Journal of Scientific & Industrial Research

Vol. 63, September 2004, pp. 729-738

Biohydrogen production as a potential energy resource Present state-of-art

Kaushik Nath and Debabrata Das*
Department of Biotechnology, Indian Institute of Technology, Kharagpur 721 302

Biological hydrogen production is one of the most challenging areas of technology development for sustainable
gaseous energy generation. The future of biological hydrogen production depends not only on research advances, i.e.
improvement in efficiency through genetically engineered microorganisms and/or the development of bioreactors, but also
on economic considerations, as compared to fossil fuels, social acceptance, and the development of hydrogen energy
systems. The present study critically updates various biohydrogenation processes with special references to their merits and
demerits. Different approaches towards improvement of the bioprocesses are also outlined.
Keywords: Hydrogen, Biophotolysis, Photofermentation, Light energy, Dark fermentation, Energy conversion efficiency
IPC Code: Int. Cl.
7
: C 12 P 1/02
1 Introduction
Hydrogen holds much promise as a dream fuel of the future against the projection of the global energy crisis.
In the past few years the concept of the hydrogen economy has been put forth as a clean and efficient
replacement for the petroleum based economy we now live under. It is a versatile energy carrier with the
potential for extensive use in power generation and in many other applications. About half of all hydrogen
produced is used in the manufacture of ammonia, which is itself mostly used in making fertilizers; a further 37
per cent is used in oil refineries for removal of impurities or for upgrading heavier oil fractions into lighter and
more valuable products; 8 per cent in methanol production and
4 per cent in a wide variety of chemical, metallurgical and other uses. 1 per cent of hydrogen production is used
in the worlds space programmes
1
(Fig. 1). The future widespread use of hydrogen is likely to be in the
transportation sector where it will help reduce pollution. Vehicles can be powered with hydrogen fuel cells,
which are three-times more efficient than a gasoline powered engine. As on today, in all these areas hydrogen
utilization is equivalent to 3 per cent of the energy consumption, but it is expected to grow significantly in
future
2
.
More than 500 b cu m of hydrogen are produced each year, for use in a wide variety of processes. This
amount of hydrogen could produce 6.5 EJ of energy, equivalent to about 1.5 per cent of world energy
consumption
3
. 99 per cent of this hydrogen is produced from fossil fuels, primarily natural gas, with chemical
production and renewable energy sources accounting for the rest. At present, all of the CO
2
generated is released
to atmosphere. Catalytic steam reforming of naphtha or natural gas, gasification of coal, and electrolysis of water
are some of the classical methods of hydrogen
manufacturing currently in vogue. But all these methods
are highly energy intensive, thereby incurring higher
cost and not always environmentally benign. On the
contrary, biological processes are particularly useful for
this application because they are catalyzed by
microorganisms in an aqueous environment at ambient
temperature and pressure. Furthermore, these techniques
are well suited for decentralized energy production in
small-scale installations in locations where biomass or
wastes are available, thus avoiding energy expenditure
and costs for transport
1
. From thermodynamic
perspective, as the organic substrates dissolved and


Fig.1Different uses of hydrogen
J SCI IND RES VOL 63 SEPTEMBER 2004


730
diluted in wastewater are in a high entropy state, it is somewhat difficult to obtain their combustion enthalpy by
mechanical means
4
. Here comes the importance of biological hydrogen production process where
microorganisms can recover and concentrate the energy from high water content organic resources such as,
industrial wastewater and sludges in a usable form. Thus, biohydrogenation, in a sense, an entropy reducing
process, which could not be realized by mechanical or chemical systems
4
.
Interest in biohydrogen started getting prominence in early 90s, when it became apparent that atmospheric
pollution by fossil fuels is not only unhealthy locally, but might also cause significant climate changes globally.
As a result, biological hydrogen production became a focus of Governmental support, particularly in Germany,
the US and Japan, with least efforts in the other countries. The present paper briefly describes state-of-the-art of
various biological hydrogen production processes. Attempts have also been made to highlight both the
advantages and bottlenecks of each process towards improvement of production and process efficiency.

