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Researchers Develop Method for Enzymatic Production of Hydrogen from Biomass at High Yields
23 May 2007
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| The synthetic metabolic pathway for conversion of polysaccharides and water to hydrogen and carbon dioxide. Click to enlarge. |
Researchers at Virginia Tech, Oak Ridge National Laboratory (ORNL), and the University of Georgia have developed a novel method using multiple enzymes as a catalyst for the direct, low-cost production of hydrogen from biomass.
Applying the principles of synthetic biology, the researchers use a combination of 13 enzymes to form an unnatural enzymatic pathway to completely convert polysaccharides—e.g., starch and cellulose—and water into hydrogen at a yield higher than the theoretical yield of biological hydrogen fermentations. Their work is described in the 23 May issue of PLoS ONE, the online, open-access journal from the Public Library of Science.
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| Hydrogen production from either 2 mM G-6-P or 2 mM starch (glucose equivalent) using the new method. Click to enlarge. |
Starch is a high energy-density carrier, with 14.8 H2-based mass%. (The DOE long-term target for hydrogen storage is 12 mass%.) The enzymes, when added to the biomass solution, use the energy in the polysaccharides to break the water up into carbon dioxide and hydrogen.
A membrane bleeds off the carbon dioxide and the hydrogen is used by a fuel cell to create electricity. The water byproduct is recycled for the starch-water reactor. Laboratory tests confirm that it all takes place at low temperature—30° C—and atmospheric pressure. The researchers estimated the cost of hydrogen production using their method of approximately $2/kg.
The stoichiometric reaction is:
C6H10O5 (l) + 7 H2O (l) → 12 H2 (g)+6 CO2 (g)
The overall process is spontaneous and unidirectional because of a negative Gibbs free energy and separation of the gaseous products with the aqueous reactants.
The vision is for the ingredients to be mixed in the fuel tank of a car. A car with an approximately 12-gallon tank could hold 27 kg of starch, which is the equivalent of 4 kg of hydrogen. One kg of starch will produce the same energy output as 1.12 kg (0.38 gallons) of gasoline.
The research was based on earlier work by Y.H. Percival Zhang, assistant professor of biological systems engineering at Virginia Tech pertaining to cellulosic ethanol production (earlier post) and the ORNL and University of Georgia researchers' work with enzymatic hydrogen production.
One of the team, Michael W.W. Adams of the University of Georgia UGA, is co-author of the first enzymatic hydrogen paper in Nature Biotechnology in 1996. The researchers were certain they could combine the processes.
In nature, most hydrogen is produced from anaerobic fermentation. But hydrogen, along with acetic acid, is a co-product and the hydrogen yield is pretty low—only four molecules per molecule of glucose. In our process, hydrogen is the main product and hydrogen yields are three-times higher, and the likely production costs are low—about $1 per pound of hydrogen.
What is more important, the energy conversion efficiency from the sugar-hydrogen-fuel cell system is extremely high—greater than three times higher than a sugar-ethanol-internal combustion engine. It means that if about 30 percent of transportation fuel can be replaced by ethanol from biomass as the DOE proposed, the same amount of biomass will be sufficient to provide 100 percent of vehicle transportation fuel through this technology.
—Y.H. Percival Zhang
The next step for the team is to increase reaction rates and reduce enzyme costs.
Resources:
“High-Yield Hydrogen Production from Starch and Water by a Synthetic Enzymatic Pathway”; Y.H. Percival Zhang, Barbara R. Evans, Jonathan R. Mielenz, Robert C. Hopkins, Michael W.W. Adams; PLoS ONE 2(5): e456. doi:10.1371/journal.pone.0000456
May 23, 2007 in Bio-hydrogen, Biotech, Hydrogen Production, Hydrogen Storage | Permalink | Comments (37) | TrackBack (0)
Comments
Posted by: xgalileo | May 24, 2007 at 06:57 AM
There are other benefits from this sugar water fuel. Because it is non-flammable there is nothing illegal in having a tank under the garage and a pump so that you can fuel your car from home. You simply order a tanker with sugar or starch water to come and fill it up once a year or so. Off cause if a hurricane or a winter storm comes by and disrupts electricity and blocks roads for a week or two you will do just fine with your supply of fuel and the cars ability to supply the house with electricity. And if there were no food to buy you could do just fine with some vitamin pills and a few gallons from the tank. Probably tastes like really bad but it is better than starving. I could imagine a lot of people will feel good about knowing that this was an option.
Posted by: Henrik | May 24, 2007 at 09:35 AM
Is there any possible potential for splitting the carbon and oxygen in CO2 and using the oxygen to burn the carbon? Could a chain reaction possibly be started to burn pure CO2?
Posted by: Ronald C Wagner | May 25, 2007 at 08:58 PM
Wagner it is called photosynthesis. You can read about it here http://en.wikipedia.org/wiki/Photosynthesis. Take you time to learn about it and you will also understand why this enzymatic sugar to hydrogen is a brilliant innovation. Good reading.
Posted by: Henrik | May 26, 2007 at 12:05 AM
Just discovered that this report indirectly discloses a price for the necessary enzymes. The report says that hydrogen can be produced enzymatically from biomass at $2 per kg of hydrogen all costs considered. We also know that 4 kg of hydrogen can be made enzymatically from 27 kg of sugar. Sugar costs 9 c per lb =0,453 kg for raw sugar. That is, (27/0,453)*9c = $5,36 for 4 kg of hydrogen without the price of the necessary enzymes. Conclusion, the cost of enzymes per kg of hydrogen is right now 2-(5,36/4) = $0,66 per kg of hydrogen. In other words, you can buy enough sugar and enzymes to drive 300 miles in a heavy SUV for as little as (4*0,66)+5,36 = $8 instead of spending 20 gallons of gasoline at $3,3 or $66.
