INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. (2015)

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3381

REVIEW PAPER

A review on biomass-based hydrogen production for

renewable energy supply
Seyed Ehsan Hosseini*,†, Mazlan Abdul Wahid, M. M. Jamil, Anis A. M. Azli
and Mohamad F. Misbah
High Speed Reacting Flow Laboratory, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor,
Malaysia

SUMMARY
This article gives an overview of the state-of-the-art biomass-based hydrogen production technologies. Various biological and
thermochemical processes of biomass are taken into consideration to find the most economical method of hydrogen produc-
tion. Biohydrogen generated by biophotolysis method, photo-fermentation and dark fermentation is studied with respect to
various feedstocks in Malaysia. The fermentation approaches of biohydrogen production have shown great potential to be
a future substitute of fossil fuels. Dark fermentation method is a simple biological hydrogen production method that uses a
variety of substrate and does not require any light as a source of energy. A promising future for biohydrogen production is
anticipated by this process both industrially and commercially. Feasibility of hydrogen production from pyrolysis and water
gasification of various biomass feedstock confirm that supercritical water gasification (SCWG) of biomass is the most cost-
effective thermochemical process. Highly moisturized biomass could be employed directly in SCWG without any high-
cost drying process. Indeed, a small amount of energy is required to pressurize hydrogen in the storage tank because of highly
pressurized SCWG process. The cost of hydrogen produced by SCWG of biomass is about US$3/GJ (US$0.35/kg), which is
extremely lower than biomass pyrolysis method (in the range of US$8.86/GJ to US$15.52/GJ) and wind-electrolysis systems
and PV-electrolysis systems (US$20.2/GJ and US$41.8/GJ, respectively). The best feedstock for biomass-based hydrogen
production is identified based on the availability, location of the sources, processes required for the preparation of the feed-
stock and the total cost of acquiring the feedstock. The cheapest and most abundantly available biomass source in Malaysia
is the waste of palm industry. Hydrogen production from palm oil mill effluent and palm solid residue could play a crucial role
in the energy mix of Malaysia. Malaysia has this great capability to supply about 40% of its annual energy demand by hydro-
gen production from SCWG of palm solid waste. Copyright © 2015 John Wiley & Sons, Ltd.

KEY WORDS
hydrogen; biomass; biological process; thermochemical process

Correspondence
*Seyed Ehsan Hosseini, High Speed Reacting Flow Laboratory, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia,
81310 UTM Skudai, Johor, Malaysia.
†
E-mail: Seyed.ehsan.hosseini@gmail.com

Received 14 March 2015; Revised 15 July 2015; Accepted 16 July 2015

1. INTRODUCTION utilized nowadays is oil, with a global energy consump-

The continued utilization of finite fossil fuels [oil, coal
and natural gas (NG)] has shifted attention to the future
energy mix of the world in the scarcity of fossil fuel re-
sources [1]. At present, fossil fuels supply approximately
80% of global energy demand [2]. According to the Sta-
tistical Review of World Energy in June 2014 by British
Petroleum (BP), the global primary energy consumption
increased by 2.3% in 2013, which is accelerated by
1.8% as compared with that in 2012. The most con-
sumed energy originated from non-renewable resources
such as oil and NG. The world’s leading fuel being
tion of 32.9% [3]. Fossil fuels such as NG and oil are
one of the greatest threats to the environment today.
The burning of fossil fuels releases high concentration
of carbon, which contributes to the greenhouse effect,
causing the global temperature to rise. This could lead
to the melting of polar ice caps, causing ocean levels
to rise and the salinity of the ocean to reduce, which
could endanger underwater organisms and poses a seri-
ous risk to the civilians and cities near the sea level
[4].The world energy demand is projected to be in the
range of 600–1000 EJ by the year 2050 [5]. Energy de-
mand of developing countries has grown because of their

Copyright © 2015 John Wiley & Sons, Ltd.