2 Biohydrogenation State-of-the-Art
Hydrogen metabolism is primarily the domain of bacteria and micro-algae. Within these groups, it involves
many microbial species, including significantly different taxonomic and physiological types, various enzymes
and metabolic pathways. Table 1 summarizes various biological hydrogen production processes with general
overall reactions involved therein, broad classification of microorganisms used and their relative advantages.
Table 1 Different biological hydrogen production processes with their advantages

Process General reactions and broad classification of
microorganisms used

Advantages
1 Direct biophotolysis

2 H
2
O + light = 2 H
2
+ O
2


Micro-algae

(i) Can produce H
2
directly from water and
sunlight
(ii) Solar conversion energy increased by 10- folds
as compared to trees, crops

2 Indirect biophotolysis

6 H
2
O + 6 CO
2
+ light = C
6
H
12
O
6
+ 6 O
2

C
6
H
12
O
6
+ 2 H
2
O = 4 H
2
+ 2 CH
3
COOH + 2 CO
2


2 CH
3
COOH + 4 H
2
O + light = 8 H
2
+ 4 CO
2

Overall reaction:
12 H
2
O + light = 12 H
2
+ 6 O
2

Microalgae, cyanobacteria

(i) Can produce H
2
from water

(ii) Has the ability to fix N
2
from atmosphere
3 Dark fermentation

C
6
H
12
O
6
+ 6 H
2
O = 12 H
2
+ 6 CO
2

Fermentative bacteria

(i) It can produce H
2
all day long without light
(ii) A variety of carbon sources can be used as
substrates
(iii) It produces valuable metabolites such as
butyric, lactic, and acetic acids as by products
(iv) It is anaerobic process, so there is no O
2

limitation problem
4 Photo -fermentation
CH
3
COOH + 2 H
2
O + light = 4 H
2
+ 2 CO
2

Purple bacteria,
Microalgae

(i) A wide spectral light energy can be used by
these bacteria
(ii) Can use different waste materials like distillery
effluents, waste, etc.
5 Hybrid reactor system
(combined dark and
photo- fermentation)
Stage I
C
6
H
12
O
6
+ 2 H
2
O = 4 H
2
+ 2 CH
3
COOH + 2 CO
2

Stage II
CH
3
COOH + 2 H
2
O + light = 4 H
2
+ 2 CO
2


Fermentative bacteria followed by anoxygenic
phototrophic bacteria (PNS)

Two stage fermentation can improve the overall
yield of hydrogen

NATH & DAS: BIOHYDROGEN PRODUCTION AS A POTENTIAL ENERGY RESOURCE


731

2.1 Direct Biophotolysis
Direct biophotolysis employs the dissociation of
water molecules under sunlight in the presence of
microalgae. It uses the same process found in plants
and algal photosynthesis, but adapts them for the
generation of hydrogen gas, instead of carbon
containing biomass
5
(Fig. 2). Green microalgae
possess the genetic, enzymatic, metabolic, and
electron transport machinery to photoproduce
hydrogen gas. Several researchers have reported algal photolysis using various species like Scenedesmus
obliquus, Chlamydomonas reinhardii, C. moewusii (ref.5). Biophotolysis is an inherently attractive process since
solar energy is used to convert a readily available substrate, water to oxygen, and hydrogen. This approach, if
successful, would allow virtually unlimited production of hydrogen from the earths most plentiful available
resources water and light
6
.
Hydrogen production by green algae requires several minutes to a few hours of anaerobic incubation in the
dark to induce the synthesis and/or activation of enzymes involved in hydrogen metabolism, including a
reversible hydrogenase enzyme. Since hydrogenase activity is extremely oxygen sensitive the concurrent
production of O
2
poses a serious limitation. This is the major bottleneck of the process. Sweeping out the
oxygen, as it is produced, could mitigate this inhibition to a great extent
7
. Although this would not be practical
for large-scale operation. Some other attempts to overcome this problem include the use of O
2
absorbers, both
reversible and irreversible, and the use of O
2
tolerant hydrogenase enzymes. But these attempts have met with
limited success
8
. One promising solution is to develop microalgae with an O
2
insensitive hydrogenase reaction.
Apart from these there are tremendous biological and engineering challenges to be overcome in realizing this
goal. Direct biophotolysis requires entire production area to be enclosed in photobioreactor, which is able to both
produce and capture H
2
and O
2
. But this approach seems to be economically not viable as handling of H
2
/O
2

mixtures in large volumes and over large areas would likely be impractical
6
. The reducing power generated by
photosynthesis must be produced as close as possible to the maximal possible solar conversion efficiency of
about 10 per cent and then efficiently transferred to hydrogenase. Currently, photosynthetic organisms like
higher plants capture only 3-4 per cent of sunlights available energy
7
.
Thus, direct biophotolysis, although theoretically attractive as a hydrogen production process, suffers from the
major limitations of oxygen sensitivity, low light conversion efficiency and gas separation (Table 2). Future
studies will pursue the possibility of "sweeping" oxygen from the system or development of a hydrogenase
engineered to be insensitive to oxygen inactivation. In addition, this method requires enclosure of the solar
capture area within a photo-bioreactor, which creates great engineering challenges.

