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Biohydrogen as a renewable energy resource—Prospects and potentials
Shireen Meher Kotay, Debabrata Das ∗
Department of Biotechnology, Indian Institute of Technology, Kharagpur 721302, INDIA Received 18 June 2007; accepted 9 July 2007 Available online 4 September 2007
Abstract Biohydrogen holds the promise for a substantial contribution to the future renewable energy demands. It seems particularly suitable for relatively small-scale, decentralized systems, integrated with agricultural and industrial activities or waste processing facilities. Biohydrogen is considered as an important key to a sustainable world power supply and is currently being seen as the versatile fuel of the future, with the potential to replace fossil fuels. It has the key prospective to become the ideal means among the range of renewable H2 production technologies presently existing. This review attempts to delineate the prospects and potentials of biohydrogen as renewable energy resource. 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Biohydrogen; Renewable energy; Waste-to-energy; Bioremediation
1. Introduction Hydrogen holds the promise as a dream fuel of the future with many social, economic and environmental beneﬁts to its credit. It has the long-term potential to reduce the dependence on foreign oil and lower the carbon and criteria emissions from the transportation sector. Only in the last decade that the idea of a post-fossil fuel hydrogen-based economy started to gain mainstream interest. Molecular H2 has the highest energy content per unit weight among the known gaseous fuels (143 GJ ton−1 )  and is the only carbon-free fuel which ultimately oxidizes to water as a combustion product. Therefore burning hydrogen not only has the potential to meet a wide variety of end use applications but also does not contribute to greenhouse emission, acid rain or ozone depletion. The use of hydrogen will contribute to signiﬁcant reduction of these energy-linked environmental impacts. H2 can be used either as the fuel for direct combustion in an internal combustion engine or as the fuel for a fuel cell. The largest users of H2 , however, are the fertilizer and petroleum industries with, respectively, 50% and 37%. Sales of hydrogen have increased by 6% annually in the last ﬁve years, which is
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closely related to the increased use of hydrogen in reﬁneries as a result of stricter standards for fuel quality . The Global Hydrogen Vision envisions hydrogen as a ﬂexible, safe, affordable, domestic energy resource to be used in all sectors of the economy and all regions of the world. Hydrogen will become world’s “clean energy choice”, joining electricity as a primary energy carrier and providing the foundation for a globally sustainable energy system . It has a wide variety of applications, including fuel for automobiles; distributed and central electricity and thermal energy generation (Fig. 1). 2. Barriers for biohydrogen production Technical challenges in achieving a hydrogen economy include lowering the cost of hydrogen production, delivery, storage, conversion, and end use applications. Although hydrogen is the most abundant element in the universe, it must be produced from other hydrogen-containing compounds such as fossil fuels, biomass, or water. Each method of production requires a source of energy, i.e., thermal (heat), electrolytic (electricity), or photolytic (light) energy (Table 1). In other words they are highly energy intensive and not always environmentally benign . Moreover, there is a growing concern arising out of the projection of fossil fuel shortfall towards the middle of twentyﬁrst century. Under this perspective, biological hydrogen
0360-3199/$ - see front matter 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2007.07.031
unlike their chemical or electrochemical counterparts are catalyzed by microorganisms in an aqueous environment at ambient temperature and pressure. industrial wastewater and sludge in a usable form. thus avoiding energy expenditure and costs for transport. and durability Genetic manipulation of established bacteria Greater understanding of the enzyme regulation and expression Mutagenic studies Low H2 partial pressure fermentation Renewable biomass as feedstock Co-digestion/use of microbial consortia which can increase the yield Development of industrially viable strain(s)/consortia Hybrid system (photo + dark fermentation) Link fermentation to a second process that makes both economically possible Application and utilization of fermentation tools such as continuous culture Development of low-cost stream sterilization technology/process that can bypass sterilization Incorporation of process engineering concepts to develop a suitable reactor for the deﬁned strain/process Flat panel or hollow tube reactor can be employed Reverse electron transport to drive H2 production past barrier Selection absorption of CO2 /H2 S Basic studies on H2 storage Fermentative Feedstock Strain Process Engineering Reactor Thermodynamic Hydrogen Lack of kinetics/appropriate reactor design for H2 production Light intensity in case of photo-bioreactor Thermodynamic barrier NAD(P)H → H2 (+4. On the contrary in biological processes microorganisms can recover and concentrate the energy from high water content organic resources such as. in a sense. Chronology of fuel usage by mankind. biohydrogen production. D. 1. Furthermore.62 kJ/mol) H2 puriﬁcation/separation Storage production assumes paramount importance as an alternative and renewable energy resource. Table 1 Scientiﬁc and technical barriers for biohydrogen production Type of barrier Basic science Organism Barrier Putative solution Bacteria do not produce more than 4 mol H2 /mol glucose naturally Hydrogenase overexpression not stable O2 sensitivity H2 feed back inhibition High cost of suitable feedstock (glucose) Low yield using renewable biomass Lack of industrial-suitable strain Commercially feasible product yield Incomplete substrate utilization Sustainable process Sterilization Enzyme (hydrogenase) Isolate more novel microbes and combinational screen for H2 production rates yields. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 259 Fig. is an entropy reducing . it is somewhat difﬁcult to obtain their combustion enthalpy by mechanical means . as the organic substrates dissolved and diluted in wastewater are in a high entropy state.S. Biological processes. these techniques are well suited for decentralized energy production in small-scale installations in locations where biomass or wastes are available. From thermodynamic perspective. Thus. Meher Kotay.