S. E. Hosseini et al.
economic growth [6]. To establish an environmentally
friendly energy for the future of the world, carbon-neu-
tral energy systems have been highlighted in recent years
[7,8]. Utilization of renewable and sustainable energy
(RSE) resources has been developed because of increas-
ing rate of greenhouse gases generation and global
warming [9]. Economic and environmental concerns are
generating a growing interest in alternative renewable
fuels [10]. Currently, less than 14% of the total energy
consumption originated from renewable resources such
as solar, wind, hydropower, biomass, biofuels, geother-
mal and hydrogen. This is due because of the technical
and geographical aspects of the renewable energy re-
sources, which are still under research and development
stages before it can emerge and replace the conventional
fossil fuels as the main energy resource. Hydrogen (H2)
as one of the most promising alternative energy carriers
is anticipated to play a great role in the future scenario
of energy sectors [11]. Hydrogen does not exist freely
in nature, and as the lightest element, it is a tasteless,
odourless and colourless gas. As a clean fuel, hydrogen
can easily be applied in fuel cells for electricity genera-
tion. Indeed, the energy content of hydrogen is about
122 kJ/g, which is 2.75 times higher than hydrocarbon
fuels [12]. Hence, utilization of hydrogen in transporta-
tion system has received much attention [13]. Vehicles
fuelled by hydrogen dramatically reduce dependence on
fossil fuel resources and significantly mitigate tailpipe
emissions [14]. The efficiency of hydrogen fuel cell ve-
hicles is three times more than gasoline engines [15].
Hydrogen can be employed as a fuel in internal combus-
tion engines without any substantial modification. Hydro-
gen as a fuel for automobiles illustrated some advantages
such as rapid burning speed, no toxic emission and a
high effective octane number [16]. Despite the great ca-
pability of hydrogen as an energy carrier, currently, the
bulk of produced hydrogen is utilized as a chemical
feedstock for food, metallurgical, petrochemical and elec-
tronics processing industries. Unavailability in nature and
the expensive production process of hydrogen are the
most important barriers that make hydrogen gas an un-
economic fuel. Indeed, utilization of hydrogen in vehi-
cles requires larger fuel tank because the energy density
of hydrogen is 10 MJ/m3, which is significantly lower
than methane (CH4) by energy density of 32.6 and pro-
pane (C3H8) by 86.7 MJ/m3 (at 15 °C and 1 atm) [17].
Nevertheless, the future scenario of hydrogen production
is the base of many RSE researches. It is anticipated that
the share of renewable resources will be 36% and 69%
of the total energy demand of the world by 2025 and
2050 respectively, with hydrogen shares of 11% in
2025 and 34% in 2050 [18]. Currently, about 95% of hy-
drogen demand in the world is provided from fossil fuel
resources followed by water electrolysis and biomass by
only 4% and 1%, respectively [19]. More than 50% of
all produced hydrogen is obtained from gasification of
NG, heavy oils, naphtha and coal [20]. At present, bio-
mass is not projected to play a significant role in
Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Biomass-based hydrogen production for renewable energy supply
hydrogen production; however, the conspicuous re-
sources of biomass in the world have attracted attention
to biomass-based hydrogen production [21]. Hydrogen
fuel from carbon-lean and carbon-free energy sources, in-
cluding biomass, could be the long-term aim of the hy-
drogen utopia [22]. Tropical countries are endowed
with abundant natural renewable biomass resources that
are potentially able to decrease their dependency to the
limited fossil fuel resources. The availability and regen-
erative capacity of biomass resources in one hand and
the low rates of replenishment and the physical finitude
characteristics of non-renewable fuel on the other hand
have clarified the importance of investment in biomass
production [23]. Palm oil, jatropha, soybean and rape-
seed are the most common vegetable oil resources in
the world. Among these biomass resources, palm oil by
about 35.5% annual total production has been introduced
as the biggest source of vegetable oil in the world [24].
2. ENERGY SUPPLY PATTERN IN
MALAYSIA
Malaysia, which is located in Southeast Asia, is a tropical
country with minor fluctuation in the weather temperature
due to its equatorial climate. The annual rainfall in Malay-
sia, which has been reported to be about 200–250 cm, is
excellent for agricultural activities [25]. Because of these
unique environmental circumstances, Malaysia has be-
come the largest producer and exporter of crude palm oil
in the world. It has been projected that oil palm cultivation
would increase to about 5.2 million hectares in 2020 [26].
Certainly, industrial sectors and the transportation system
consume around 43% and 36% of the total energy demand
of Malaysia [27]. Hence, depletion of fossil fuel resources
in the country and population growth are the main conse-
quences of increasing fossil fuel consumption in Malaysia
[26,27]. The population of Malaysia increased from
17.7 million in 1997 to 27.73 million in 2008 [28], and it
is expected to increase to 33.4 million in 2020 and, possi-
bly, to 37.4 million in 2030 [29], which is anticipated to
raise energy consumption significantly. In 2007, energy
consumption in Malaysia was recorded at 310 million GJ,
which showed 33.7% enhancement compared with that in
the year 1990 by 71 million GJ. Tick et al. [30] pointed
out that the period from 1990 to 2000 was the period of
rapid economic growth where double-digit growth was re-
corded in the demand for electricity. Lau et al. [31] stipu-
lated that the rate of energy demand in Malaysia
increases around 5–7% per year during the next two de-
cades. This high energy demand is anticipated to be contin-
ued to reach 130 million tonnes of oil equivalent in 2030
[32]. Although Malaysia is benefitted with fossil fuel re-
sources, the country will deplete its non-renewable energy
sources as it is predicted to hold out only for the next 30 to
40 years. Table I demonstrates the most important energy
resources and their consumption pattern in Malaysia [33].
Biomass-based hydrogen production for renewable energy supply S. E. Hosseini et al.

Table I. Energy consumption pattern in Malaysia (million gigajoules)

Year Hydropower Coal and coke Petroleum Natural gas Crude oil Total

2000 65.3 104
59.9 1104 907.4 2120.8

2001 70.6 124.3
80.2 1073.8 987.6 2176.1
2002 55.6 152.4
21.8 1092.7 948.1 2227
2003 44.2 222.5
58.2 1141.1 1 061.10 2410.7
2004 55.6 277.6
1.5 1220.2 1 060.70 2612.6
2005 54.9 288.4
3.1 1419.8 1 019.00 2779
2006 65.6 305.5
61.7 1497.8 1 042.80 2850
2007 63.2 370.4
41.6 1543 1 112.40 3047.4
2008 82.2 409.5
95.5 1644.9 1 121.00 3162.1
2009 68.1 447.7 4 1501 1 104.70 3125.5
2010 66 618.6 105.5 1546.4 941.4 3277.9
2011 77.4 618.4 93.1 1496.3 1 033.20 3318.4
2012 89.9 664.9
45.9 1618.1 1 174.50 3501.5

2.1. Biomass-based energy and Despite significant potential of biomass resources in

environmental issues in Malaysia
Biomass is an advantageous RSE that can be employed as
a fuel to generate electricity and other forms of energy.
Biomass feedstock is any organic matter available on a re-
newable basis for conversion to energy. Agricultural crops
and residues, farm animal wastes, industrial wood and log-
ging residues, food residues and the organic portion of mu-
nicipal waste are all types of biomass feedstock. Muis et al.
[34] pointed out that biomass is a proven option for elec-
tricity generation in Malaysia. The economy of Malaysia
could be bolstered by biomass utilization in energy mix
of the country by providing job opportunities in rural areas.
Utilization of biomass can decrease the dependence on for-
eign energy sources, as is currently the case in many devel-
oping countries. Deployment of biomass-based energy
generation can create various job opportunities for utility,
power equipment and agricultural equipment industries
[35]. On the other hand, the increasing rate of total carbon
dioxide (CO2) emissions from fossil fuels can be controlled
by biomass-based energy utilization.
Besides CO2, other greenhouse gases such as methane
(CH4), nitrogen oxide (NO) and sulfur oxide are generated
by increasing rate of fossil fuel consumption. Conse-
quently, the average temperature has risen by 0.5 °C to
1.5 °C in peninsular Malaysia, while the temperature in-
crease in East Malaysia is approximately 1 °C [36]. During
the past 40 years, the value of CO2 emissions in metric tons
per capita in Malaysia has reached a maximum value of
7.81 in 2008 and a minimum value of 1.34 in 1970 [37].
Because an abundance of renewable biomass resources
has been known in Malaysia, utilization of this alternative
fuel could play an effective role in environmental protec-
tion of the country. Among all RSE resources, biomass
has the highest potential to be employed as a renewable
source of energy in Malaysia [38]. The total land area in
Malaysia is 32.90 million ha, which includes 20.10 ha
(61%) under natural forest cultivation and 4.89 ha (14.9%)
agricultural sector [39]. Various types of available biomass
are listed in Table II [40].
Malaysia, it has not been seriously taken into consideration
in the energy mix of the country [41].
In Malaysia, the main produced agricultural crops are oil
palm, rubber, cocoa, rice and coconut. In terms of acreage,
oil palm and rubber plantations are the major plantations in
Malaysia. The Malaysian government has focused on using
renewable biomass from the oil palm industry, which in-
cludes empty fruit bunches, fibre and shells, to produce en-
ergy. Because Malaysia is one of the largest palm oil
producers in the world, around 85.5% of total available bio-
mass in the country is palm oil waste (around 55.73 million
tonnes per year) [42]. Ong et al. [43] pointed out that ap-
proximately 19 million tonnes per annum of biomass waste
is produced in the form of empty fruit bunches, shells and fi-
bre in Malaysian palm oil mills. The cost of palm solid waste
is estimated to be US$1772m per year [44].
After palm solid residue (PSR) and wood waste, rice
husk from rice mills is the third most important biomass re-
source in Malaysia [45]. Moreover, biomass from paddy
straws has been named as an important source of biomass
in the country [36]. Other biomasses from cocoa, coconut
and sugarcane cultivation are of minor importance because
of their lesser annual available quantities [39].
3. FEASIBILITY STUDY OF
HYDROGEN PRODUCTION IN
MALAYSIA
The feasibility of hydrogen production in Malaysia can be
determined by taking into account several aspects such as
availability of feedstock, complexity and capability of cur-
rent production technologies and economic issues. As
shown in Table III, there are various technologies that are
available for hydrogen production in Malaysia. However,
the selection of these technologies and the required feed-
stock are restricted to the cost and economic issues.
The important parameters in choosing the best feed-
stock for hydrogen production are the availability, location

Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
S. E. Hosseini et al. Biomass-based hydrogen production for renewable energy supply

Table II. Annual biomass production in Malaysia

Biomass Average Potential Current

Biomass Moisture production calorific biomass amount
production content in dry weight value energy of produced
Crops (million tons/year) (%) (million tons/year) (Megajoule/kg) production (PJ) energy (PJ)

Oil palm Empty fruit 38.55 60 15.42 6.028 92.95 —

bunches
Fruit fibres 1.32 40 0.792 11.34 8.98 0.14
Palm shell 4.41 20 3.528 18.84 66.47 0.08
Paddy plants Rice husk 0.3755 13-14 0.3267 14.93 4.88 —
Coconut trees Coconut husk 0.171 11.5 0.1513 19.6 2.97 0.0139
Sugarcane Bagasse 0.2037 50 0.1019 14.4 1.47 0.0025
Logging Logging residues 2.649 12 2.3311 18.41 42.92 —
Wood industry Wood residues 3.652 12 3.2138 18.41 59.17 0.0219
1 tonne, 1000 kg; PJ, petajoule; potential biomass energy production = biomass production in dry weight × average calorific value;

9
1 MJ = 1 x 10 PJ

Table III. The main hydrogen production technique

Overall efficiency
Method Feedstock Drawbacks (%)

Steam reforming Natural gas, oil Pollutant, unstable price of feedstock 70–80
Biomass gasification/pyrolysis Biomass Pollutant 42–48
Coal gasification Coal Pollutant 50–80
Electrolysis Water Electricity cost 35–50
Thermochemical Water Corrosion 50

of the sources, processes required for the preparation of the
feedstock and the total cost of acquiring the feedstock. For
instance, although coal is one of the most famous fossil
fuel feedstock for hydrogen production [46], this feedstock
is infeasible economically and technically for hydrogen
production in Malaysia. The cheapest and most abundantly
available fossil fuel is coal, and the Malaysia coal reserve
is currently about 1712 million tons of various coals rang-
ing from lignite to anthracite. Malaysia’s coal deposits are
mainly located in the rural and remote areas where infra-
structures are poor, and the development of infrastructures
to transport these coals requires high cost. Furthermore, the
majority of the coal deposits are located underground,
which requires underground mining and consequently
higher cost. Because of the high cost of locally sourced
coal, 90% of the coal demands in Malaysia are fulfilled
by importing coals from Australia, Indonesia, China and
South Africa [47]. As a result of high extraction cost of lo-
cal coals, the coal gasification technology is not feasible
for hydrogen production in Malaysia. The steam-reforming
technology is the most feasible method in producing hy-
drogen in large scale. This is because the most feasible
feedstock available for hydrogen production remains to
be fossil fuels, although Malaysia has diverse renewable
energy resources such as solar energy, wind energy and
biofuels. When NG is not available, higher hydrocarbons
can be used as feedstock, taking advantage of the surplus
of various hydrocarbon streams in many refineries [48].
Because of the efficiency and economic benefits of
steam-reforming method, many studies had been carried
out to improve this technology. Recently, better materials
for reformer tubes, better control and understanding of car-
bon limits and better catalysts and process concepts with
high feedstock flexibility have been incorporated to steam
reforming technology, contributing to less costly and more
efficient plants [49]. In Malaysia, the diversity of natural
resources supported the government initiatives in promot-
ing renewable energy development based on the 5th Fuel
Policy. The renewable resources such as biomass are abun-
dantly available in Malaysia. Biomass is a promising re-
newable resource to produce hydrogen. Malaysia is
located in a strategic location and is blessed with a variety
of biomass such as residues from palm oil, rice, sugarcane
and the wood industry. However, issues regarding trans-
portation and preparation of biomass are the main chal-
lenges. The cost for transportation and preparation of
biomass is fundamentally very high. This results in the con-
struction of small hydrogen plants without considering the
economical aspect. One solution to this issue is by building
a hydrogen plant near the biomass resources as to minimize
the transportation cost. Another challenge in biomass-based
hydrogen production is that it requires better catalysts to im-
prove yields and selectivity, as bio-fuels are more difficult to
reform because of its large composition of carbon atoms [50].
Table IV shows the sources of biomass and the potential of
these biomass sources as a fuel to generate hydrogen [51].

Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Biomass-based hydrogen production for renewable energy supply S. E. Hosseini et al.