2.2 Indirect Biophotolysis
Cyanobacteria (also known as blue-green algae, cyanophyceae, or cyanophytes) are a large and diverse group
of photoautotrophic microorganisms, which can evolve hydrogen by indirect biophotolysis of water (Fig. 3).
Photosystem II utilizes the energy of sunlight in photosynthesis to extract electrons from water molecules.
Electrons released upon the oxidation of water are transported to the Fe-S protein ferredoxin on the reducing
side of photosystem I. The hydrogenase in the stroma of the algal chloroplast accepts electrons from reduced
ferredoxin and donates them to two protons to generate one H
2
molecule
5
. For photobiological hydrogen
production, cyanobacteria have been adjudged as one of the ideal candidates since they have simple nutritional
requirements as they can grow in air (N
2
and CO
2
), water and mineral salts, with light as the only energy
sources
9
. Hydrogen production by cyanobacteria has been studied for over three decades and has revealed that
efficient photoconversion of H
2
O to H
2
is influenced by many factors. Hydrogen production has been assessed in
various species and strains, within at least 14 genera, under a vast range of culture conditions
10
. The need of light
for hydrogen evolution, nitrogenase, oxygen sensitivity, and lower hydrogen evolution vs acetylene reduction
are some

Fig. 2Direct biophotolysis

J SCI IND RES VOL 63 SEPTEMBER 2004


732


Fig. 3Indirect biophotolysis

of the important factors of biophotolysis
10
. The cultivation of cyanobacteria in nitrate-free media under air and
CO
2
, followed by incubation in light under argon and CO
2
atmosphere, has rapidly become standard, since it
results in immediate hydrogen production. Localization of nitrogenase in heterocysts provides an oxygen-free
environment and the ability of heterocystous cyanobacteria to fix nitrogen in air
11
. Hydrogenase and nitrogenase
inhibitors are used in an attempt to screen for aerobic hydrogen evolution potential. It has been observed that
these inhibitors allow for hydrogen to be released from aerobic cultures in amounts similar to those in argon
11
.
Photobiological technology holds great promise but because oxygen is produced along with the hydrogen the
technology must overcome the limitation of oxygen sensitivity of the hydrogen-evolving enzyme systems.
Table 2Major bottlenecks of the processes and various approaches to overcome

Processes Major limitations Approaches to overcome References

1 Direct (a) O
2
sensitivity of hydrogenase (a)
biophotolysis enzyme (i) Use of O
2
absorbers, both irreversible (glucose-
oxidase, dithionite) and reversible (hemoglobin)
6
(ii) Use of O
2
tolerant uptake hydrogenase 13
(b)Low light conversion efficiency (b)
(i) Genetic manipulation of light gathering antenna 14
(ii) Optimization of light input into photobioreactor 15

2 Indirect
biophotolysis
(a) Enzyme inhibition by O
2
(a) To achieve O
2
tolerant hydrogenase activity by
classical mutagenesis
13
(b) H
2
consumption by an uptake
hydrogenase
(b) Genetic modification of strains to eliminate uptake
hydrogenase
16
(c) Overall low production rate (c) Genetic modification to increase levels of
bidirectional hydrogenase activity
17

3 Dark fermentation (a) Relatively lower achievable
yields of H
2

(a) Metabolic shift of biochemical pathways to arrest the
formation of alcohol and acids
18
(b) As yields increase, H
2

fermentation becomes
thermodynamically unfavorable
(b) Maintaining low partial pressure of H
2
19
(c) Product gas mixture contains
CO
2
which has to be separated
(c) Efficient removal of gases 20

