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Hydrogen Fuel from Formic Acid

A simple new process generates hydrogen for fuel cells.

By Prachi Patel

Thursday, May 15, 2008

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New research shows that formic acid could be used as a safe, easy-to-transport source of hydrogen for fuel cells. Matthias Beller and his colleagues at the Leibniz Institute of Catalysis, in Rostock, Germany, have found a way to convert formic acid, a common preservative and antibacterial agent, into hydrogen gas at low temperatures.

Hydrogen on demand: A generating unit extracts hydrogen from formic acid and feeds it to a polymer electrolyte membrane fuel cell that runs a laptop.
Credit: Wiley-VCH

While hydrogen produced using this method might not find use in fuel-cell vehicles anytime soon, the researchers say that the process could produce sufficient quantities for micro fuel cells that power portable electronic devices, such as cell phones and laptops.

The challenge of producing, storing, and transporting hydrogen affordably has kept fuel cells from becoming popular. Instead of transporting hydrogen gas, it is more practical to have a hydrogen-containing material that can be broken down to generate the gas where it is needed. Currently, methane and methanol top the list of hydrogen sources for fuel-cell vehicles. They are typically broken down via steam reforming, which requires temperatures of more than 200 °C and a reforming unit.

Processes that work at cooler temperatures would not need a reformer or much energy, and therefore could be more suitable for producing hydrogen for smaller fuel cells that power portable electronic devices. The new process, which Beller and his colleagues outline in Angewandte Chemie, works at temperatures of 26 to 40 °C. The researchers mix formic acid with amines and expose the mixture to a ruthenium-based catalyst, which breaks down the acid into hydrogen and carbon dioxide.

"The advantage of formic acid is [that] it's a liquid . . . and is relatively easily handled," Beller says. While the pure acid is corrosive, the mixture of the acid with amines is benign, he says.

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Formic acid can also be used directly in a fuel cell. That might be easier because it saves the extra step of first converting it into hydrogen. Tekion, based in Burnaby, Canada, is working with Germany-based chemical giant BASF, the largest producer of formic acid, to commercialize a fuel cell that uses formic acid directly. Tekion, which does not have a product on the market yet, claims that its formic-acid fuel cells are smaller and less complex than direct methanol fuel cells. But direct formic-acid fuel cells have the same drawback that makes methanol fuel cells expensive: both technologies are less efficient than hydrogen fuel cells.

Beller points out that using formic acid to make hydrogen also has drawbacks. Compared with methane and methanol, formic acid has much less hydrogen. If you use all the hydrogen in a kilogram of methanol, you get 4.19 kilowatt-hours of energy, while the hydrogen in a kilogram of formic acid gives 1.45 kilowatt-hours.

Comments

  • Not too useful
    Generates one CO2 for every H2, which wipes out the primary reason one would use a hydrogen fuel cell.  You're better off using a fuel cell that burns methanol.
    Rate this comment: 12345

    jpdemers
    05/15/2008
    Posts:40
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    • Re: Not too useful
      That's a good point about CO2, but realize that most of the methods for producing the hydrogen have a CO2 load of their own.  We can't consider only the emissions from the vehicle.  Unfortunately, few discussions of these technologies study the overall energy and waste balances.

      What is the fate of the amine?  That's a disposal issue and a drain on efficiency unless it can be recycled.

      I'm not sure if we'll see enough formic acid gereation to fuel vehicles, etc.  However, if the CO from a syngas stream is converted to formic acid, this could be a good way to make use of that energy on its way to CO2.
      Rate this comment: 12345

      fkearney
      05/15/2008
      Posts:4
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      4/5
      • Re: Not too useful
        There is that Aluminium-Gallium pellets + water and

        Out comes H2 AlO2 and Gallium works as a catalyst and does not react.

        AlO2  and Gallium can be sored and recycled. AlO2 is restured to Al the same Gallium is added back and O is released.

        Basically energy goes from refurb. plant to car no side effects if the energy is green.

        http://www.autobloggreen.com/2007/08/29/purdue-on-demand-hydrogen-from-aluminum-gallium-and-water/
        Rate this comment: 12345

        nuubik
        05/15/2008
        Posts:2
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        1/5
    • Re: Not too useful
      "Generates one CO2 for every H2, which wipes out the primary reason one would use a hydrogen fuel cell.  You're better off using a fuel cell that burns methanol."

      Uhh -- "burning methanol" is going to release CO2 as well.  Nice try.