Table IV. Energy/ hydrogen potential from biomass major ingredients of lignocellulose [54]. The molecular
weights of the first three parts are high with much mass,
Potential annual Potential
while the molecular size of the last item is small and avail-
Production generation capacity
Sources (kton/year) (GWh) (MW)
able in little quantity [55]. Cellulose could also be col-
lected in different forms of domestic and industrial
Rice mills 424 263 30 wastes. Sealre et al. [56] stipulated that a fair amount of
Wood industry 2177 598 68 cellulosic waste comes from uneaten food and garden clip-
Palm oil mills 17 980 3197 365 pings (lawn grass, tree branches, etc.).
Biogases 300 218 25 The high molecular weight cellulose has a linear
Palm oil 31 500 1587 177 syndiotactic polymer of β → 1, four-linked D-glucose units,
mill effluent which can emerge as a highly crystalline material [57]. A
schematic framework of lignocellulosic biomass is shown
in Figure 1 [54].
The supercritical water gasification (SCWG) of biomass as In order to enhance the liquid yields, thermochemical
a new effective technology to produce hydrogen has attracted conversion techniques such as pyrolysis [58], liquefaction
attention. The theoretical amount of hydrogen production via [59], gasification [60,61] and supercritical fluid extraction
SCWG of oil palm waste could be about 2.16 × 1010 kgH2/ [62] have been developed. However, these technologies
year from 184.6 million tons of worldwide oil palm wastes are not economically competitive with NG steam
[52]. Malaysia, being the world’s largest producer and ex- reforming for hydrogen production because of the high-
porter of palm oil, has a great potential in utilizing SCWG cost biomass harvesting, growing and transporting pro-
technology for hydrogen production. It was claimed that more cesses. The price of biomass-based hydrogen from direct
than 40% of total energy demand of Malaysia could be gener- gasification is approximately three times higher than hy-
ated by hydrogen produced by SCWG of oil PSR. The annual drogen from SMR [63]. However, compared with the fossil
oil palm fruit production in Malaysia is approximately 100 fuel-based hydrogen, the rate of released CO2 reduces in
million tonnes, in which the solid waste of the fruits is capable biomass-based hydrogen production because the released
to generate around 1.05 × 1010 kgH2 (1.26 EJ) via the SCWG CO2 in the gasification of biomass was previously
process. Currently, the hydrogen production from supercriti- absorbed from the environment and fixed by photosynthe-
cal water biomass gasification in Malaysia is still developing. sis in the growing plants [64]. Improvement of CO2 bal-
Further research into improving and understanding the de- ance by about 30% is one of the main advantages of
tailed processes for this hydrogen production technology is re- biomass-based hydrogen production [65]. Among various
quired as this technology is found to be feasible for hydrogen production technologies from RSE resources
Malaysia’s energy [53]. (such as solar to hydrogen, wind to hydrogen, geothermal
and tidal energy to hydrogen), biomass-based hydrogen
production has posed the best condition in terms of eco-
nomic and environmental issues [66]. Based on the feed-
4. BIOMASS-BASED HYDROGEN stock, the cost of biomass-based hydrogen is various. In
PRODUCTION an economic point of view, availability and the low prices
of biomass feedstock, and in an environmental aspect, sul-
The chemical structure and organic components of bio- fur removal system and CO2 capture and storage, play im-
mass, which include cellulose (40–50%), hemicelluloses portant parameters that make biomass-based hydrogen
(25–30%), lignin (15–20%) and extractives, are the four competitive with fossil fuel-based hydrogen production

Figure 1. Framework of lignocellulose.

Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
S. E. Hosseini et al.
[67]. The major pathways of biomass-based hydrogen pro-
duction are illustrated in Figure 2 [68].
Gasification (steam gasification and SCWG), steam
reforming of bio-oils and pyrolysis are the most well-
known thermochemical processes of biomass-based hydro-
gen production. Moreover, photo-fermentation, bio-pho-
tolysis of water using green algae and blue-green algae
(cyanobacteria), dark-fermentation and hybrid reactor sys-
tem are the most important biological hydrogen production
processes. The high efficiency (thermal to hydrogen is up
to 52%) and low cost of biomass-based hydrogen produc-
tion via thermochemical process are the most important
characteristics of this method [69].
5. BIOLOGICAL BIOMASS-BASED
HYDROGEN PRODUCTION
Biohydrogen [67] production with anaerobic bacteria started
in the 1980s. Because of special attention to sustainable de-
velopment and waste management, biohydrogen research
has significantly increased over the last decade [68,69].
The most important technologies for biohydrogen produc-
tion include the following: water–gas shift hydrogen produc-
tion, direct photolysis hydrogen production from water by
cyanobacteria or green algae, photo-fermentative hydrogen
production, dark-fermentative hydrogen production process
during the acidogenic phase of anaerobic digestion and
two-stage dark/fermentative [70]. Photolysis and photo fer-
mentation are light-dependent, while dark fermentation is
light-independent that takes place in the dark [71]. Compared
Figure 2. Pathways of biomass-based hydrogen production.
Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Biomass-based hydrogen production for renewable energy supply
with the thermochemical biomass-based hydrogen production
processes, biohydrogen method displays less energy intensity
[72,73].
5.1. Biophotolysis
Splitting of water molecules (H2O) to form oxygen (O2)
and hydrogen (H2) with light as a source of energy is
biophotolysis [74]. This process is categorized into two
kinds: direct biophotolysis and indirect biophotolysis. Di-
rect biophotolysis is a biological process that can produce
hydrogen directly through energy conversion in the form
of hydrogen from solar to chemical energy using photosyn-
thesis process of microalgae in water [75]. Direct photoly-
sis involves a photosynthetic ability of the microorganisms
to break water nonstop into O2 and H2. The main advan-
tage of this process is that water is used as the major
source, which is readily in abundance. Another merit for
this process is that even in low light, green algae and anaer-
obic conditions are still able to convert almost 22% of light
energy by using hydrogen as an electron donor in the pro-
cess of fixation of CO2. Production of oxygen by microor-
ganisms, in addition to hydrogen production, is a negative
point because when organisms sense oxygen, hydrogen
production is stopped [76]. Indeed, to prevent building up
of oxygen, the ratio of oxygen production (photosynthesis)
to oxygen consumption (respiration) should be changed
[77]. Although it was found that addition of sulfate to the
solution is effective for depression of oxygen production,
the rate of hydrogen production also decreases [78]. Fur-
thermore, because H2 and O2 are the main products of this
Biomass-based hydrogen production for renewable energy supply
technique, significant safety is required. Low efficiency
and non-continuous process of hydrogen production are
the main tremendous challenges [79].
5.2. Hydrogenase and nitrogenase enzymes
Hydrogenase enzymes are biological enzymes divided into
two types: iron–iron (fe–fe) and nickel–iron (Ni–Fe) enzymes
[76,77]. Iron and nickel are metals that are easy to obtain and
cheap. Fe–Fe is mostly used because it is more efficient than
Ni–Fe [80]. This enzyme is commonly found in microorgan-
isms like cyanobacteria green algae. Therefore, hydrogen is
obtained through conversion of protons with production of ox-
ygen. Hence, this enzyme is sensitive to oxygen change [81].
Nitrogenase enzymes convert nitrogen molecules to pro-
duce hydrogen in anaerobic condition [82]. Cyanobacteria
is the only microorganism tested to contain this type of en-
zyme in biohydrogen production [83]. It is divided into nitro-
gen fixation (which requires ATP) and non-nitrogen fixation.
Figure 3 demonstrates how a heterocyst prepares an oxy-
gen-free condition to the oxygen-sensitive nitrogenase that
decreases molecular nitrogen into NH3 and protons into hy-
drogen based on reaction (1) [84]. In an N2-containing envi-
ronment (such as air), N2 fixation is the dominant reaction,
while hydrogen is a minor byproduct. Based on reaction
(2), higher rates of H2 could be constituted in the absence
of molecular N2. The required energy for hydrogen evolu-
tion is provided by neighbour cells or derived from the en-
ergy-rich carbohydrate (CH2O). The efficiency of energy
conversion from light to H2 by nitrogenase is low (<1%) be-
cause of the high energy demand (four ATP per hydrogen)
[85].
N2 þ 8Hþ þ 8e
þ 16 ATP → 2NH3 þ H2
þ16 ADP þ 16 Pi nitrogen fixation reaction
(1)
8Hþþ 8e- þ 16 ATP→4H2 þ 16 ADP (2)
þ16 Pi non-nitrogen fixation reaction
Indirect biophotolysis process uses cyanobacteria and
Figure 3. Nitrogenase-mediated hydrogen evaluation in a heterocyst of nitrogen-fixing heterocystous cyanobacteria.
S. E. Hosseini et al.
microalgae in water, and hydrogen is produced through en-
ergy conversion from sunlight to chemical energy using dif-
ferent approaches of light and no-light approaches such as
dark aerobic fermentation, biomass production by photosyn-
thesis and biomass concentration. Water and CO2 are the
major inputs involved in the growth of microalgae and
cyanobacteria using hydrogenase enzyme as catalytic bacte-
ria for the production of hydrogen [86]. Water is the donor in
the hydrogen production; thus, biophotolysis does not re-
quire any substrate as nutrients. The method of hydrogen pro-
duction using cynanobacteria and microalgae is of advantage
because of the fact that it uses light as energy source and wa-
ter as a substrate; if appropriately utilized, the hydrogen pro-
duced could be used in fuel cell to generate electricity [87].
5.3. Photo fermentation
In photo fermentation or so-called photosynthetic bacterial
hydrogen production, the nitrogenase characteristic of pur-
ple non-sulfur bacteria plays a crucial role to evolve H2. In
order to scavenge transferred light energy to membrane
reaction centres, light-harvesting pigments such as
phycobilins, carotenoids and chlorophylls are employed.
Water is converted into electrons, protons and oxygen by
sunlight energy. By utilization of nitrogenase catalyst in
the process, the protons and electrons react with nitrogen
and ATP to make ADP, H2 and ammonia [88]. The process
is performed in the lack of nitrogen circumstance
employing primarily infrared light energy. One of the most
advantages of this technique is that oxygen does not inhibit
the process. Furthermore, the bacteria (which use the hy-
drogen byproduct to reinvigorate other energy-requiring
processes via the uptake hydrogenase enzyme) can be used
in various circumstances (such as polyurethane foam, po-
rous glass or continuous cultures) [12]. Nevertheless, some
important parameters such as high amount of required en-
ergy for the process, re-oxidation of hydrogen, slow nitro-
genase enzyme and limited availability of organic are
named as disadvantages of this process [76]. By engineer-
ing the ratio of carbon to nitrogen nutrients, the required
energy for the process decreases and the activity of
Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
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S. E. Hosseini et al.
nitrogenase enhances. Indeed, to reduce the nitrogenase
dependent on the high levels of nitrogen nutrients, enzyme
engineering should be maintained.
5.4. Dark fermentation
Dark fermentation is requiring complex organic com-
pounds; it appears to be favourable among the methods
of hydrogen production, and it operates in anaerobic condi-
tion (without oxygen). Hydrogen is produced at high rate
and low cost with various organic substrate and wastewa-
ters enriched with carbohydrates. Three types of bioreac-
tors could be used to yield hydrogen in dark fermentation
process. In fermentative hydrogen production, many feed-
stocks were used, which includes biomass, agricultural
waste, food processing waste, sewage sludge and livestock
effluents [89]. Dark fermentation under anaerobic is con-
sidered more encouraging, given that the hydrogen pro-
duced is optimum with little cost using wastewaters
carbohydrate-based substrate [90]. Based on temperature
distribution, dark fermentation processes are classified into
low (mesophiles), medium (thermopiles) and high
(Hyperthermophiles) temperature process. Aerobes mi-
crobes, anaerobes organisms and facultative anaerobes were
tested using different temperature ranges. Ferchichi et al.
[91] found that Clostridium saccharoperbutylacetonicum
ATCC 27021 grown on pure carbohydrate (disaccharides)
and hydrogen yield was more than twice 2.81 mol-H2/mol
sugars greater than monosaccharide 1.29 mol-H2/mol hex-
ose. It was claimed that the rate of production of hydrogen
with monosaccharide is much higher than disaccharides
[92]. Because carbohydrates are the main source of hydrogen,
complex carbohydrates, biomass rich in sugars and sewages
may appear to be suitable for biohydrogen production [93].
In dark fermentation, hydrogen is usually produced by
pyruvate. Pyruvate is produced through Embden–Meyer-
hof–Parnas (EMP) pathway, which is divided into acetyl-
CoA and formate by PFL (pyruvate formate lyase) under
anaerobic conditions [94]. The substrate can be exogenic
or endogenic. Hydrogen is obtained through conversion
of pyruvate dark condition. The pyruvate disintegration is
controlled by two enzymes, namely, PFL and pyruvate
ferridoxin oxido-reductase [95]. Oxygen is not produced
in dark fermentation. Dark fermentation-based hydrogen
is not competitive with the commercialized hydrogen pro-
duction processes (from fossil fuels) in terms of reliability,
efficiency and cost. The efficiency of fermentation hydro-
gen is about 1–5%, which shows that the process needs
to advance in terms of efficiency [96].
Although anaerobic digestion of organic waste includ-
ing agricultural and municipal waste and wastewater
sludge has illustrated its sustainability for H2 production,
the low yields of hydrogen realized from the fermentation
of even the simplest sugars restrict current H2 production
[97]. Kotay et al. [98] pointed out that a combination of
dark and photo-fermentation in a two-stage hybrid system
ameliorates the overall yield of hydrogen. The first step is
decomposition of starch or glucose by anaerobic bacteria
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Biomass-based hydrogen production for renewable energy supply
via acetate fermentative metabolism, and the second step
is conversion of resultant acetate to hydrogen by photosyn-
thetic bacteria in another reactor. Twofold hydrogen yield
is reported by Tao et al. [99] in comparison with that using
only dark-fermentation. It was claimed that by utilization
of two-step photo-fermentation, the total hydrogen produc-
tion increases from 3.6 to 6.63 mol H2/mol sucrose.
Rittmann et al. [100] stipulated that the discontinuous
monitoring of culture parameters and the emergence of un-
stable culture circumstances due to sample removal and/or
inhibition of biohydogen production by buildup of liquid
and gaseous metabolic products are the most important
drawbacks of dark fermentation technique. Manipulation
to the culture needs to disrupt at least one physical factor,
which results in non-continuous cultivation conditions
and making the application of closed batch technique
rather unattractive [101]. In dark fermentation, beside pure
hydrogen, a mixed biogas containing primarily H2, CO2
and lesser amounts of CH4, CO and hydrogen sulfide
(H2S) is generated [102].
5.4.1. Factors that influence dark fermentation
5.4.1.1. Organic loading Rate. Organic loading rate
(OLR) affects the rate of biohydrogen production. Studies
have shown this effect using different types of substrate
loading when wastewater was used as a substrate. Microor-
ganism acts on organic substrate to yield hydrogen. OLR is
evaluated using two quantities: hydraulic retention time
(HRT) and chemical oxygen demand (COD). Glucose
sugar was used, and the OLR was measured in g/L day,
which is equivalent to the extent of the COD (g/L) fed at
a certain period of time. Thus, the high OLR does not nec-
essary result in higher hydrogen production. However, it is
significant to consider certain range of the OLR due to the
microbial growth and hydrogen production [103]. In an ex-
perimental investigation of hydrogen production via dark
fermentation process, implemented by Mariakakis et al.
[104], it was found that the maximum hydrogen production
reaches to 1.72 mol H2/mol hexose for HRT equal to 1.6 d
and OLR of 20 g sucrose/(L∙d), while no hydrogen gas pro-
duction could be established for OLRs lower than 10 g su-
crose/(L∙d), a value that can be considered as threshold.
5.4.1.2. Temperature. Temperature is an environ-
mental factor that affects the biological hydrogen produc-
tion. There are three ranges of temperatures that acted on
the bacteria during biohydrogen production: psychrophilic
0–20 °C, mesophilic bacteria 20–42 °C and thermophilic
bacteria 42–75 °C [105]. Reports have shown how the tem-
perature effects proportionally on the production rate of hy-
drogen. Hydrogen production rate using thermopiles was
observed to be higher than that in mesophilic bacteria
[103]. However, no standard was observed yet regarding
the exact temperature to be used in biological hydrogen pro-
duction. The best possible temperature to be used in dark fer-
mentation depends on the type of biocatalyst and the type of
employed substrate and carbon source. Both mesophilic and
thermophilic temperatures were applied to be optimal for
Biomass-based hydrogen production for renewable energy supply S. E. Hosseini et al.