4 Photofermentation (a) Light conversion efficiency is (a)
very low, only 1-5 per cent (i) Elimination of competing microorganisms (e.g.
micro- algae) using light filters
21
(b) Inhomogeneity of light
distribution
(ii) Co-cultures of photo heterotrophic bacteria with
different light utilization characteristics
22
(c) O
2
is a strong inhibitor of
hydrogenase
(iii) Control of photosynthetic protein expression to
allow efficient absorption of light energy
6
(b) Improvement in photoreactor design with light
diffuser
6

5 Hybrid reactor
system
Relatively newer approach,
techno-economic feasibility is yet
to be studied
23


NATH & DAS: BIOHYDROGEN PRODUCTION AS A POTENTIAL ENERGY RESOURCE


733
Researchers are addressing this issue by screening for
naturally occurring organisms that are more tolerant of
oxygen, and by creating new genetic forms of the
organisms that can sustain hydrogen production in the
presence of oxygen
12
. A new system is also being
developed that uses a metabolic switch (sulphur
deprivation) to cycle algal cells between a
photosynthetic growth phase and a hydrogen production
phase
12
.

2.3 Photofermentation
The efficiency of light energy used for the production
of hydrogen by photosynthetic bacteria is theoretically
much higher compared with cyanobacteria. The
advantages of phototrophic bacteria can be attributed to the following facts:

(i) High theoretical conversion yields,
(ii) Lack of O
2
evolving activity, which otherwise causes O
2
inactivation problems in different biological
systems,
(iii) Ability to use wide spectral light energy, and
(iv) Ability to consume organic substrates derived from wastes in association with wastewater treatment.

These organisms have an important role in the anaerobic cycling of organic matter as producers
(photoautrophs, utilizing CO
2
as their carbon source and H
2
as their electron donor), and as consumers
(photoheterotrophs, using organic molecules as their carbon source and electron donor)
24
. Production of
hydrogen by photosynthetic bacteria takes place under illumination and in the presence of an inert anaerobic
atmosphere (such as argon or helium), from the break down of organic subtracts like, malate and lactate (Fig. 4).
These anions of organic acids are preferred substrates. Apart from different organic acids and carbohydrates,
several wastewaters have also been attempted to explore their suitability to be used as substrates for PNS
bacteria to produce hydrogen.
The efficiency of phototrophic bacteria for biological production of hydrogen is closely associated with
several important variables. Photochemical efficiency is one of those. A generalized expression for
photochemical efficiency has been put forward by Akkerman et al.
12


Efficiency (per cent) =
H
2
production rate
Hydrogen energy content
Absorbed light energy


For the photoautotrophic hydrogen production, photochemical efficiencies are only 3-10 per cent when the
oxygen is totally and immediately removed. Such low efficiencies of photoautotrophic process pose a major
limitation towards its commercial acceptance. On the other hand, photochemical efficiency of
photoheterotrophic bacteria is comparatively higher than that of photoautotrophs. However, this is essentially
based on artificial light, the efficiency of which can reach 10 per cent or even more by only at low light
intensities with low hydrogen production rates
12
. The energy conversion efficiency of light energy into hydrogen
in the presence of phototosynthetic bacteria varies under different light sources. It is believed that the hydrogen
production by photosynthetic bacteria may depend on the spectral distribution, since the bacteria utilize the
specific light wavelengths for photosynthesis. An approach for the improvement of hydrogen production by
photosynthetic bacteria is the control of photosynthetic protein expression to allow efficient absorption of light
energy. A method for the enhancement of the bacterial light-dependent hydrogen production is proposed by
Miyake et al.
4
by rearrangement of light harvesting systems. Genetic manipulation of photosynthetic pigment
content of bacteria by promoter competition method can be controlled for making the light penetration easy
4
.


