BioHydrogen pp 19-30 | Cite as

The Technology of Biohydrogen

  • John R. Benemann


Hydrogen produced by microalgae and bacteria is biohydrogen. There are currently no practical biohydrogen production processes. However, several concepts have promise for near- to long-term process development.

The conversion of CO to H2, the microbial shift reaction, operates at ambient temperatures in a single-stage process, compared to the two-stage, high-temperature, chemical catalyst processes currently used. Process development is just beginning, but this concept appears promising for near- to mid-term practical applications.

H2 yields from dark fermentations of organic wastes are typically less than 20% (on a heating value basis) compared to CH4 fermentations. Higher yields might be possible at elevated temperatures, with nutrient limitations, and through metabolic engineering of the bacteria. Photofermentations, the conversion of organic substrates to H2 by nitrogen-fixing photosynthetic bacteria, achieve high H2 yields, but low solar conversion efficiencies. The inefficiency of the nitrogenase enzyme suggests that biohydrogen processes must be based on reversible hydrogenases. Even then, dark fermentations of wastes to H2 would be preferable to light-driven processes, in part due to the high cost of photobioreactors. The production of H2 from organic wastes is of mid-term potential but limited by resources and competition from other processes.

Larger-scale biohydrogen production requires biophotolysis processes—H2 production from water and sunlight. Photobioreactor costs and solar conversion efficiencies are main challenges in the development of practical processes. Direct biophotolysis couples the reductant produced by photosynthesis directly to hydrogenase, producing O2 and H2 simultaneously, while indirect processes separate these basically incompatible reactions through intermediate CO2 fixation. Direct, but not indirect, biophotolysis processes require hydrogenase activity in the presence of high O2 levels, something not known to occur. Hybrid indirect processes using both algae and photosynthetic bacteria have been proposed and even tested outdoors, but are complex and inefficient. The simplest indirect process would use the same algal cells for both CO2 fixation/O2 evolution and H2 production, at separate times or even in different reactors. The H2 reactions would take place both in the dark and light. Light-driven H2 evolution requires suppression of the O2 evolution process. Biophotolysis process must achieve the highest possible solar conversion efficiencies, which will require development of algal strains with reduced light-harvesting (“antenna”) pigment content.

A preliminary economic analysis of a large-scale, two-stage, indirect process suggests that biohydrogen costs close to $10/GJ, lower than for PV-electrolysis processes. This assumed use of very large, low-cost (<$10/m2) open ponds for the first (CO2 fixation) stage operating at a 10% solar conversion efficiency, and much smaller (approximately 10% of the total area) photobioreactors (<$150/m2) for the second H2 production stage. Single-stage biophotolysis systems require low-cost (<$50/m2) photobioreactors, but may be suitable for much smaller-scale (perhaps even roof-top) applications.

The development of practical biohydrogen production systems will require focusing on the more promising alternatives and critical R&D issues and could be accelerated through international basic and applied R&D collaborations.


