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International Journal of Hydrogen Energy 33 (2008) 258 – 263

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

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.
䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Biohydrogen; Renewable energy; Waste-to-energy; Bioremediation

1. Introduction closely related to the increased use of hydrogen in refineries

as a result of stricter standards for fuel quality [2]. The Global
Hydrogen holds the promise as a dream fuel of the future with Hydrogen Vision envisions hydrogen as a flexible, safe, afford-
many social, economic and environmental benefits to its credit. able, domestic energy resource to be used in all sectors of the
It has the long-term potential to reduce the dependence on for- economy and all regions of the world. Hydrogen will become
eign oil and lower the carbon and criteria emissions from the world’s “clean energy choice”, joining electricity as a primary
transportation sector. Only in the last decade that the idea of a energy carrier and providing the foundation for a globally sus-
post-fossil fuel hydrogen-based economy started to gain main- tainable energy system [3]. It has a wide variety of applications,
stream interest. Molecular H2 has the highest energy content including fuel for automobiles; distributed and central electric-
per unit weight among the known gaseous fuels (143 GJ ton−1 ) ity and thermal energy generation (Fig. 1).
[1] and is the only carbon-free fuel which ultimately oxidizes
to water as a combustion product. Therefore burning hydrogen
2. Barriers for biohydrogen production
not only has the potential to meet a wide variety of end use
applications but also does not contribute to greenhouse emis-
Technical challenges in achieving a hydrogen economy in-
sion, acid rain or ozone depletion. The use of hydrogen will
clude lowering the cost of hydrogen production, delivery, stor-
contribute to significant reduction of these energy-linked envi-
age, conversion, and end use applications. Although hydrogen
ronmental impacts.
is the most abundant element in the universe, it must be pro-
H2 can be used either as the fuel for direct combustion in an
duced from other hydrogen-containing compounds such as fos-
internal combustion engine or as the fuel for a fuel cell. The
sil fuels, biomass, or water. Each method of production requires
largest users of H2 , however, are the fertilizer and petroleum
a source of energy, i.e., thermal (heat), electrolytic (electricity),
industries with, respectively, 50% and 37%. Sales of hydrogen
or photolytic (light) energy (Table 1). In other words they are
have increased by 6% annually in the last five years, which is
highly energy intensive and not always environmentally benign
∗ Corresponding author. Tel.: +91 3222 278053, +91 3222 283758; [4]. Moreover, there is a growing concern arising out of the
fax: +91 3222 255303. projection of fossil fuel shortfall towards the middle of twenty-
E-mail address: (D. Das). first century. Under this perspective, biological hydrogen
0360-3199/$ - see front matter 䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
S. Meher Kotay, D. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 259

Fig. 1. Chronology of fuel usage by mankind.

Table 1
Scientific and technical barriers for biohydrogen production

Type of barrier Barrier Putative solution

Basic science
Organism Bacteria do not produce more than 4 mol Isolate more novel microbes and combinational screen for H2
H2 /mol glucose naturally production rates yields, and durability
Genetic manipulation of established bacteria
Enzyme (hydrogenase) Hydrogenase overexpression not stable Greater understanding of the enzyme regulation and expression
O2 sensitivity Mutagenic studies
H2 feed back inhibition Low H2 partial pressure fermentation

Feedstock High cost of suitable feedstock (glucose) Renewable biomass as feedstock
Low yield using renewable biomass Co-digestion/use of microbial consortia which can increase the
Strain Lack of industrial-suitable strain Development of industrially viable strain(s)/consortia
Process Commercially feasible product yield Hybrid system (photo + dark fermentation)
Incomplete substrate utilization Link fermentation to a second process that makes both economi-
cally possible
Sustainable process Application and utilization of fermentation tools such as continuous
Sterilization Development of low-cost stream sterilization technology/process
that can bypass sterilization