Improving reactor design and optimizing the operating parameters such as pH. TiO2 is illuminated as the catalyst. One is light dependent and the other is light independent process. particularly in Germany. Energy from water-containing biomass such as sewage sludge. This H2 O splitting can be achieved either in photochemical cells where. The processes of biological hydrogen production can be broadly classiﬁed into two distinct groups. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 process. there are many logistical and market challenges that must also be overcome before a hydrogen economy can become a reality: biomass + O2 → CO + H2 + CO2 + energy. but might also cause signiﬁcant climate changes globally. and relatively long-term (> 10 yr) basic and applied R&D. hydraulic retention time. such as bioreactor design and operating parameters. the quest for ideal microbe(s) for microbial H2 production has thrust the researchers to screen various sources. and has solved the problem of converting hydrogen to electricity by means of the biocatalyst. Independent of the source of hydrogen. Microbial H2 production is an attractive process for supplying a signiﬁcant share of the H2 required for the near future. and Clostridium are reported (Table 3) to produce hydrogen through dark fermentation . This enzyme regulates the hydrogen-metabolism of uncountable prokaryotes and some eukaryotic organisms including green algae. and efﬂuents produced in the human habitat. ﬁrst to dispose of excess reducing equivalents or as a byproduct in nitrogen ﬁxation. As a result. One of the important factors governing the hydrogen conversion efﬁciency is process engineering. agricultural and livestock efﬂuents as well as animal excreta are recovered mainly by microbial fermentation. An attractive and even more favored possibility is the direct splitting of water to generate hydrogen by solar radiation . the US and Japan. it is currently more expensive to produce hydrogen from biomass than it is to derive it from natural gas. Realization of practical processes for biohydrogen production would result in a major. While renewable hydrogen technologies that use low value waste biomass as feedstock have great potential to become cost competitive. Biomass as energy source is characterized in the form of both ﬂow and stock. novel biological source of sustainable and renewable energy. the fermentative route is a promising method of biohydrogen production due to its higher rate of H2 evolution . Despite its relatively lower yields of hydrogen. Nevertheless. which indirectly utilize solar radiation for the electrolysis of water into H2 and O2 . as well as hydrogenase.260 S. In addition. belonging to the genera Enterobacter. lignocellulosic products such as wood and wood waste. 2). For H2 to be renewable. which could not be realized by mechanical or chemical systems. waste from food processing and aquatic plants and algae. The unstable hydrogen production is possibly attributed to the metabolic shift of hydrogen producing bacteria. they have proved to be some of the most complex and ingenious bioinorganic structures known. Biophotolysis involves light-driven decomposition of water in the presence of micro-algae or cyanobacteria (Table 4 ). Microbiology of biohydrogen production Nature in the form of microorganisms has been using hydrogen as a primary fuel source for billions of years. many of the processes which produce hydrogen from biomass are complementary to those that produce biomaterials. If these resources were used under appropriate control. they would become the major source of energy in the future. Citrobacter. and temperature could enhance the hydrogen conversion efﬁciency. Meher Kotay. 4. including signiﬁcantly different taxonomic and physiological types. can produce hydrogen. Bacillus. Light mediated processes include direct or indirect biophotolysis and photofermentation whereas dark fermentation is the major light independent process (Fig. development of such practical processes will require signiﬁcant scientiﬁc and technological advances. when it became apparent that atmospheric pollution by fossil fuels is not only unhealthy locally.4]. Apart from pure cultures. hydrogenase (Table 2). it must come from renewable sources. Biological hydrogen production now has gained such a tremendous impetus that more than 30 countries have chosen to invest in the concerned research [3. Major resources in biomass include agricultural crops and their waste byproducts. countries with large agricultural economies have potential for signiﬁcant economic development through incorporation of bioenergy into bioindustry. and this could be minimized by the study of microbial growth. 