Section 3: Hydrogen theory
From carbon to hydrogen energy
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Sources of hydrogen
Biophotolysis: natural hydrogen production

Towards the end of the 1800s, scientists discovered that algae and bacteria produced hydrogen. The bacteria produce it in the process of fermentation (digesting glucose) as they make heavy compounds that are poisonous to humans. In fact Clostridium butyricum, which makes 4.3 cubic feet of hydrogen per pound, is probably know for causing the disease known as botulism. Some produce cyanides.

In the United States, the National Science Foundation started soliciting awards for hydrogen production after the oil embargos of the 1970s.

Two sources of natural hydrogen production are microorganisms:
  • bacteria - by digesting its food
  • algae - photosynthesis (its breathing)
Bacteria hydrogen production
  • Bacteria even exist in the large intestines of humans to digest sugars, carbohydrates, starches, and fiber. The bacteria release hydrogen, methane, and carbon dioxide. We are interested in the ones that release hydrogen.



Algae hydrogen production
  • Tricking of Chlamydomonas

      Dr. Anastasios Melis, a biochemist at the University of California Berkeley figured out a way to trick green algae into producing hydrogen. Normally the single-celled Chlamydomonas in its photosynthesis is very similar to normal green land plant photosynthesis covered in the hydrogen science-background-section of this project (see above). When Chlamydomonas is deprived of sulphur and is still exposed to the sunlight, it switches to another metabolic state after about one day (20 or so hours). Rather than suffocate, they go into a hydrogenase mode.

      Hydrogenase is an enzyme that reverses the charge separation (see light cycle above) giving the hydrogen proton an electron to release hydrogen gas.

      In this process the alga recycles its proteins to get sulphur to survive. It produces hydrogen that is 87% pure. The rest is 12% nitrogen and 1% carbon dioxide. 1 milliliter of algae produces 3 milliliters of hydrogen per hour. After 150 hours the algae have consumed all of their proteins and must be allowed to photosynthesize with sulphur to charge up again. But they can be used over and over again. 1 pond can fuel 12 hydrogen cars for a week.

        REF: Melis, A.; Zhang, L.; Forestier, M.; Ghirardi, M.; and Seibert, M.; Sustained photobiological hydrogen gas production upon reversible inactivation of oxygen evolution in the green alga Chlamydomonas reinhardtii; Plant Physiology 122; pages 127-135.


  • High school study of natural hydrogen production


      Kristin Volle of Fairview High School in Boulder, Colorado, USA, received funding from the National Renewable Energy Laboratory to study cyanobacterium and algae using hydrogenase enzymes to see how it affected production of hydrogen to be used as an alternative fuel.

  • Team Canada science project - Secondary School

      Kiran Sah displayed a fuel cell in the 1997 national science fair. Sah used a bacteria, Proteus vulgaris, on the anode to generate hydrogen and a blue-green algae, Anabaena cylindrica on the cathode to produce oxygen. The bacteria ate sucrose. The cell used platinum electrodes. During the display, the cell was powering a fan.

      Iceland plans to be 100% free of fossil fuel use by 2040. The country is perfect for producing hydrogen from stagnant green algae pools (Chlamydomonas reinhardtii). See the details in the reference below.
Producing hydrogen from trash with bacteria
    Jonathan Woodward at ORNL's Chemical Technology Division discovered in 1996 how to make hydrogen from glucose with bacteria called "extremophiles." ORNL defines these kinds of bacteria as tough, because they thrive in hot places, such as deep beneath the earth. He discovered that these bacteria use an enzyme that converts glucose and gluconic acid into hydrogen. Woodward and his staff have been making hydrogen from biomass (sources of cellulose, such as old newspapers and grass clippings). The lab has succeeded in an amazing yield of 12 hydrogen molecules for each cellulose molecule. That's a 97% yield. They have been working with a hydrogenase produced by the bacteria, Pyrococcus furiosus. Hydrogenase enzymes, as mentioned earlier, accept electrons from HADPH (see photosynthesis discussion earlier) to release gaseous hydrogen.

    To summarize, the process that ORNL works with consists of the following steps:
    • Use the enzyme cellulase to add water to the cellulose.
    • Breaking down the cellulose to glucose.
    Currently, the disposal of wood and paper products produces carbon dioxide either in the biodegradation or incineration. Woodard alleges that the cellulose from waste newspapers in the United States for one year could produce enough hydrogen to meet the energy needs of 37 cities of population of 27,000 each.


    The history of fermentation of cellulose is very interesting. During World War II, the US Army discovered that cotton and paper products quickly rotted in the tropics. The Quartermaster Corps brought the bacteria home for study in the US Army Natick Research and Development Command laboratory (NARADCOM).

    NARADCOM developed the technology to develop an alternative source of food (glucose) from cellulose after the war with the hope of providing food to the world's starving. Work continued until 1979, when this intellectual property was transferred by executive order to the Department of Energy, shortly after it was established, and to universities. In the late 1970s the US federal government realized that these experiments with bacteria and enzymes could not only produce alternative food sources (sugars), but renewable, clean fuels, and other useful chemicals. At this time, the US government stopped funding research in this area at NARADCOM and funded it through the other federal agencies and labs through the Department of Energy.