Hydrogen Production Photosynthetic Bacterium International Energy Agency Open Pond Dark Fermentation 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Andrews, G.F., and Noah, K.S., 1995, Design of gas-treatment bioreactors, Biotech. Prog., 11:498–509.CrossRefGoogle Scholar
  2. Augenstein, D.C., Benemann, J.R., and Hughes, E., 1994, Electricity from biogas, in Proceedings of Second Interamerican Biomass Conference, Reno, Nevada, October.Google Scholar
  3. Bard, A.J., and Fox, M.A., 1995, Artificial photosynthesis: solar splitting of water to hydrogen and oxygen, Accounts Chem. Res., 28:141–145.CrossRefGoogle Scholar
  4. Benemann, J.R., 1973, A model system for nitrogen fixation and hydrogen evolution by non-heterocystous blue-green algae, Fed. Proceed., 32:632.Google Scholar
  5. Benemann, J.R., 1977, Hydrogen and methane production through microbial photosynthesis, in Living Systems as Energy Converters, Buvet, R. et al. (eds.), Elsevier/North-Holland Press, Amsterdam, pp. 285–298.Google Scholar
  6. Benemann, J.R., 1990, The future of microalgae biotechnology, in Algal Biotechnology, Cresswell, R.C. et al. (eds.), Longman, London, pp. 317–337.Google Scholar
  7. Benemann, J.R., 1993, Utilization of carbon dioxide from fossil fuel-burning power plants with biological systems, Energy Cons. Mgmt., 34:999–1004.CrossRefGoogle Scholar
  8. Benemann, J.R., 1994, Feasibility analysis of photobiological hydrogen production, in Hydrogen Energy Progress X, Proceedings of the 10th World Hydrogen Energy Conference, Block, D.L., and Versiroglu, T.N. (eds.), Cocoa Beach, Florida, United States, June 20–24, 1994, pp. 931–940.Google Scholar
  9. Benemann, J.R., 1996, Hydrogen biotechnology: progress and prospects, Nature Biotechnology, 14:1101–1103.PubMedCrossRefGoogle Scholar
  10. Benemann, J.R., 1998, Processes analysis and economics of biophotolysis: a preliminary assessment, Report to the International Energy Agency, Subtask B, Annex 10, Photoproduction of Hydrogen Program, in press.Google Scholar
  11. Benemann, J.R., Berenson, J.A., Kaplan, N.O., and Kamen, M.D., 1973, Hydrogen evolution by a chloroplast-ferredoxin-hydrogenase system, in Proceedings of the National Academy of Sciences (USA), 70:2317–2320.CrossRefGoogle Scholar
  12. Benemann, J.R., Miyamoto, K., and Hallenbeck, P.C., 1980, Bioengineering aspects of biophotolysis, Enzyme and Microbial Technology, 2:103–111.CrossRefGoogle Scholar
  13. Benemann, J.R., and Weare, N.M., 1974, Hydrogen evolution by nitrogen-fixing Anabaena cylindrica cultures, Science, 184:1917–175.CrossRefGoogle Scholar
  14. Benemann, J.R., and Zaborsky, O.R., 1996, Biohydrogen: market potential, in Proceedings of the Annual Meeting of the National Hydrogen Association, Washington D.C., April 1996.Google Scholar
  15. Berenson, J.A., and Benemann, J.R., 1977, Immobilization of hydrogenase and ferrodoxins on glass beads, FEBS Letters, 76:105–107.PubMedCrossRefGoogle Scholar
  16. Block, D.L., and Melody, I., 1992, Efficiency and cost goals for photoenhanced hydrogen production processes, Int. J. Hydrogen Energy, 17:853–861.CrossRefGoogle Scholar
  17. Bolton, J.R., 1996, Solar photoproduction of hydrogen, Report to the International Energy Agency, under Agreement on the Production and Utilization of Hydrogen, IEA/H2/TR-96, September 1996.Google Scholar
  18. Copeland, R.J., 1991, Low cost hydrogen systems, presented at U.S. Department of Energy/Solar Energy Research Institute Hydrogen Program Review, Washington, D.C., January 23–24.Google Scholar
  19. Gaffron, H., and Rubin, J., 1942, Fermentative and photochemical production of hydrogen in algae, J. Gen. Physiol., 26:219–240.CrossRefGoogle Scholar
  20. Gest, H., and Kamen, M.J., 1949, Photoproduction of molecular hydrogen by Rhodospirillum rubrum, Science, 109:558–559.CrossRefPubMedGoogle Scholar
  21. Ghirardi, M.L., Togasaki, R.K., and Seibert, M., 1997, Oxygen sensitivity of algal hydrogen production, App. Biochem. Biotech., 63:141–151.Google Scholar