Reactor Lack of kinetics/appropriate reactor design Incorporation of process engineering concepts to develop a suitable
for H2 production reactor for the defined strain/process
Light intensity in case of photo-bioreactor Flat panel or hollow tube reactor can be employed
Thermodynamic Thermodynamic barrier NAD(P)H → H2 Reverse electron transport to drive H2 production past barrier
(+4.62 kJ/mol)
Hydrogen H2 purification/separation Selection absorption of CO2 /H2 S
Storage Basic studies on H2 storage

production assumes paramount importance as an alternative and costs for transport. From thermodynamic perspective, as the
renewable energy resource. organic substrates dissolved and diluted in wastewater are in a
Biological processes, unlike their chemical or electrochemi- high entropy state, it is somewhat difficult to obtain their com-
cal counterparts are catalyzed by microorganisms in an aqueous bustion enthalpy by mechanical means [5]. On the contrary in
environment at ambient temperature and pressure. Furthermore, biological processes microorganisms can recover and concen-
these techniques are well suited for decentralized energy pro- trate the energy from high water content organic resources such
duction in small-scale installations in locations where biomass as, industrial wastewater and sludge in a usable form. Thus,
or wastes are available, thus avoiding energy expenditure and biohydrogen production, in a sense, is an entropy reducing
260 S. Meher Kotay, D. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263

process, which could not be realized by mechanical or chem- bacteria, and this could be minimized by the study of microbial
ical systems. The aim is to develop a blue print for hydrogen growth.
from biomass plant [4,5].
4. Microbiology of biohydrogen production
3. Biohydrogen as renewable energy
Nature in the form of microorganisms has been using hy-
Interest in biohydrogen started getting prominence in early drogen as a primary fuel source for billions of years, and has
90s, when it became apparent that atmospheric pollution by solved the problem of converting hydrogen to electricity by
fossil fuels is not only unhealthy locally, but might also cause means of the biocatalyst, hydrogenase (Table 2). Although they
significant climate changes globally. As a result, biological hy- catalyze a deceptively simple reaction, they have proved to be
drogen production became a focus of Governmental support, some of the most complex and ingenious bioinorganic struc-
particularly in Germany, the US and Japan, with meager efforts tures known. Microorganisms generate hydrogen for two prin-
in the other countries. Biological hydrogen production now has ciple reasons, first to dispose of excess reducing equivalents or
gained such a tremendous impetus that more than 30 countries as a byproduct in nitrogen fixation.
have chosen to invest in the concerned research [3,4]. Realiza- Microbial H2 production is an attractive process for sup-
tion of practical processes for biohydrogen production would plying a significant share of the H2 required for the near
result in a major, novel biological source of sustainable and future. Galore microbial species, belonging to the genera En-
renewable energy, without greenhouse gas emissions or envi- terobacter, Citrobacter, Bacillus, and Clostridium are reported
ronmental pollution. However, development of such practical (Table 3) to produce hydrogen through dark fermentation
processes will require significant scientific and technological [6]. Apart from pure cultures, various mixed micro-flora and
advances, and relatively long-term (> 10 yr) basic and applied co-cultures have also been explored for hydrogen production
R&D. For H2 to be renewable, it must come from renewable from carbohydrates [6–8]. Nevertheless, the quest for ideal mi-
sources. crobe(s) for microbial H2 production has thrust the researchers
Major resources in biomass include agricultural crops and to screen various sources.
their waste byproducts, lignocellulosic products such as wood
and wood waste, waste from food processing and aquatic plants 5. Biohydrogen production: conventional and novel
and algae, and effluents produced in the human habitat. Energy approaches
from water-containing biomass such as sewage sludge, agri-
cultural and livestock effluents as well as animal excreta are Biological processes are carried out largely at ambient tem-
recovered mainly by microbial fermentation. Biomass as en- peratures and pressures, and hence are less energy intensive than
ergy source is characterized in the form of both flow and stock. chemical or electrochemical ones. A large number of microbial
If these resources were used under appropriate control, they species, including significantly different taxonomic and physi-
would become the major source of energy in the future. ological types, can produce hydrogen. Biological processes use
Biomass has the potential to become a significant source the enzyme hydrogenase or nitrogenase as hydrogen produc-
of renewable hydrogen. In addition, many of the processes ing protein. This enzyme regulates the hydrogen-metabolism
which produce hydrogen from biomass are complementary to of uncountable prokaryotes and some eukaryotic organisms in-
those that produce biomaterials. Therefore, countries with large cluding green algae. The functioning of nitrogenase, as well as
agricultural economies have potential for significant economic hydrogenase, is linked with the utilization of the products of
development through incorporation of bioenergy into bioindus- photosynthetic reactions that generate reductants from water.
try. While renewable hydrogen technologies that use low value The processes of biological hydrogen production can be
waste biomass as feedstock have great potential to become cost broadly classified into two distinct groups. One is light depen-
competitive, it is currently more expensive to produce hydro- dent and the other is light independent process. Light mediated
gen from biomass than it is to derive it from natural gas. In- processes include direct or indirect biophotolysis and photofer-
dependent of the source of hydrogen, there are many logistical mentation whereas dark fermentation is the major light inde-
and market challenges that must also be overcome before a hy- pendent process (Fig. 2). Biophotolysis involves light-driven
drogen economy can become a reality: decomposition of water in the presence of micro-algae or
cyanobacteria (Table 4 ). An attractive and even more favored
biomass + O2 → CO + H2 + CO2 + energy.
possibility is the direct splitting of water to generate hydrogen
The critical challenges of the hydrogen fermentation are low by solar radiation [4]. This H2 O splitting can be achieved either
hydrogen conversion efficiency and unstable hydrogen produc- in photochemical cells where, for example, TiO2 is illuminated
tion [7]. One of the important factors governing the hydrogen as the catalyst, or by applying photovoltaics, which indirectly
conversion efficiency is process engineering, such as bioreac- utilize solar radiation for the electrolysis of water into H2 and
tor design and operating parameters. Improving reactor design O2 [5]. Photosynthetic microorganisms are able to convert
and optimizing the operating parameters such as pH, hydraulic directly solar energy to hydrogen from organic or inorganic
retention time, and temperature could enhance the hydrogen substrates or from water. Despite its relatively lower yields
conversion efficiency. The unstable hydrogen production is pos- of hydrogen, the fermentative route is a promising method of
sibly attributed to the metabolic shift of hydrogen producing biohydrogen production due to its higher rate of H2 evolution
S. Meher Kotay, D. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 261

