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A Better Way to Make Hydrogen?

A Purdue researcher claims aluminum alloys could make fuel-cell vehicles practical.

By Kevin Bullis

Wednesday, September 05, 2007

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A new process for using aluminum alloys to generate hydrogen from water could make fuel-cell vehicles more practical, says Jerry Woodall, a professor of electrical and computer engineering at Purdue.

Gassing up: This aluminum alloy quickly pulls oxygen from water, in the process forming aluminum oxide and releasing hydrogen gas. The hydrogen could be used in place of gasoline in cars.
Credit: Jerry Woodall, Purdue University

Hydrogen fuel cells are attractive because they produce no harmful emissions, but hydrogen gas is hard to transport, and hydrogen vehicles have a limited range because it's difficult to store large amounts of hydrogen onboard. Many researchers are developing methods for storing more hydrogen, including packing it into carbon nanotubes or temporarily storing it in chemical compounds. Woodall's solution is to store hydrogen as water, splitting hydrogen from oxygen only when it's needed to power the vehicle.

Earlier this year, Woodall reported successfully generating significant amounts of hydrogen using a combination of aluminum and gallium. In those experiments, however, the alloy contained mostly gallium, which both limited the hydrogen-generating capacity of the material and kept costs high. At a nanotechnology conference on Friday, Woodall will present new work that shows that the process succeeds with an alloy containing 80 percent aluminum. This could make the system far more practical by reducing the amount of expensive gallium while increasing the amount of active material.

Woodall's process works because of aluminum's strong affinity for oxygen, which causes the metal to break water apart, forming aluminum oxide and releasing hydrogen. This basic chemical process is, of course, well known, but the problem has been that as soon as aluminum is exposed to air, it quickly forms a thin layer of aluminum oxide that seals off the bulk of the aluminum and prevents it from reacting with water. Woodall's insight, says Sunita Satyapal, who heads the Department of Energy's (DOE) hydrogen-storage program, is to use gallium to prevent this layer from completely sealing off the aluminum. Although the molecular mechanisms are still not understood, it's known that the gallium causes gaps in the oxide layer that allow the aluminum to react quickly with the oxygen in water, but not with the oxygen in air.

Woodall envisions a system in which aluminum pellets would be delivered to fueling stations where drivers would load about 50 kilograms of pellets and 20 kilograms of water into separate containers, with the two mixed as needed to generate hydrogen and aluminum oxide. (This would provide the equivalent of about 60 kilograms of gasoline, Woodall says.) The aluminum oxide can be recycled employing the same process used for aluminum cans, and the gallium can be easily separated from the aluminum oxide and used again.

But the electricity needed to recycle the aluminum could be a problem, since it would be a major source of pollution unless it comes from clean sources such as solar or wind. Also, Satyapal says that the energy efficiency of the process falls short of DOE goals.

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The DOE, together with oil and car companies, has set goals for the amount of hydrogen that should be stored onboard a vehicle, aiming to provide the same range as gasoline-powered cars without changing vehicle designs or reducing cargo and passenger space. Woodall says that he can meet the goals for cars and other light vehicles, in part by recycling water produced by the fuel cells. The DOE, however, estimates that Woodall's process would take up too much room because, among other reasons, recycling water will likely not be practical, Satyapal says.

Woodall is working with AlGalCo, a startup based in West Lafayette, IN, to commercialize the process. The company's initial products will be fuel-cell generators that run on hydrogen produced with a version of his aluminum alloy.

Comments

  • Aluminum-Galium Least Green
    Aluminum production produces as bad or worse carbon footprint than other hydrogen production methods. 

    The electrolytic production of aluminum liberates at least an equal amount of carbon dioxide to the aluminum produced.  In addition, huge amounts of electrical power are required due to aluminum's high electrical potential.

    A bigger payoff for the use of aluminum in transportation would be as a stucteral material to reduce the weight of vehicles.  Secondly, with aluminum's high electrical potential, it's use as a battery material might be more efficient.