fermentative H2 production. Thermophilic conditions were 5.5. Substrate

reportedly advantageous because of its thermodynamics
[95,96], which gives higher reaction rates with better process
performance and decreased problems with contaminating
hydrogen-consuming microorganisms. The most selected
temperature is between 37 and 45 °C for enterobacter species
[83]. The optimum temperature of 60 °C was found for hy-
drogen production using thermoanaerobicterium thermo-
saccharolyticum PSU-2 [106].
5.4.1.3. Hydraulic retention time. Hydraulic reten-
tion time factor is mostly related to change of volume of
the substrate during fermentation period. The quantity of
the liquid feedstock is retained over time in the working
liquid inside the reactor. Increase in HRT also results in
higher hydrogen production [103]. The highest amount of
hydrogen produce was observed at optimal HRT of 36 h
while the lowest was recorded at 12 h [107].
5.4.1.4. pH. The influence of pH in dark biohydrogen
production is mostly related to the metabolism of the feed-
stock that is used during fermentation period. Hydrogenase
is an enzyme that plays a role in PH changes during hydro-
gen production. Generally, pH value that is more acidic is al-
ways considered favourable. It was reported that the best pH
for fermentation should be in the range of 5.5 to 6.0 [108].
Highest yield of hydrogen using mixed microflora as a sub-
strate was obtained at a pH of 4.5 [103]. It is also observed
that the changes of pH are attached to the bacterial action
on the substrate during production. Hence, the most impor-
tant parameter is obtaining the first initial value of pH and
managing the value over the period of production.
The selection of the best substrate is classified based on the
availability, cost, purity of substrate and biodegradability.
Various types of substrate have been employed in fermen-
tative hydrogen production, which are classified into agri-
cultural waste, biomass, lignocelluloses products (include
herbaceous, wood waste; food-based substrate are used
from food processing waste, aquatic plants and algae, sew-
age sludge, animal excreta and livestock effluents). A sum-
mary of biohydrogen production based on various
feedstocks is presented in Table V [95,97,98].
Generally, the renewable feedstock used for hydrogen
production is categorized into three major groups that in-
clude pure carbohydrate, food-substrate and wastewater
sludge. In fermentative hydrogen production, high carbohy-
drate contents are the main source of hydrogen to be ob-
tained in a substrate [109]. Food-based feedstock is usually
derived from industrial wastes (food-related wastes, munici-
pal wastes and food residue) [93]. Carbohydrate-based sub-
strates are always preferred to the protein and fat wastes
because the carbohydrate-based substrate is about 20 times
higher than protein waste and fat-based wastes during hydro-
gen production [110]. The amount of hydrogen produced
from food-based wastes was reported in the ranges of
0.68 mol-H2/mol-hexose to 2.70 mol-H2/mol hexose, which
is close to production obtained from pure carbohydrate
[111]. Proper utilization of the municipal waste will help
most of the developing countries to make some step towards
the eradication of the wastes and at the same time results in
H2 production. In this regard, hydrogen production from
some waste substrate such as paper mill waste [112],

Table V. Biohydrogen from various substrates

Substrate Microorganism/inoculum Yield mol H2/mol of substrate Reference

Glucose Anaerobic digester sludge 2.69 [100]

