They are commodities which can be stored, transported when and where desired, and used as required. Thus, they can be used to provide energy which can be distributed as electricity when and where it is wanted.
Fuels such as the synthetic oil described in the above article cannot compete with fossil fuels because they and fossil fuels are both stores of solar energy collected by photosynthesis. But in each year the described synthetic fuel can only provide the energy from photosynthesis during that year whereas fossil fuels are the result of the energy from photosynthesis conducted over geological ages.
We should be grateful that nature has done so much expensive energy collection and concentration for us because we do not have geological ages available to us so we can imitate nature. And, because, we do not have geological ages to conduct the collection of solar energy, the described synthetic fuel cannot be economically competitive with fossil fuels which we can dig or pump out of the ground.
Richard

Howard
March 30, 2011 5:21 pm

Not to worry. The Marxist dictator in the White House, the EPA gestapo, and the climate change environuts will find a way to stop any sensible solution to energy development and production in America. Sieg Heil Momar Obama.

Ian L. McQueen
March 30, 2011 6:51 pm

Apologies if this is a repeat. I hit the Tab key twice and everything vanished.
We have a fuel. We burn it for energy. It produces CO2. We use the CO2 plus sunlight to produce fuel. Isn’t this equivalent to discharging and recharging a storage battery, with sunlight as the energy to recharge the battery? I wonder if it would be simpler and more efficient just to use the sunlight directly. Expressed another way, the only way that this process makes sense is if CO2 must be removed from the atmosphere. And since it has never been proved scientifically that CO2 causes measurable warming, that supposition does not hold water.
IanM

JPE
March 30, 2011 7:12 pm

Oh, Joy!
Wouldn’t it be the ‘ultimate irony’ if pumping carbon dioxide into the ground (sequestration) actually did produce oodles of petroleum naturally? Perhaps it should be pumped into landfills (where the bateria are). Let’s see… first we foul the earth with nasty garbage (methane), then we foul it further with nasty coal buring (CO2), and we ultimately create MORE nasty petroleum — that we use to go to buy stuff to put in landfills. Circular insults?

philincalifornia
March 30, 2011 8:46 pm

Colin, Richard,
Well, I spend more money on food than I do on gas in a given week, and the energy it gives me to type this is, I think, free sunlight-derived (counterintuitively including the mushrooms).
If you don’t like free sunlight as the source of energy that fuels your own temporary fight against entropy, try some other source for a few weeks, and then get back to us on how that went.
My point being, of course, that because of life’s aqueous catalysis, evolution of sophisticated biochemistry within certain microorganisms (that can be hugely concentrated in a fermentor), and the fact that rudimentary biofuel technology is already comparable with food energy and in concentrated liquid form, don’t write off the future of biofuels.

sak
March 31, 2011 1:09 am

Sounds interesting and I suppose the CO2 supply could be found by ducting from a coal fired plant to an adjacent production facility. However, at what cost to produce…and is there even a net energy production?

Cold Englishman
March 31, 2011 1:55 am

It is a clever idea, but as is often the case, the devil will be in the detail. What you can do in the lab, is not always easy to scale up to an industrial level.
This is one of those schemes however that deserves serious funding, because it provides a long and uninterrupted fuel source, it could change the geopolitical landscape, and make western countries more self reliant on fuel.
The obvious connection is of course to place it side by side with a coal or gas generator, so that “free” CO2 is directly available. This would also solve the non problem of “emissions”, which should please the greens (well hardly), but you can try.

Smoking Frog
March 31, 2011 4:33 am

Frank Lee MeiDere says: Whereas, by taking CO2 from the atmosphere (providing the process worked, and providing it worked efficiently), the only thing stopping a global extinction from CO2 scarcity within 100 years is the moral integrity and ethical characters of those controlling the trillions and trillions of energy dollars.
See my point?

Not really. You haven’t addressed the obvious objection that burning the fuel would return the CO2 to the atmosphere. Some of the carbon would go to carbon monoxide, but that doesn’t defeat the objection, since carbon monoxide is converted to CO2 after a while. Maybe something else would defeat it. I don’t know.

Colin
March 31, 2011 5:08 am

phil, you need to understand some basic physics. The human body is a 200 watt machine, using about 100 watts for metabolic purposes and about 100 watts available for useful work. It illustrates the fact that the energy available from biologic systems is trivial on a per unit of mass basis. Why do you think we no longer burn wood for heating and powering our cities? Because the energy density is far too low. It was too low in 1300, let alone today, which is why mediaeval Europe switched to coal.
It’s ultimately why the fossil fuel system will ultimately fail. Not because we run out of them but because they are too low density to sustain a completely urbanized world. There’s a limit to how many tankers can be loaded in the Persian Gulf and moved through the Straits of Hormuz, for example, and we’re now getting close to that limit. Energy density is why all the renewable options fail, except hydro-electric, and nearly all of that is already in service.