      In any event, if we're talking about using this for small devices only, the amount of CO2 produced is going to be completely negligible compared to other large producers.
      Rate this comment: 12345

      johnnybravo4...
      05/15/2008
      Posts:2
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      • Re: Not too useful
        Yes, but you get much more energy from the methanol, using much less hardware.  I probably should have said that you "might as well" use a methanol fuel cell.  In a fuel cell/ICE hybrid vehicle, the methanol can also fuel an internal combustion engine when peak power is needed.

        Methanol can come from coal or syngas, which is a plus if we're tying to cut oil imports.  (I don't know where formic acid comes from, but I suspect it can be traced to syngas.)  Neither fuel "solves" the CO2 problem, but the efficiency of hybrids ought to cut emissions substantially.
        Rate this comment: 12345

        jpdemers
        05/16/2008
        Posts:40
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  • Units!
    An absolute quantity (energy) was expressed in terms of a rate (power) here:

    "Beller points out that using formic acid to make hydrogen also has drawbacks. Compared with methane and methanol, formic acid has much less hydrogen. If you use all the hydrogen in a kilogram of methanol, you get 4.19 kilowatts of power, while the hydrogen in formic acid gives 1.45 kilowatts."

    I'm guessing you meant kWh.
    Rate this comment: 12345

    dansteingart
    05/15/2008
    Posts:2
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    • Re: Units!
      Yeah -- and that would be kWh of ENERGY, not power.  If you are a science/technology journalist, please take the time to get your units of power/energy correct.  I see this mistake made all the time and it drives me nuts.
      Rate this comment: 12345

      johnnybravo4...
      05/15/2008
      Posts:2
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      • Re: Units!
        Me too! Good point to make. It's like walking around with your zipper down. You might say something smart, but who's listening when your zipper's down?
        Rate this comment: 12345

        MakeSense
        05/16/2008
        Posts:93
        Avg Rating:
        3/5
  • Ruthenium?
    Small wonder that they don't see this working for FCVs - Ruthenium is one of the rarest elements on Earth and very expensive.
    Rate this comment: 12345

    MakeSense
    05/16/2008
    Posts:93
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  • Ruthenium ~ 1/3 price of gold
    Today, Ruthenium runs ~270USD per troy ounce.
    Gold at ~900USD per troy ounce.
    Rate this comment: 12345

    nekote
    05/16/2008
    Posts:138
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    • Re: Ruthenium ~ 1/3 price of gold
      Ruthenium is very rare, but it is also usually in low demand. When new demands occur, the price reacts quickly. The average price of Ru has been coming back from a recent high of $870/oz. Average price for the past month is $385, while today's bid price on the spot market is $270 ($340 Ask). The price soared when demand for its use in hard drives doubled and there was speculation of a new use in dye-sensitized solar cells.
      Rate this comment: 12345

      MakeSense
      05/16/2008
      Posts:93
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  • Magnesium Oxidization
    Since every one seems to be stating better ideas I though that I would throw out the oxidizing magnesium idea.

    You take finely ground magnesium powder and mix it with water. The Oxygen in the water binds with the magnesium releasing the H2 “enter fuel cell”. When the magnesium is all converted into magnesium oxide you return it to the store and get some new stuff. Much like LP tank exchange. At this point a laser can be used to de-oxidize the magnesium. This method is as clean as the energy source used to power the laser. A kitten fired steam generator for all I care.
    Rate this comment: 12345

    zig158
    05/17/2008
    Posts:64
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    • Re: Magnesium Oxidization
      Comparable to the aluminum-gallium alloy mentioned above.  These are, essentially, very elaborate versions of batteries: electrical energy is stored as chemical potential energy in a reactive zero-valent metal, and the energy is released in a chemical reaction and converted back to electricity.  The disadvantages are in the complexity of the hardware, and the fact that "recharging" involves lugging the metal oxides back to a reprocessing plant.  The big advantage is in the high energy density of pure, light metals like Ga, Mg or Al.  I'm not aware of any working energy storage system based on boron, but in theory it should be the ideal element for such an approach.
      Rate this comment: 12345

      jpdemers
      06/19/2008
      Posts:40
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      • Re: Magnesium Oxidization
        Magnesium metal is Mg(0), which is readily oxidized to Mg(II) by giving up two electrons. In HCl, there is lots of H+ available, and this is readily reduced by the electrons provided by Mg(0), forming H2 gas as a result. The Mg(II) is left with two Cl- ions, making MgCl2, which is dissolved in solution. The end observation is that the ribbon dissolves with much fuss and bubbling, and maybe even a flame due to the exothermic nature of the redox reaction.
        Is't correct?
        Read my blog too
        http://hidrogen-fuel.blogspot.com/
        Rate this comment: 12345

        leeboon
        09/11/2009
        Posts:1

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