Fig. 4Schematic of hydrogen production by photosynthetic
bacteria

J SCI IND RES VOL 63 SEPTEMBER 2004


734
Inhomogeneity of the light distribution in the reactor also contributes to lower the overall light conversion
efficiency. To enhance the total efficiency of light to hydrogen conversion in a photobioreactor, light energy
should be equally distributed throughout the reactor. The spectrum of light in the reactor also affects hydrogen
evolution. An important point of the application of solar energy is the efficiency of the conversion. It is said that
the plant photosynthesis is done with energy conversion efficiency as low as 1 per cent
4
.
Another limitation of photofermentation is lower achievable yield of hydrogen. Koku et al.
25
have proposed
several conditions for maximum hydrogen production. Among these maintaining a maximal activity of
nitrogenase and minimal activity of hydrogenase, a favorable molar ratio of carbon source to nitrogen source and
availability of uniform distribution of light through the culture are important. Efforts to improve hydrogen
production by photosynthetic bacteria also include elimination of competing microorganisms, such as micro
algae, using light filters, as proposed by Ko and Noike
21
. The use of co-cultures of photoheterotrophic bacteria
with different light utilization characteristics
22
, novel photobiorector designs
26
and use of specific waste streams
as substrates for photo-fermentation
27
have also been explored as alternative options for improving the efficiency
of photosynthetic processes.
The main bottleneck for practical application of photobiological hydrogen production is the required scaling-
up of the system. A large surface area is needed to collect light. Construction of a photobioreactor with a large
surface/volume ratio for direct absorption of sunlight is expensive. A possible alternative is the utilization of
solar collectors. Again, a drawback of these collector systems is the high production cost with the currently
available technology.

2.4 Dark Fermentation
Carbohydrates, mainly glucose, are the preferred carbon sources for fermentation process, which
predominantly give rise to acetic and butyric acids together with hydrogen. Here, pyruvate the product of
glucose catabolism is oxidized to acetyl-CoA, which can be converted to acetyl phosphate and results in
generation of ATP and excretion of acetate. Pyruvate oxidation to acetyl-CoA requires ferredoxin (Fd)
reduction. Reduced Fd is oxidized by hydrogenase, which generates Fd and releases electrons as molecular
hydrogen.

Pyruvate + CoA + 2 Fd(ox) Acetyl-CoA + 2Fd(red) + CO
2

2 Fd(red) 2 Fd(ox) + H
2


Despite having higher evolution rate of hydrogen the yield of hydrogen from fermentation process is lower
than that of other chemical/electrochemical processes, and thus the process is not economically viable in its
present form. The pathways and experimental evidences cited in literature reveal that a maximum of four mole
of hydrogen could be obtained from one mol of glucose. The relatively low yield of hydrogen during
fermentation is a natural consequence of the fact that fermentations have been optimized by evolution to produce
cell biomass and not hydrogen. Thus, a portion of the substrate (pyruvate) is used to produce ATP giving a
product (acetate), which is excreted. Moreover, in many organisms the actual yields of hydrogen are reduced by
hydrogen recycling owing to the presence of one or more uptake hydrogenase, which consume a part of
hydrogen produced
6
.
The generation of hydrogen by fermentative bacteria also accompanies the formation of organic acids as
metabolic products, but these anaerobes are incapable of further breaking down the acids. Accumulation of these
acids causes a sharp drop of culture pH and subsequent inhibition of bacterial hydrogen production
28,29
. Bacteria
cannot sustain at pH smaller than 5.0 and this necessitates to evolve a way to reduce acid production or to carry
out certain biochemical reactions which reduces the proton concentration on the outside of the cell in proportion
to the culture pH (ref. 30). The use of an aciduric facultative anaerobe of which the lower limit of pH for H
2

production is as low as possible to reduce alkali consumption might be an option. Another approach to improve
the hydrogen yield is to block the formation of these acids through redirection of metabolic pathways
18,31
. The
hydrogen yield is reportedly increased to 3.8 mol/(mol glucose) by blocking the pathways of organic acid
formation by proton-suicide technique
18
using NaBr and NaBrO
3
.
NATH & DAS: BIOHYDROGEN PRODUCTION AS A POTENTIAL ENERGY RESOURCE


735
Gas sparging has been found to be a useful technique to reduce hydrogen partial pressure in the liquid phase
for enhancement of its yield. Mizuno
et al.
19
have observed that specific hydrogen production rate has increased from 1.446 mL hydrogen/min/g
biomass to 3.131 mL hydrogen/min/g biomass under nitrogen sparging conditions. With N
2
sparging at a flow
rate approx 15-times the hydrogen production rate the hydrogen yield was 1.43 mol H
2
/(mol glucose). This
shows about 50 per cent increase in hydrogen yield with nitrogen sparging.