Posted by: Henrik | May 26, 2007 at 04:48 AM
Needless to say that with the above low cost of enzymes it seems that the only left over show stoppers for the enzymatic sugar plug-in fuel cell vehicle is the speed of this enzymatic process as well as the ability to bring down the current high cost of the hydrogen fuel cell to the 4k target. Does anyone have any idea of the prospects for increasing the speed of these enzymatic processes?
Posted by: Henrik | May 26, 2007 at 05:04 AM
I think this development is awesome for several reasons:
1) The fuel can be grown pratically anywhere, minimizing shipping costs.
2) It's carbon neutral.
3) Everything described in Henrik's numbers. If his numbers are right, I can't possibly make a better financial or mechanical argument.
To answer some questions raised so far based on my limited (undergraduate) knowledge of biochemistry:
Enzymes are catalysts and shouldn't be consumed. They can denature and therefore will probably need to be replaced eventually. Enzyme stability is probably going to be the limiting factor here. It'll influence how often you'll need to replace the enzymes, how cheap they will be (the more stable they are, the easier they are to produce, purify and store) and how hot you can run the reactions. The guideline the reaction rate doubles for every 10 Kelvin increase in temperature (~18ºF ?). Given the amount of research effort there is into enzymes in general, I'm optimistic that enzyme stability can be increased. Hope that helps.
I'm curious as to why the article describes recycling water back into the fuel cell. It's already a water solution to begin with (so water will probably already be in excess) and diluting the mixture will only slow down the reaction rates...
Posted by: Philip T | May 27, 2007 at 11:02 AM
Two more thoughts:
1) In the context of biological processes, a thirteen step pathway is not long. For example, glycolysis, the first of three processes in our cells that convert glucose to ATP energy has already 10 enzymes in the main pathway.
2) This technology will benefit from the enzymatic research in cellulosic ethanol, allowing this technology to both receive starch-derived sugars and cellulose-derived sugars.
Posted by: Philip T | May 27, 2007 at 11:28 AM
Thank you Philip. Now that you “have seen the perspective” go for a Ph.D. in this. Every man and woman counts. I can see that you are probing. That and hard patient work is very much what it takes to make a difference.
I have discovered an error in my calculation though not big enough to chance the conclusions in any important way. I have now learned that the correct formula for translating kilograms of H2 and kWh is this: One kilo of hydrogen is 142MJ/(3.6MJ/kWh*100%) = 39,4 kWh. Source http://uplink.space.com/showflat.php?Cat=&Board=tech&Number=449378&page=0&view=collapsed&sb=9&o=0&fpart=3&vc=1. This is not the best source if somebody can give us a better one please submit one.
Anyway, the error made is that 4 kilo of hydrogen does not compare to 110 kWh of fuel cell output. Instead it should be 4kg*39,4 kWh*55% efficiency of fuel cell = 86,8 kWh. And not 110 kWh. Another error is that I refer to the Sequel when in fact it is the smaller GM Volt that uses 4 kilo of hydrogen to drive 300 miles. Sorry, I was rushing it through so I made errors.
Posted by: Henrik | May 27, 2007 at 12:01 PM
I wonder why the time issue could not be addressed by a storage system? Clearly the on-demand generation of H2 is ideal but could the H2 be pressurized as it is produced offline or overnight and stored in a 5 bar tank? The cost of the high pressure pump increases system cost but at $8. for 4 kg H2 a couple $ more for a storage system seems reasonable.
Posted by: gr | June 09, 2007 at 10:32 AM
two small suggestions for grokking where Zhang's work IS going..as there are few trained botanists any more, a self-tutorial on 'celluloses' might help wrap ones brain around this amazingly elegant stuff.. think '3-D' and 'packaging'.. at least 400+ glucoses in more/less the same space..a density thing..as in structural molecules..so now one suddenly has 400x those 12 hydrogens...that's where the yields are coming from. Second suggestion is to check back into this quickly evolving site every week or so..so far he's published everything but the specific protocols..including materials lists/ supplies/vendors..the reactions now are 'spontaneous' and 'extracellular'(no mutagens)..and folks can (temporarily) keep their ICE's( butanol) or switch to 'sugar'(hydrogen) at their economic leisure...only things left are the membrane materials.stay tuned..this guy really does rock..and did i mention that he's using scary terms like 'scalable' and 'mobile' as of late..hope this helps a little..TN
Posted by: tn | August 27, 2007 at 05:52 PM
two small suggestions for grokking where Zhang's work IS going..as there are few trained botanists any more, a self-tutorial on 'celluloses' might help wrap ones brain around this amazingly elegant stuff.. think '3-D' and 'packaging'.. at least 400+ glucoses in more/less the same space..a density thing..as in structural molecules..so now one suddenly has 400x those 12 hydrogens...that's where the yields are coming from. Second suggestion is to check back into this quickly evolving site every week or so..so far he's published everything but the specific protocols..including materials lists/ supplies/vendors..the reactions now are 'spontaneous' and 'extracellular'(no mutagens)..and folks can (temporarily) keep their ICE's( butanol) or switch to 'sugar'(hydrogen) at their economic leisure...only things left are the membrane materials.stay tuned..this guy really does rock..and did i mention that he's using scary terms like 'scalable' and 'mobile' as of late..hope this helps a little..TN
Posted by: tn | August 27, 2007 at 05:56 PM
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It looks very very good. Chavez, Fidel Castro and friends will be upset about this. USA know-How at its best.