Glucose Anaerobic digester sludge 2.8 [103]
Xylose Anaerobic mixed culture 2.25 [151]
Xylose Enterobacter aerogenes 2.2 [152]
Arabinose Mixed culture sludge 1.98 [83]
Arabinose Escherichia coli strain 1.02 [106]
DJT135
Galactose Escherichia coli strain 0.69 [106]
DJT135
Mannose Enterobacter aerogenes 0.98 [107]
strain HO-39
Mannose Citrobacter sp. CMC-1 1.93 [108]
Sucrose Anaerobic digester sludge 1.9 [153]
Potato processing wastewater Soil inoculums 0.004 [154]
Cheese whey Clostridium saccharobutylacetonicum 0.0079 [88]
ATCC27021
Sugarbeet juice Anaerobic digester sludge 1.7 [153]
Food waste and sewage sludge Anaerobic digester sludge 0.005 [107]
Wheat starch co-product Anaerobic digester sludge 1.3 [109]
Thin stillage Acclimatized anaerobic digester sludge 0.77 [93]
Sugarcane bagasse Clostridium butyricum 1.73 [110]
Sugar cane bagasse hydrosylate Elephant dung 0.84 [111]

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S. E. Hosseini et al.
municipal solid waste [113], starch effluent [114], food-pro-
cessing wastewater [115], rice wastewater [116], distillery
and molasses-based wastewater [117] and domestic waste-
water [118] were experimented by various researchers.
6. HYDROGEN PRODUCTION FROM
PALM OIL MILL EFFLUENT
Palm oil mill waste is categorized into liquid, solid and
gasses waste. Hydrogen production from palm oil gasses
waste has not been developed properly yet. When looking
into liquid waste, it is definite that the waste will be re-
leased to the river or water stream system as it the most
economic manner to manage the waste. Palm oil mill efflu-
ent (POME) is the water waste that is being discharged
from the sterilization process of oil palm fruit, crude oil
clarification process and cracked mixture separation pro-
cess [119]. Discharging POME to the environment is
harmful to the aquatic ecosystem because of creating
highly acidic environments or causing algal growth, which
occurs on the surface of the water because of the COD and
biological oxygen demand. Hence, an alternative way to
make POME become useful and harmless to the environment
is to produce hydrogen from POME. Several discussions
were made based on POME waste to produce hydrogen. Atif
et al. [120] discussed about anaerobic production of hydro-
gen from POME by anaerobic microflora in 5-1 bioreactor
at 60 °C and pH 5.5. They found that in a fed batch reactor,
hydrogen yields a total of 4.708 l H2/1 POME. In 2006,
POME was adopted as supplementary substrate in the anaer-
obic contact filter system under mesophilic conditions by
Vijayaraghavan and Ahmad [121], signifying a cumulative
gas generation of 11.8 l/week (56% hydrogen) corresponding
to COD removal of 67%. Figure 4 shows the schematic
diagram of up-flow anaerobic contact filter for hydrogen gen-
eration. In this experiment, the mixed type reactor unit in-
cludes acrylic column (100 ID × 1200 mm height), and 40-
mm diameter rigid circular porous plastic balls are employed
as a packing material. The openings in porous ball were
3 mm with a cross fluted at every one-fourth of the ball
diameter [121].
Prasertsan et al. [122] optimized hydrogen production
from POME by thermoplilic fermentative process. The
waste sample was held in a constructed bioreactor for
2 days at 60 °C to increase the yield of hydrogen. A maxi-
mum hydrogen yield of 0.27 l H2 g/COD was reported by
the authors. A 50 L of continuous stirred tank reactor was
employed by Yusoff et al. [123] to produce hydrogen from
POME. The result indicated that lab-scale hydrogen pro-
duction efficiency did not correlate well when up-scaled
to pilot plant. The rate of hydrogen yield was obtained at
74 mL/h/L-POME (70% hydrogen content) and 33 mL/h/
L-POME (25% hydrogen content) in lab scale and pilot
plant, respectively. Singh et al. [124] employed cell immo-
bilization techniques to produce hydrogen using
immobilized anaerobic sludge as the seed culture. POME
was used as the substrate carbon source. They found that
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DOI: 10.1002/er
Biomass-based hydrogen production for renewable energy supply
with a POME concentration of 20 g COD/l in the feed,
the suspended-cell-containing reactor was able to produce
hydrogen at an optimal rate of 0.348 L H2/(L POME h) at
HRT of 6 h. The immobilized cell-containing reactor illus-
trated a better hydrogen production rate of 0.589 L H2/(L
POME hour), which occurred at HRT of 2 h. When the
immobilized-cell-containing reactor was scaled up to 5 L,
the hydrogen production rate was 0.500–0.588 L H2/(L
POME hour) for HRT of 2 to 10 h, but after a thermal treat-
ment of POME for 1 h at 60 °C, the rate increases to 0.632
L H2/(L POME hour) at HRT of 2 h. The main soluble me-
tabolites were butyric acid and acetic acid, followed by
propionic acid and ethanol. Successful researches in hydro-
gen production from POME indicate that utilization of
POME (as material to produce hydrogen through various
methods) will be implemented in large-scale hydrogen pro-
duction in the future.
7. HYDROGEN FROM BIOMASS
PYROLYSIS
Biomass pyrolysis is a route of gaseous, liquid (tar and
other organics) and solid (char) production for generation
of alternate sources of energy [125]. The required temper-
ature for pyrolysis is between 352 and 502 °C, and the re-
lated pressure is 0.1–0.5 MP in the absence of air [126].
Because of the operating system, the pyrolysis process is
known as fast pyrolysis and slow pyrolysis. High-tempera-
ture gas and low-temperature tar is produced in biomass
fast pyrolysis, while high charcoal continent is generated
in slow pyrolysis [127]. High-temperature fast pyrolysis
in very short residence times yields higher rates of hydro-
gen [128]. Because the major product of slow pyrolysis
is charcoal, this process is not taken into account for hydro-
gen production. In the fast pyrolysis process, the biomass
feedstock is heated quickly in the absence of air to form va-
pour and condense to a dark brown mobile bio-liquid. The
products of fast pyrolysis include gaseous products (CH4,
H2, CO, CO2 and other gases based on the organic nature
of the biomass feedstock); liquid products (tar and oils
such as acetic acid and acetone, which are liquid at room
temperature); and solid products (composed of char and
pure carbon plus other inert materials). Although pyrolysis
processes are applied for biofuel production, biomass-
based hydrogen can be generated directly through fast py-
rolysis in high-temperature circumstance and sufficient
volatile phase residence time (reaction 3).
Biomass þ heat→ CH4 þ CO þ H2 (3)
þ other products
To raise the rate of hydrogen production from fast py-
rolysis mechanism, steam reformation of methane and
other produced hydrocarbon vapours is carried out based
on reaction (4).
Biomass-based hydrogen production for renewable energy supply