  22. Gibbs, M., Hollaender, A., Kok, B., Krampitz, L.O., and San Pietro, A., 1973, in Proceedings of the Workshop on Bio-Solar Hydrogen Conversion, September 5–6, Bethesda Maryland, United States.Google Scholar
  23. Gibbs, M., Gfeller, R.P., and Chen, C., 1986, Fermentative metabolism of Chalmydomonas reinhardii, Plant Physiol., 82:160–166.PubMedGoogle Scholar
  24. Grasso, D., Strevett, K., Fisher, R., 1995, Uncoupling mass transfer limitations of gaseous substrates in microbial systems, Chemical Eng. J., 59:195–204.Google Scholar
  25. Greenbaum, E., 1980, Simultaneous photoproduction of hydrogen and oxygen by photosynthesis, Biotech. Bioeng. Symp., 10:1–13.Google Scholar
  26. Greenbaum, E., 1988, Energetic efficiency of hydrogen photoevolution by algal water splitting, Biophys. J., 54:365–368.PubMedGoogle Scholar
  27. Hallenbeck, P.C., and Benemann, J.R., 1979, Hydrogen from algae, in Photosynthesis in Relation to Model Systems, Barber, J. (ed.), Elsevier/North-Holland Biomedical Press.Google Scholar
  28. Happe, R.P, Roseboom, W., Pierik, A.J. and Bagley, K.A., 1997, Biological activation of hydrogen, Nature, 385:126.PubMedCrossRefGoogle Scholar
  29. Healy, F.P., 1970, The mechanism of hydrogen evolution by Chlamydomonas moewusii, Plant Physiol., 45:153–159.CrossRefGoogle Scholar
  30. Heijnen, S.J., 1995, Thermodynamics of microbial growth and its implications for process design, Trends in Biotechnology, 12:483–492.CrossRefGoogle Scholar
  31. Hollaender, A., Monty, K.J., Paerlstein, R.M., Schidt-Bleek, F., Snyder, W.T., and Volkin, E., 1972, An inquiry into biological energy conversion, Workshop Report (October 12–14, 1972), Gatlinburg, Tennessee NSF-RANN, University of Knoxville, December 1972.Google Scholar
  32. Jackson, D.D., and Ellms, J.W., 1986, On odors and tastes of surface waters with special reference to Anabaena, a microscopial organsim found in certain water supplies of Massachusetts, Report to the Massachusetts State Board Health, pp. 410–420.Google Scholar
  33. Kerby, R.L., Hong, S.S., Ensign, S.A., Copoc, L.J., Ludden, P.W., and Roberts, G.P., 1992, Genetic and physiologiclal characterization of the Rhodospirillum rubrum carbon monoxide dehydrogenase system, J. Bactriol., 174:5284–5294.Google Scholar
  34. Klasson, K.T., Gupta, A., Claussen, E.C., and Gaddy, J.L., 1993, Evaluation of mass-transfer and kinetic parameters for Rhodospirillum rubrum in a continuous stirred tank reactor, App. Biochem. Biotech., 39/40:549–557.Google Scholar
  35. Kok, B., 1973, Photosynthesis, in Proceedings of the Workshop on Bio-Solar Hydrogen Conversion, Gibbs, M. et al. (eds.), September 5–6, Bethesda, Maryland, pp. 22–30.Google Scholar
  36. Krampitz, L.O., 1977, Potentials of hydrogen production through biophotolysis, in Symposium Papers: Clean Fuels from Biomass and Wastes, January 25–28, Orlando, Florida, Institute of Gas Technology, Chicago, Illinois, pp. 141–151.Google Scholar
  37. Lien, S. and San Pietro, A., 1975, An inquiry into biophotolysis of water to produce hydrogen, Report to the National Science Foundation.Google Scholar
  38. Mann, M., 1996, Technical and economic assessment of renewable hydrogen production, presented at the Annual Review of the U.S. Department of Energy Hydrogen Program, Miami, Florida, April 29–May 3.Google Scholar
  39. Markov, S.A., Weaver, R., and Seibert, M., 1996, Hydrogen production using microorganisms in hollow-fiber bioreactors, in Proceedings of Hydrogen 96, Suttgart, Germany.Google Scholar
  40. McTavish, H., Sayavedra-Soto, L.A., and Arp, D.J., 1995, Substitution of Azotobacter vinelandii hydrogenase small subunit cysteins by serines can create insensitivity to inhibition by O2 and preferentially damages H2 oxidation over H2 evolution, J. Bact., 177:3960–3964.PubMedGoogle Scholar
  41. Melis, A., 1991, Dynamics of photosynthetic membrane composition and function, Biochim Biophys. Acta (Reviews on Bioenergetics), 1058:87–106.CrossRefGoogle Scholar