    The army developed chemicals during that time to treat clothing that seals off the food supply from the bacteria, thus preventing the deterioration of uniforms in tropical areas.

      REF: DRCDL-101; Posture Report FY 79; US Army - Natick Research and Development Command; pages 113, 114, 115, and 163.

    The US produces 170 million tons of garbage a year, which is the same energy capability as 70 million tons of coal or 45,000,000 barrels of oil per day.

    US garbage consists of the following:
    • 41% paper
    • 18% yard waste (grass clippings, etc.)
    • 9% metal cans
    • 8% glass containers
    • 7% plastic

    Here's what happens: the decaying process produces hydrocarbons (CnHm). Once the hydrocarbons are captured, the hydrogen is produced either by spraying steam on it or by heating it, like so:

      Steam: CnHm + H2O + HEAT -> nCO + (n + ½m) x H2

      Heat alone: CnHm + HEAT -> nC + (½m x H2)

        Peavey, Michael A.; Fuel From Water - Energy Independence with Hydrogen; Louisville, KY; Merit, Inc.; pages 75 & 76.

Hydrogen as a byproduct of making agricultural fertilizer

    Dr. Paul Bishop of NC State in his working with USDA research has worked with bacteria living in the soil that "fix" nitrogen using various types of nitrogenases. Iron nitrogenases enable bacteria to produce twice the amount of hydrogen as those using molybdenum. These bacteria fix nitrogen and produce hydrogen, using solar energy.

More on iron hydrogenase
The bacteria in our intestines
    Humans give off carbon dioxide, hydrogen, and methane during the digestive process. Just like the other bacteria processes mentioned above, some processes give off carbon dioxide and methane, which are greenhouse gasses. However, if the methane is reformed, hydrogen is produced with carbon dioxide.
Reformation of natural gas (methane) Solar cells used in producing electricity
    Solar cells are only 10% efficient, yet a square grid of photovoltaic cells 75 miles by 75 miles in Arizona could produce 1,000,000 megawatts, which is the electrical need of the United States this year (2000).

    Solar power could manufacture hydrogen from water through electrolysis (see below). Solar Power Corporation in San Diego, California believes the costs per kilowatt of power in the future will be:
    • $0.0285 for solar power
    • $0.0285 for hydropower or natural gas
    • $0.0775 for nuclear power
    • $0.0993 for coal


      REF: Peavey, Michael A.; Fuel From Water; Louisville, KY, Merit, Inc.; 1998; page 45.

    The solar systems are not a joke. Sacramento (local government) in California USA generates power for 1,000 users. This interconnected mini-grid makes hundreds of homes mini power plants. They are committed to being competitive in the technology, hoping to capitalize on that as the world moves away from fossil fuels.


    The U.S. Department of Energy has as its strategic vision goals to develop and lower the costs of producing hydrogen from water and sunlight.
    BMBF has invested $129,000,000 in solar production of hydrogen in the past 10 years. They feel that the hydrogen economy will become dominant in the next 30 to 50 years. Deutsche Aerospace invested $89,000,000 in solar production of hydrogen, but stopped because of the costs. Apparently the solar production of hydrogen is not commercially viable yet (profit margin is not sufficient to operate).
    An alternative to photosynthesis is to use a magnifying glass to focus sunlight, where temperatures of 4,946°F break down water into hydrogen and oxygen. Roy McAlister, President of the American Hydrogen Association says that 12,000 square miles is enough area using this technology to meet the energy needs of the United States.

    The biggest problem with this is keeping the hydrogen and oxygen apart. One solution is using a centrifuge to separate the heavier oxygen from the lighter hydrogen. The problem is finding a porous membrane that would allow separation, because none is known that will sustain the high temperature.

      REF: Peavey, Michael A.; Fuel From Water; Louisville, KY, Merit, Inc.; 1998; page 57.
Wind Power
    Wind power, likewise could be used to produce hydrogen by electrolysis (see below).

    The wind power of the 48 United States is 400 billion kilowatts, the residential consumption in the US from 1970 to 1985 (a 15 year period). This is the total electrical consumption in the US for about 5 years.

      REF: Peavey, Michael A.; Fuel From Water; Louisville, KY, Merit, Inc.; 1998; page 49.


Canada - hydroelectric hydrogen
Petroleum Magazine reported in December 1999 that within the next two years, Canada could become an inexpensive source of hydrogen due to her cheap hydroelectric power capability.

The on-line story found in e-Petroleum tells about Hydro-Quebec's development of 40-foot hydrogen containers for shipping of hydrogen overseas.

The article notes how Germany, France, and Belgium already have hydrogen pipelines. In fact Germany has two hydrogen distribution centers. Germany has had pipelines for fifty years.


Other sources for this page
REF: DOE Hydrogen Research Program
http://www.eren.doe.gov/hydrogen/research.html#production

REF: Morgan, Daniel; Congressional Research Service Report for Congress - Hydrogen: Technology and Policy;April 28, 1995.
http://www.cnie.org/nle/eng-4.html




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