    The only thing going for producing hydrogen this way is convienience, another non-green throw-away technology.
    Rate this comment: 12345

    nick47g
    09/05/2007
    Posts:18
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    • Re: Aluminum-Galium Least Green
      "The electrolytic production of aluminum liberates at least an equal amount of carbon dioxide to the aluminum produced."

      not if it is produced using green energy.

      Can you invent a jet engine that uses batteries?

      http://www.instructables.com/id/SODA-CAN-HYDROGEN-GENERATOR/
      Rate this comment: 12345

      Biotele
      12/24/2007
      Posts:8
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      3/5
  • 1% Good, and 99% Bad Idea
    You have created a system that has only one benefit using water. Why even waste the time knowing in advance Aluminum and Gallium are simply bad choices?

    Let alone using a fuel cell to compound the problems. They are still far from being commercially usable.

    There are better cheaper safer sources out there, take the blinders off....
    Rate this comment: 12345

    JonD
    09/05/2007
    Posts:4
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    3/5
  • Aluminum to the rescue
    This work is well documented and available from Technion in Israel.  The process is a little different but works well.  They are seeking funding and indeed may have the funding. I was a potential investor. Let us in! 
    Rate this comment: 12345

    Silacon
    09/05/2007
    Posts:46
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    2/5
  • Energy overestimate?
    I believe that Professor Woodall is substantially overestimating the useful energy he is getting out of this arrangement. According to my calculations, the energy content plus fuel cell efficiency in cars would make his hydrogen equivalent to about 10 kg of gasoline, not 50 kg.

    OK, chemistry students. It appears to me that the Al is more than enough to convert all the water to H2. (This assumes 100% efficiency in this process, which is probably not true either.)

    20 kg of H20 yields 2.22 e3 moles of atomic H. H has heat of combustion 147 kJ/g. 1 mole of H weighs 1 g.

    Gasoline has 47 J/kg heat of combustion and density 2.79 kg/gal.

    The H then has the equivalent energy of 6.8 kg or 2.4 gal of gasoline.

    A gasoline car can have efficiency of 30% (http://en.wikipedia.org/wiki/Fuel_efficiency) and a fuel-cell powered car about 45% (http://en.wikipedia.org/wiki/Fuel_cell).

    So we will give the fuel cell a 50% efficiency advantage (45% vs 30%) and boost the equivalent amount of gasoline from 6.8 kg to 10 kg.

    It would appear that Prof. Woodall is making some very unfavorable assumptions about gasoline to boost his approach. The same Wikipeda article with the efficiency of gasoline engines mentions that diesel engines have an efficiency of about 45%. Hybrid technology can help optimize gasoline or diesel efficiency.

    It does not seem attractive to carry around a total of 70 kg of Al-Ga alloy + H2O to replace 10 kg (3.6 gal) of gasoline.

    Maybe this is OK, however, if, say, you could get the equivalent of 50 mi/gal so that the equivalent of 3.6 gal of gas would carry you 180 miles. But let's be honest and accurate.

    Have I made any errors?


    Rate this comment: 12345

    tech80
    09/05/2007
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    • Re: Energy overestimate?
      Errors? Hydrogen exists as H2 (two atomic hydrogens per molecular hydrogen).  I didn't check the combustion heats of H or H2 but from prior research I checked gasoline vs. hydrogen's (H2) Joules of energy per the same charge of air for internal combustion engine cylinders; I found that gasoline had about 10-20% more energy available.  However one can increase Diesel efficiency using 30% water + Biodiesel emulsion (by ultrasonication) and further, by 5-10% H2 injected for combustion.  The very best brake specific fuel consumption at maximum economy is 0.260 lbs/hp/hour and at maximum power is 0.278 lbs per hp per hour (see http://people.bath.ac.uk/ccsshb/12cyl/ ) at over 50% thermal efficiency (>50% of the energy in the fuel in converted to motion).  I would question the fuel cell overall status and go for more H2 and less carbon based fuel combustion.
      Rate this comment: 12345