3. is linked with the utilization of the products of photosynthetic reactions that generate reductants from water. Biohydrogen as renewable energy Interest in biohydrogen started getting prominence in early 90s. Therefore. Galore microbial species. various mixed micro-ﬂora and co-cultures have also been explored for hydrogen production from carbohydrates [6–8]. Microorganisms generate hydrogen for two principle reasons. and hence are less energy intensive than chemical or electrochemical ones. Photosynthetic microorganisms are able to convert directly solar energy to hydrogen from organic or inorganic substrates or from water. D. Although they catalyze a deceptively simple reaction. for example. Biohydrogen production: conventional and novel approaches Biological processes are carried out largely at ambient temperatures and pressures. biological hydrogen production became a focus of Governmental support. Biomass has the potential to become a signiﬁcant source of renewable hydrogen. However.5]. with meager efforts in the other countries. The critical challenges of the hydrogen fermentation are low hydrogen conversion efﬁciency and unstable hydrogen production . or by applying photovoltaics. without greenhouse gas emissions or environmental pollution. Biological processes use the enzyme hydrogenase or nitrogenase as hydrogen producing protein. A large number of microbial species. The aim is to develop a blue print for hydrogen from biomass plant [4. 5. The functioning of nitrogenase.
Various approaches of biohydrogen production.) Mixed microﬂora Mixed microﬂora Mixed microﬂora (Mesophilic) Glucose Molasses Molasses Glucose Glucose Glucose Glucose Glucose Glucose Wheat starch co-product 0. The goal is to increase the biohydrogen yield to .  Tanisho et al. Y19 Rhodopseudomonas palustris P4 Mixed culture (predominantly Clostridium sp.17 1.  Oh et al.5 h N2 sparging continuous Chemostat HRT: 17 h Anaerobic and acidogenic digestion Mahyudin et al.  Tanisho et al.  Mizuno et al. (blocking metabolites formation) Ar sparging. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 Table 2 Physiological diversity of biohydrogen production Heterotrophic Fermentative H2 production from biomass by heterotrophic bacteria (C6 H12 O6 + 2H2 O → 2CH3 COOH + 2CO2 + 4H2 ) H2 production from CO by photosynthetic bacteria (CO + H2 O → H2 + CO2 ) Photoheterotrophic 261 Biophotolytic H2 production by green algae or cyanobacteria (water splitting) (12H2 O → 12H2 + 6O2 ) Photoproduction of H2 from biomass by phototrophic bacteria (C6 H12 O6 + 6H2 O → 6CO2 + 12H2 ) Table 3 Imperative hydrogen producing microbial strains reported and their H2 yield Organism Substrate Process Maximum yield of H2 (mol H2 /mol substrate) 1. Meher Kotay.49 2.14 1.52 1.58 0.3 2. On the other hand.4–2.  Kumar and Das  Kumar et al.  Lay  Lin and Chang  Fig.  Kataoka et al.  Oh et al.S.43 1. with intermittent purging of Ar N2 sparging. Anaerobic heterotrophic microorganisms can form hydrogen during the oxidation of organic substrates.76 1. While fermentation is fast. in the absence of any light source as well as the versatility of the substrates used. fermentation today converts only about 15% of the energy to hydrogen .  Hussy et al.9 2. 2.75% soluble starch Sewage-sludge Batch. it is not yet efﬁcient for capturing the energy value of biomass to hydrogen. batch Batch N2 sparging continuous Continuous (immobilized bioreactor) Continuous (immobilized bioreactor) Batch Ar sparging Batch. A great advantage of fermentation is fast degradation of solids and other complex organics found in wastes and agricultural products. D.8 2. continuous HRT:8.3 3.7 References Enterobacter aerogenes HU-101 (mutant AY-2) Enterobacter aerogens Enterobacter aerogens Clostridium butyricum Enterobacter cloacae IIT BT 08 Enterobacter cloacae DM11 Citrobacter sp.