Table 2
Physiological diversity of biohydrogen production

Heterotrophic Photoheterotrophic

Fermentative H2 production from biomass by heterotrophic bacteria Biophotolytic H2 production by green algae or cyanobacteria (water splitting)
(C6 H12 O6 + 2H2 O → 2CH3 COOH + 2CO2 + 4H2 ) (12H2 O → 12H2 + 6O2 )
H2 production from CO by photosynthetic bacteria Photoproduction of H2 from biomass by phototrophic bacteria
(CO + H2 O → H2 + CO2 ) (C6 H12 O6 + 6H2 O → 6CO2 + 12H2 )

Table 3
Imperative hydrogen producing microbial strains reported and their H2 yield

Organism Substrate Process Maximum References

yield of H2
(mol H2 /mol

Enterobacter aerogenes HU-101 Glucose Batch, (blocking metabolites formation) 1.17 Mahyudin et al. [9]
(mutant AY-2)
Enterobacter aerogens Molasses Ar sparging, batch 1.58 Tanisho et al. [10]
Enterobacter aerogens Molasses Batch 0.52 Tanisho et al. [10]
Clostridium butyricum Glucose N2 sparging continuous 1.4–2.3 Kataoka et al. [11]
Enterobacter cloacae Glucose Continuous (immobilized bioreactor) 2.3 Kumar and Das [16]
Enterobacter cloacae DM11 Glucose Continuous (immobilized bioreactor) 3.8 Kumar et al. [17]
Citrobacter sp. Y19 Glucose Batch Ar sparging 2.49 Oh et al. [18]
Rhodopseudomonas Glucose Batch, with intermittent purging of Ar 2.76 Oh et al. [19]
palustris P4
Mixed culture (predominantly Glucose N2 sparging, continuous HRT:8.5 h 1.43 Mizuno et al. [12]
Clostridium sp.)
Mixed microflora Wheat starch co-product N2 sparging continuous 1.9 Hussy et al. [13]
Mixed microflora 0.75% soluble starch Chemostat HRT: 17 h 2.14 Lay [14]
Mixed microflora Sewage-sludge Anaerobic and acidogenic digestion 1.7 Lin and Chang [15]

Fig. 2. Various approaches of biohydrogen production.

in the absence of any light source as well as the versatility of complex organics found in wastes and agricultural products.
the substrates used. On the other hand, fermentation today converts only about 15%
Anaerobic heterotrophic microorganisms can form hydro- of the energy to hydrogen [7]. While fermentation is fast, it
gen during the oxidation of organic substrates. A great advan- is not yet efficient for capturing the energy value of biomass
tage of fermentation is fast degradation of solids and other to hydrogen. The goal is to increase the biohydrogen yield to
262 S. Meher Kotay, D. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263