      H24meNu
      09/06/2007
      Posts:10
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    • Re: Energy overestimate?
      Errors? Hydrogen exists as H2 (two atomic hydrogens per molecular hydrogen).  I didn't check the combustion heats of H or H2 but from prior research I checked gasoline vs. hydrogen's (H2) Joules of energy per the same charge of air for internal combustion engine cylinders; I found that gasoline had about 10-20% more energy available.  However one can increase Diesel efficiency using 30% water + Biodiesel emulsion (by ultrasonication) and further, by 5-10% H2 injected for combustion.  The very best brake specific fuel consumption at maximum economy is 0.260 lbs/hp/hour and at maximum power is 0.278 lbs per hp per hour (see http://people.bath.ac.uk/ccsshb/12cyl/ ) at over 50% thermal efficiency (>50% of the energy in the fuel in converted to motion).  I would question the fuel cell overall status and go for more H2 and less carbon based fuel combustion.
      Rate this comment: 12345

      H24meNu
      09/06/2007
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      • Re: Energy overestimate?
        I took the 2H into account by the number of moles produced.

        Yes, diesel cars are more efficient than gasoline ones. That would only reduce the claimed advantage of H fuel cell cars.

        I got efficiencies from references quoted. If you have other sources, please specify.
        Rate this comment: 12345

        tech80
        09/06/2007
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    • Re: Energy overestimate?
      "The same Wikipeda article with the efficiency of gasoline engines mentions that diesel engines have an efficiency of about 45%"

      these diesels are large power plants that operate at high temperatures and low RPM, not in trucks or cars.

      "Modern gasoline engines have an average efficiency of about 25 to 30% when used to power an automobile."

      http://en.wikipedia.org/wiki/Engine_efficiency  
      Rate this comment: 12345

      Biotele
      12/24/2007
      Posts:8
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  • What about the oxygen balance?
    A really sustainable technology should not compete for oxygen with living creatures. One of the good features of electrolysis in water is that it releases O2 in the atmosphere thus making fuel cells potentially O2 neutral. But if you bind the oxygen to the aluminum you are no longer oxygen neutral: O2 goes lost into metal oxides which are waste. The article says you can recycle the alumina like cans, thus freeing up the O2 again at the cost of energy. The fact that such a little percentage of cans are actually recycled today makes me fear that we might not do a good job at recycling the Al waste from cars either.
    Rate this comment: 12345

    mscand
    09/05/2007
    Posts:1
  • Burning aluminum, the hard way.
    The process splits water into hydrogen and aluminum oxide, then burns the hydrogen to make water again. The net result of this elaborate dance is aluminum oxidized to aluminum oxide. The aluminum oxide is intended to be reduced back to aluminum by electrolysis. Thus, aluminum is being used here as the energy carrier, just as hydrogen is the carrier in the standard "hydrogen economy" models.

    In fact, the whole scheme is a Rube Goldberg variation of an aluminum battery: instead of simply recharging the battery, the battery is reduced to its components, the spent aluminum(III) is transported to a remote location to be reduced back to aluminum(0), and the aluminum(0) is transported back to the vehicle, where the "battery" is reassembled. Adding to the inefficiency is the intermediate, temporary splitting of water, an unnecessary detour on the way to releasing the energy of the aluminum(0).

    I can only speculate that funds for "hydrogen research" are what made it possible to concoct such a scheme. Research into aluminum batteries per se would be a more productive way to explore the feasibility of using aluminum as an energy carrier.

    Aluminum is a viable candidate for an energy carrier, and aluminum batteries have a higher power density than lithium batteries. There is, in fact, a fascinating proposal for the export of power from Iceland: ship-sized self-propelled aluminum batteries, charged in Iceland using cheap hydropower, then sailed to Europe or North America to be plugged into the grid:
    www.zpenergy.com/modules.php?name=News&file=article&sid=717
    (An electric vehicle, with real range!)
    Rate this comment: 12345