2.5 Hybrid Reactor System
The idea of combined dark and photofermentation system takes into consideration the very fact of relatively
lower achievable yield of hydrogen in dark fermentation and also the non-utilization of the acids produced
therein. The combination of photosynthetic bacteria with that of anaerobic could provide an integrated system
for maximization of hydrogen yield
32
. In such a system, anaerobic fermentation of carbohydrate (or organic
wastes) produces intermediates such as, low molecular weight organic acids, which are then converted to
hydrogen by photosynthetic bacteria in the second step in a photobioreactor. Lee et al.
23
have studied the
combination of purple nonsulphur photosynthetic bacteria and anaerobic bacteria for efficient conversion of
wastewater into hydrogen. In this study, effluents from three carbohydrate-fed reactors (CSTR, ASBR, and
UASB) have been used for hydrogen production. In another study, Kim et al.
33
have combined dark fermentation
with photofermentation to improve hydrogen productivity from food processing wastewater and sewage sludge.
The conversion efficiency of light energy to hydrogen, with the supply of an appropriate carbon source, is one
of the key factors for hydrogen production by biological systems. Anaerobic bacteria decompose carbohydrates
to obtain both energy and electron. Because reaction with only negative free energy could be possible, organic
acids formed by the anaerobic digestion could not be decomposed to hydrogen any more. Complete degradation
of glucose to hydrogen and carbon dioxide is virtually impossible by anaerobic digestion. But photosynthetic
bacteria could use light energy to overcome the positive free energy of reaction (bacteria can utilize organic
acids for hydrogen production)
5
. The conversion of malate and lactate to hydrogen by photosynthetic bacteria
(mainly purple non-sulphur) is well documented
22, 25
. The main products of anaerobic fermentation are acetic and
butyric acids. Thus, further conversion of these acids into hydrogen by photofermentation underlines the synergy
of the integrated process. This combination of both kinds of bacteria not only reduces the light energy demand of
the photosynthetic bacteria but also enhances the hydrogen yield as well
5,34
.
Dark hydrogen fermentation is an incomplete oxidation, yielding not only hydrogen and CO
2
, but also organic
acids like, acetic acid. Therefore, for an economically sound process the remaining carbonaceous compounds are
to be converted, either in a photo-bioreactor to H
2
and CO
2
or in a methane reactor to CH
4
and CO
2
. If the dark
hydrogen fermentation is not followed by further conversion the H
2
yield will not warrant economic feasibility.

3 Energy Potentials of Biohydrogen and other Bioenergy Resources
Biohydrogen, bioethanol, and biomethane have many comparable points of resemblance, both in terms of
renewablity of their raw materials for production and their end-uses as fuels. However, bioethanol is a liquid
fuel, which unlike any gaseous fuel requires the process of distillation and dehydration during production.
Considering yields of ethanol from glucose as 1.6 mol/mol glucose, lower heating value of ethanol and glucose
as 296 and
712 kcal/mol, the distillation energy of ethanol as
50 per cent of the energy of the produced ethanol produced
35
, therefore,

Energy recovered as ethanol from glucose
= ( )
0.50
296 1.6 100 per cent
712

= 33.25 per cent

A simplified stoichiometric equation for producing hydrogen by utilization of glucose as substrate can be
written as:

C
6
H
12
O
6
+ 6H
2
O = 12H
2
+ 6CO
2
... (1)
J SCI IND RES VOL 63 SEPTEMBER 2004


736

The stoichiometric coefficients of the two gasses on the right hand side indicate that the volumetric ratio of
hydrogen to carbon dioxide should be 2 to 1. It is interesting to note that half the produced hydrogen comes from
glucose and half from water, which is split in this reaction.
The gross heating value of hydrogen is 68.6 kcal/mol, so that the energy yield per mol of glucose reacted can
be calculated as follows:

Hydrogen energy yield = 68.6 kcal/mol 12 mol
= 823.2 kcal

This can be compared to the energy yield of methane from anaerobic digestion, with reaction:

C
6
H
12
O
6
= 3CH
4
+ 3CO
2
... (2)

In Eq. (2), 180 g of glucose produces 48 g of methane and 132 g of CO
2
. The gross heating value of methane
is 212.27 kcal/mol.