Table 4
Comparison of important biological hydrogen production processes

Process Advantages Representative organism Maximum References

reported rate
(mmol H2 /L h)

Direct biophotolysis Can produce H2 directly from water and sunlight Chlamydomonas reinhardtii 0.07 [8,9]
Solar conversion energy increased by tenfold as
compared to trees, crops
Indirect biophotolysis Can produce H2 from water Has the ability to fix Anabaena variabilis 0.36 [10,11]
N2 from atmosphere
Photo fermentation A wide spectral light energy can be used by these Rhodobacter spheroides 0.16 [12]
Can use different waste materials like distillery ef-
fluents, waste, etc.
Dark fermentation It can produce H2 all day long without light Enterobacter cloacae DM 11 75.60 [13]
A variety of carbon sources can be used as substrates Clostridium sp. strain No. 2 64.50 [14]
It produces valuable metabolites such as butyric,
lactic and acetic acids as by products
It is anaerobic process, so there is no O2 limitation
Two-stage fermentation Stoichiometric yield of 12 mol H2 per mol hexose Enterobacter cloacae 51.20 [15]
(dark + photo) represents the ultimate target for biohydrogen DM 11 + Rhodobacter
sphaeroidesOU 001
Mixed microbial flora + 47.92 [16]
Rhodobacter sphaeroides
OU 001

around 85%. While hydrogen fermentations have been demon- Both basic and applied R&D activities on biological produc-
strated in the laboratory, yields have been low and it is uncer- tion of hydrogen have drawn significant attention over past few
tain whether this technology can be developed to provide high decades. Research progress for identifying the major techno-
yields of hydrogen and become economically competitive with economic bottlenecks of various bioprocesses for commercial
gasoline or with alternative hydrogen production pathways. It production of hydrogen appears promising. However, high hy-
is speculated that a fermentation yield of 10 mol of hydrogen drogen yield remains to be the ultimate goal and challenge
per mole of glucose and a glucose cost of 5 cents per dry pound for the biohydrogen research and development. Enhancement
will be required for this process to approach hydrogen costs in hydrogen yield may be possible by using suitable micro-
that are competitive with traditional fuels. bial strain, process modification, efficient bioreactor design and
However, a combination of dark and photofermentation in a also genetic and metabolic engineering technique, to redirect
two-stage hybrid system can improve the overall yield of hy- metabolic pathway [20]. Hydrogen is currently more expensive
drogen [20–22]. The synergy of the process lies in the maxi- than other fuel options, so it is likely to play a major role in
mum utilization of the substrate which otherwise fails to achieve the economy in the long run, if technology improvements suc-
complete conversion due to thermodynamic limitation. ceed in bringing down costs. Biological hydrogen production,
In the first stage, the biomass is fermented to acetate, carbon employing renewable biomass may be a potential answer to
dioxide and hydrogen in a thermophilic dark fermentation. In a overcome some of the economic constraints to fulfill many of
separate photobioreactor acetate is converted to hydrogen and our energy needs. There is scope to use sugarcane juice, mo-
carbon dioxide [23,24]. The combination could be expected to lasses or distillery effluent as substrates, because they contain
reach as close to the theoretical maximum production of 12 mol sugar in significant quantities. Therefore, production as well
of H2 (mol glucose)−1 equivalent as possible, according to the as unit energy cost of biohydrogen would be reduced drasti-
following reactions: cally. However, a rigorous techno-economic analysis is nec-
essary to draw a cost-effective comparison between biologi-
(i) Stage I—dark fermentation (facultative anaerobes) cally produced hydrogen and the various other conventional
fossil fuels.
C6 H12 O6 + 2H2 O → 2CH3 COOH + 2CO2 + 4H2 .
6. Conclusions
(ii) Stage II—Photofermentation (photosynthetic bacteria)
The vision for a hydrogen future is one based on clean sus-
2CH3 COOH + 4H2 O → 8H2 + 4CO2 . tainable renewable energy supply of global proportions that
S. Meher Kotay, D. Das / International Journal of Hydrogen Energy 33 (2008) 258 – 263 263

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