    jpdemers
    09/06/2007
    Posts:40
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    • Re: Burning aluminum, the hard way.
      Looks good but old.  There is no better way to make hydrogen unless big oil gets a large chunk of the change.  We've had a century of big oil religious warfaring idolatry.  Now things are warming up.  Will it change?  Will we?  It's like treading on ourselves being taxed without representation.
      Apparently the aluminum battery hasn't been perfected or it wasn't let into this country.  I refer to a rechargeable type battery.  The only way I know to replate/reduce aluminum ions to metal is by molten salts (the conventional Hall-Heroult process) where carbon dioxide is a byproduct or an expensive organometallic form of aluminum electroplated onto a cathode under non-aqueous electrolyte under inert gas.  So, apparently the aluminum battery isn't rechargeable.
      As long as cheap electricity exists in Iceland and they are going completely to an Hydrogen power economy why not electrolyze water under reverse proton exchange membrane (rPEM) conditions?  Electrons plus water make hydrogen plus oxygen.  Such cells exist to work under pressurized conditions to over several thousands of psi.  They electrolyze water directly into the pressurized storage vessels, no fuss, no muss.
      I still like the idea of gallium-catalyzed aluminum oxidative hydrogen production of water.  Just replace the computer nerd from the equation with formulation (Electro-)chemists (like me!).  Then again I'd rather have the nerd shot when push comes to shove.
      Rate this comment: 12345

      H24meNu
      09/06/2007
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      • Re: Burning aluminum, the hard way.
        You can do the gallium catalyzed reaction at home using $10 worth of liquid metal bought on Ebay

        http://www.instructables.com/id/SODA-CAN-HYDROGEN-GENERATOR/
        Rate this comment: 12345

        Biotele
        12/24/2007
        Posts:8
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  • Price of Aluminum
    The article talks about filling your tank with 50 kgs of aluminum.  The wholesale price of aluminum today is $2382/ton. So even if you could buy pellets at wholesale and assuming that millions of cars using the technology would not drive the price of aluminum through the roof, it would cost $131 to fill up your tank according to my calculation. 
    Rate this comment: 12345

    mwhitehe
    09/11/2007
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    • Re: Price of Aluminum
      Actually it is 70 kg of Al which would cost $184. This would be the equivalent of 3.6 gal of gas according to my notes above. This does seem rather expensive.

      Unfortunately, the kind of thinking and hype behind this kind of project goes almost unchallenged, and decisions with huge consequences are made based on very flawed reasoning. I believe that ramping up corn-based ethanol is an example of a process that is going to produce serious, adverse environmental consequences without saving any energy. But it is now conventional wisdom that this is a good idea.
      Rate this comment: 12345

      tech80
      09/14/2007
      Posts:3
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      • Re: Price of Aluminum
        If you go to your gas (aluminum?) station and pay x dollars for the aluminum and then get a credit for your spent aluminum for (x dollars – processing fee), then all you are paying is the processing fee and since we have free market the person that can remove the oxygen from the spent aluminum the most efficiently will be able to sell it.  The aluminum is just being used as a battery.  The energy comes from the aluminum processor, which could be nuclear, wind, solar, etc.
        Rate this comment: 12345

        CPL
        11/04/2007
        Posts:1
  • Stupid idea
    I did a back of the envelop calculation and the energy released with the burning of the aluminum that releases the hydrogen is about equal to the energy in the hydrogen. That in my book makes this a really stupid idea. Since I can figure this out with a very limited knowledge of chemistry I'd like to know why these researchers wasted their time on this work?
    Rate this comment: 12345

    sculptor
    09/20/2007
    Posts:8
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    • Re: Stupid idea
      If the energy in the H2 is about equal that from the Al-O2 reaction, that makes this a highly energy efficient storage medium, not a bad one. 
      Rate this comment: 12345

      mdcaldwell
      09/28/2007
      Posts:2
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      3/5
  • You Can Do a Similar Reaction at Home
    I was able to generate ample amounts of hydrogen from aluminum by modifying the Purdue experiment.

    I bought $10 worth liquid metal from Ebay and had a similar reaction with Aluminum.

    You can follow these instructions to make hydrogen quickly, easily and safely:

    www.instructables.com/id/SODA-CAN-HYDROGEN-GENERATOR/
    Rate this comment: 12345

    Biotele
    12/24/2007
    Posts:8
    Avg Rating:
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