Methane energy yield = 212.27 kcal/mol 3 mol
= 636.81 kcal

Therefore, theoretically it is evident that the energetic of hydrogen production compares favourably with
methane production.
Anaerobic conversion of carbohydrates into methane gas is well known. In the biomethanation process the
appropriate residues produce volatile acids in such a manner that it allows methanogens to build up, resulting in
the formation of CH
4
and CO
2
. Several studies with energy crops producing methane are found in literature with
algae, kelp and water hyacinth
36, 37
. It has been observed that conversion efficiencies of various crops grown for
methane production are generally under 50 per cent, depending on degree of mixing and the content of
celluloses/hemicelluloses. Energy recovery in biomethanation of distillery waste, both with and without
recycling of spent slurry varies within 56-65 per cent
38
. In another study, using live stock waste 32 GJ of
methane was obtained from an overall energy input of 82.5 GJ
39
. This shows that overall energy conversion of
this process of biomethanation is only 38.78 per cent. A comparison of production costs, conversion efficiency,
and net CO
2
emissions for different hydrogen production processes are given in Table 3. In the biological
hydrogen production from biomass, CO
2
is one of the products. Besides CO
2
and H
2
, no other gaseous products
are expected from the dark fermentation.
NATH & DAS: BIOHYDROGEN PRODUCTION AS A POTENTIAL ENERGY RESOURCE


737
Hydrogen is currently more expensive than other fuel options, so it is likely to play a major role in the
economy in the long run, if technology improvements succeed in bringing down costs. Biological hydrogen
production, employing renewable biomass may be a potential answer to overcome some of the economic
constraints to fulfill many of our energy needs. There is scope to use sugarcane juice; molasses or distillery
effluent as substrates, because they contain sugar in significant quantities. Therefore, production as well as unit
energy cost of biohydrogen would be reduced drastically. However, a rigorous techno-economic analysis is
necessary to draw a cost-effective comparison between biologically produced hydrogen and the various other
conventional fossil fuels. But economic survey, based on fuel cost estimation, turns out to somewhat
complicated when applied in practical terms. This is because of the intervening several other techno-economic
parameters. The socially relevant cost of bringing any fuel to market must also include such factors as pollution
and other short and long-term environmental cost, as well as direct and indirect health cost. When these factors
are taken into consideration, together with its initial cost competitiveness, hydrogen is surely the most logical
choice for a worldwide energy medium.

4 Concluding Remarks
It is widely acknowledged that hydrogen can offer tremendous potentials as a clean and renewable energy
currency. As a consequence, biological hydrogen production has been the subject of basic and applied research
for several decades. Many research works are available on the biochemistry, enzymology, and process
technology of biohydrogen production processes. Each process has its pros and cons in terms of technology and
productivity. Most of these works focus on the enhancement of hydrogen yield and also energy efficiencies of
the respective processes. But unfortunately, all these processes have yet to be evaluated rigorously in terms of
the cost for commercialization. Therefore, it is particularly imperative to address several techno-economic
challenges for cost-effective production as well as commercial application of biohydrogen.
Acknowledgement
Financial assistance obtained from the Department of Biotechnology, Government of India, is acknowledged.

References
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2 Boyles D, Bio-energy technology Thermodynamics and costs (John Wiley & Sons, New York) 1984, pp 8-13.
3 Nath K & Das D, Hydrogen from biomass, Cur Sci, 85 (2003) 265-271.
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Biotechnol, 70 (1999) 89-101.
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28.
Table 3 Comparison of hydrogen production costs, conversion efficiency and net CO
2
emissions

Production processes Conversion efficiency Production costs CO
2
emissions References
(per cent) (US$/Nm
3
H
2
) (kg/Nm
3
H
2
)

Natural gas reforming 75 0.45 0.8 40
Electrolysis of water with conventional electricity N A 0.32 1.8 40
Electrolysis with electricity from wind turbines ~75 0.35 0 40
Steam-reforming of bio-methane ~20 0.45 0 40
Photobiological hydrogen ~ 10 ~10** 0 10
Electrolysis with electricity from photovoltaic cells N A 4.13 0 40
2-stage bioprocess for hydrogen from biomass 15 0.35 0 40
Indirect micro-algal biophotolysis ~7 10* N A 41,42
Cyanobacterial biophotolysis N A 15* N A 43
Fermentative hydrogen ~22 ~ 40** N A 5
Hydrogen from coal/biomass N A 4** N A 44
* US$/GJ
** US$/MBTU
N A Not available

J SCI IND RES VOL 63 SEPTEMBER 2004


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_________
*Author for correspondence
Tel: +91-3222-278053, 283758; Fax: +91-3222-255303
E-mail: ddas@hijli.iitkgp.ernet.in