  42. Mitsui, A., 1974, The utilization of solar energy for hydrogen production by cell free system of photosynthetic organisms, in Hydrogen Energy, Part A, Veziroglu, T.N. (ed.), pp. 309–316.Google Scholar
  43. Mitsui, A., 1992, Biological hydrogen photoproduction (task B), in Proceedings of 1992 U.S. Department of Energy/National Renewable Energy Laboratory Hydrogen Program Review, May 6–7, Honolulu, Hawaii, NREL/CP-450-4972, pp. 129–156.Google Scholar
  44. Miyamoto, K., 1994, Hydrogen production by photosynthetic bacteria and microalgae, in Recombinant Microbes for Industrial and Agricultural Applications, Murooka, Y., and Imanaka, T. (eds.), Marcel Dekker, New York, pp. 771–786.Google Scholar
  45. Myers, J., 1957, Algal culture, Encyclopedia of Chemical Technology, Interscience, New York, pp. 649–680.Google Scholar
  46. Myers, J., 1977, Bioengineering Approaches and Constraints, in Biological Solar Energy Conversion, Mitsui, A. et al. (eds.), Academic Press, New York, pp. 449–454.Google Scholar
  47. Pauss, A., Andre, G., Perrier, M., and Guiot, S.R., 1990, Liquid-to-gas mass transfer in anaerobic processes: inevitable transfer limitations of methane and hydrogen in the biomethanation processes, App. Env. Microbiol., 56:1636–1644.Google Scholar
  48. Sasikala, K., Ramana, C.V., Rao, P.R., and Kovacs, K.L., 1993, Anoxygenic phototrophic bacteria: physiology and advances in hydrogen technology, Adv. Appl. Microbiol., 38:211–295.CrossRefGoogle Scholar
  49. Schink, B., 1997, Energetics of syntrophic cooperation in methanogenic degradation, Microbiol. and Molecular Biol. Reviews, 61:262–280.Google Scholar
  50. Spruit, C.J.P., 1958, Simultaneous photoproduction of hydrogen and oxygen by Chlorella, Mededel. Landbouwhogeschool Wageningen, 58:1–17.Google Scholar
  51. Thauer, R., 1976, Limitation of microbial hydrogen formation via fermentation, in Microbial Energy Conversion, Schlegel, H.G., and Barnea, J. (eds.), Erich Goltze, Gottingen, pp. 201–294.Google Scholar
  52. Turpin, D.H., Layzell, D.B., and Elrifi, I.R., 1985, Modeling the carbon economy of Anabaena flos-aquae, Plant Physiol., 78:746–752.PubMedGoogle Scholar
  53. Ueno, Y., Morimoto, M., Ootsuka, S., Kawai, T., and Satou, S., 1995, Process for the production of hydrogen by microorganisms and for wastewater treatment, U.S. Patent, 5,464,539 (November 7, 1995).Google Scholar
  54. Weare, N.M., and Benemann, J.R., 1974, Nitrogenase activity and photosynthesis by Plectonema boryanum 594, J. Bacteriol., 119:258–268.PubMedGoogle Scholar
  55. Weaver, P.F., Lien, S., and Seibert, M., 1980, Photobiological production of hydrogen, Solar Energy, 24:3–45.CrossRefGoogle Scholar
  56. Weaver, P., Maness, P.C., Fank, A., Li, S., and Toon, S., 1995, Biological water-gas shift activity, in Proceedings of the Annual Review Meeting of the U.S. Department of Energy Office of Utility Technologies Hydrogen Program Review, Miami, Florida.Google Scholar
  57. Weetall, H.H., 1979, Biophotolysis of Water, U.S. Patent 4,148,690.Google Scholar
  58. Weissman, J.C., and Benemann, J.R., 1977, Hydrogen production by nitrogen-fixing cultures of Anabaena cylindrica, Appl. Env. Microbiol., 33:123–131.Google Scholar
  59. Weissman, J.C., Goebel, R.P., and Benemann, J.R., 1988, Photobioreactor design: comparison of open ponds and tubular reactors, Bioeng. Biotech., 31:336–344.CrossRefGoogle Scholar
  60. Woodward, J., Mattingly, S.M., Danson, M., Hough, D., Ward, N., and Adams, M., 1996, In vitro hydrogen production by glucose dehydrogenase and gydrogenase, Nature Biotechnology.Google Scholar
  61. Zurrer, H., and Bachofen, R., 1979, Hydrogen production by the photosynthetic bacterium Rhodospirillum rubrum, App. Envron. Microbiol., 37:789–793.Google Scholar

Copyright information

© Plenum Press, New York 1998

Authors and Affiliations

  • John R. Benemann
    • 1
  1. 1.Walnut Creek

Personalised recommendations