a combination of dark and photofermentation in a two-stage hybrid system can improve the overall yield of hydrogen [20–22]. There is scope to use sugarcane juice. yields have been low and it is uncertain whether this technology can be developed to provide high yields of hydrogen and become economically competitive with gasoline or with alternative hydrogen production pathways. However.11]  Enterobacter cloacae DM 11 Clostridium sp. It can produce H2 all day long without light A variety of carbon sources can be used as substrates It produces valuable metabolites such as butyric. efﬁcient bioreactor design and also genetic and metabolic engineering technique. high hydrogen yield remains to be the ultimate goal and challenge for the biohydrogen research and development. crops Can produce H2 from water Has the ability to ﬁx N2 from atmosphere A wide spectral light energy can be used by these bacteria Can use different waste materials like distillery efﬂuents.07 References Conventional Direct biophotolysis Indirect biophotolysis Photo fermentation Dark fermentation Can produce H2 directly from water and sunlight Solar conversion energy increased by tenfold as compared to trees. Enhancement in hydrogen yield may be possible by using suitable microbial strain.50   Novel Two-stage fermentation (dark + photo) Enterobacter cloacae DM 11 + Rhodobacter sphaeroidesOU 001 Mixed microbial ﬂora + Rhodobacter sphaeroides OU 001 51. Research progress for identifying the major technoeconomic bottlenecks of various bioprocesses for commercial production of hydrogen appears promising.24]. Therefore. However.9] Anabaena variabilis Rhodobacter spheroides 0. according to the following reactions: (i) Stage I—dark fermentation (facultative anaerobes) C6 H12 O6 + 2H2 O → 2CH3 COOH + 2CO2 + 4H2 . process modiﬁcation.20  47. However. waste.92  around 85%. While hydrogen fermentations have been demonstrated in the laboratory. Both basic and applied R&D activities on biological production of hydrogen have drawn signiﬁcant attention over past few decades. because they contain sugar in signiﬁcant quantities. if technology improvements succeed in bringing down costs. production as well as unit energy cost of biohydrogen would be reduced drastically.60 64. Biological hydrogen production. etc. Hydrogen is currently more expensive than other fuel options.16 [10. so it is likely to play a major role in the economy in the long run. molasses or distillery efﬂuent as substrates. a rigorous techno-economic analysis is necessary to draw a cost-effective comparison between biologically produced hydrogen and the various other conventional fossil fuels. Meher Kotay. Conclusions (ii) Stage II—Photofermentation (photosynthetic bacteria) 2CH3 COOH + 4H2 O → 8H2 + 4CO2 . strain No. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 Table 4 Comparison of important biological hydrogen production processes Process Advantages Representative organism Maximum reported rate (mmol H2 /L h) 0.262 S. 6. It is speculated that a fermentation yield of 10 mol of hydrogen per mole of glucose and a glucose cost of 5 cents per dry pound will be required for this process to approach hydrogen costs that are competitive with traditional fuels. 2 75. carbon dioxide and hydrogen in a thermophilic dark fermentation. employing renewable biomass may be a potential answer to overcome some of the economic constraints to fulﬁll many of our energy needs. The combination could be expected to reach as close to the theoretical maximum production of 12 mol of H2 (mol glucose)−1 equivalent as possible. lactic and acetic acids as by products It is anaerobic process. In a separate photobioreactor acetate is converted to hydrogen and carbon dioxide [23. so there is no O2 limitation problem Stoichiometric yield of 12 mol H2 per mol hexose represents the ultimate target for biohydrogen Chlamydomonas reinhardtii [8. The synergy of the process lies in the maximum utilization of the substrate which otherwise fails to achieve complete conversion due to thermodynamic limitation. D. In the ﬁrst stage. to redirect metabolic pathway .36 0. The vision for a hydrogen future is one based on clean sustainable renewable energy supply of global proportions that . the biomass is fermented to acetate.
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