Figure 4. Schematic of up-flow anaerobic contact filter for hydrogen production.
CH4 þ H2 O →CO þ 3H2 (4)
Moreover, water–gas shift reaction (reaction 5) is ap-
plied to enhance the rate of hydrogen production.
CO þ H2 O→CO2 þ H2 (5)
Based on water solubility, the oily byproducts of pyrol-
ysis are separated into two fractions. The water-soluble
byproducts are applied for hydrogen production, while
the water-insoluble byproducts are used for adhesive pro-
duction. Type of catalyst, temperature, heating rate and
residence time are the most important parameters that con-
trol hydrogen yield from pyrolysis biomass process. The
adjusting of these parameters is implemented by the selec-
tion of reactor type and heat transfer modes, such as solid–
solid conductive heat transfer and gas–solid convective
heat transfer [129]. In pyrolysis biomass hydrogen produc-
tion, high temperature, high heating rate and long volatile
phase residence time are crucial [130]. The yield of hydro-
gen from pyrolysis of biomass is augmented significantly
when Ni-based catalyst is employed. Further, hydrogen
could be produced by using additional steam reforming
and water–gas shift reaction [77]. The heat transfer modes
and features of various reactors are listed in Table VI.
From this table, it can be found that fluidized bed reactor
S. E. Hosseini et al.
type demonstrates higher heating rates, and thus, it seems
to be the promising reactor type for pyrolysis biomass-
based hydrogen production [129].
Because gasification of tar is difficult, extensive studies
have been carried out on the catalytic effect of inexpensive
dolomite and CaO on the decomposition of hydrocarbon
compounds in tar [126,127].
The catalytic effects of Ni-based catalysts [131],
K2CO3, Na2CO3 and CaCO3 [132], Y-type zeolite [133]
and various metal oxides (Al2O3, SiO2, ZrO2, TiO2 [134]
and Cr2O3 [132]) have been studied by various researchers.
It was found that among the various metal oxides, Al2O3
and Cr2O3 demonstrate better catalytic effect than the
others. Among the catalysts, Na2CO3 is better than
K2CO3 and CaCO3. Noble metals Ru and Rh are more ef-
fective than Ni catalyst and less susceptible to carbon for-
mation; however, they are not commonly used because of
their high costs [135].
Hydrogen production from pyrolysis of various bio-
mass feedstock such as peanut shell; post-consumer wastes
like plastics, trap grease, mixed biomass and synthetic
polymers [136], rapeseed [137]; and agricultural residue
[138] was experimented by different researchers. Czernik
et al. [136] pointed out that hydrogen could be efficiently
generated from plastics where 34 g hydrogen was achieved
from 100 g of polypropylene, which is 80% of the stoichio-
metric potential. Abedi et al. [138] stipulated that the rate
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S. E. Hosseini et al.
Table VI. Pyrolysis reactor types, heat transfer modes and typical features
Reactor type Mode of heat transfer (%)
Ablative 95 conduction
4 convection
1 radiation
Fluidized bed 90 conduction
9 convection
1 radiation
Circulating fluidized bed 80 conduction
19 convection
1 radiation
Entrained flow 4 conduction
95 convection
1 radiation
of hydrogen production from pyrolysis process would be
5–7% higher when the reforming is followed by water–
gas shift processing of carbon monoxide in the product
gas. To improve the process of hydrogen production from
biomass pyrolysis, fluidized catalyst beds are applied to
overcome the problem of reduced reforming performance
caused by coke and char deposition on the catalyst surface
and in the bed itself [139]. An economic study about bio-
mass pyrolysis process for hydrogen production performed
by Padró and Putsche [140] demonstrated that the cost of
hydrogen production by biomass pyrolysis is significantly
lower than hydrogen production by wind-electrolysis sys-
tems and photovoltaic (PV) electrolysis systems. It was es-
timated the hydrogen production cost of biomass pyrolysis
to be in the range of US$8.86/GJ to US$15.52/GJ; how-
ever, hydrogen production by wind-electrolysis systems
and PV-electrolysis systems is US$20.2/GJ and US$41.8/
GJ, respectively [140].
8. HYDROGEN FROM BIOMASS
GASIFICATION
Gasification consists of combustion and pyrolysis pro-
cesses to prepare heat for the endothermic pyrolysis reac-
tions. Gasification is usually performed at high
temperatures to increase the rate of gas production. Ther-
mal decomposition of solid biomass takes place at temper-
atures around 602–1002 °C. At the end of gasification
process, a combination of H2, CH4, CO, N2 and CO2 is
Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Biomass-based hydrogen production for renewable energy supply
Typical features
Accepts large size feedstock
Very high mechanical char abrasion from biomass
Compact design
Heat supply problematical
Heat transfer gas not required
Particulate transport gas not always required
High heat transfer rates
Heat supply to fluidizing gas or to bed directly
Limited char abrasion
Very good solids mixing
Particle size limit <2 mm in smallest dimension
Simple reactor configuration
High char abrasion from biomass and char erosion
Leading to high char in product
Char/solid heat carrier separation required
Solids recycle required
Increased complexity of system
Maximum particle sizes up to 6 mm
Possible liquids cracking by hot solids
Possible catalytic activity from hot char
Greater reactor wear possible
Low heat transfer rates
Particle size limit <2 mm
Limited gas/solid mixing
generated. The combination of final produced gases in
the gasification process (reaction 6) is influenced by the
composition of biomass feedstock, the gasifying agent
and the gasification process.
Biomass þO2 ðor H2 OÞ→H2 O ; CO ; CO2 ; CH4 ; H2 (6)
þother CHs þ char þ tar þ ash
Thermochemical decomposition of the cellulose, hemi-
celluloses and lignin compounds with production of vola-
tiles and char is the first step of the biomass gasification
process [141]. Further, the char gasification and some other
equilibrium reactions take place. Compared with biomass
pyrolysis, biomass gasification is performed in higher tem-
peratures, resulting in a mixture of gases with H2 content
ranging from 6 to 6.5% [142]. A combination of O2, N2,
CO, CO2, CH4 called synthetic gas and tar are produced
by biomass gasification. It has been stipulated that elimina-
tion of tar from biomass gasification products is more com-
plicated than physical dust removal process [143]. It has
been stipulated that the type of reactor (downdraft fixed
beds, fluidized bed and entrained flow gasifier) and process
temperature effect on the composition of synthetic gas
from biomass gasification [144]. In order to increase the
performance of gasifier, tars and inorganic impurities
should be removed and water–gas shift reaction should
be implemented to convert CO to H2. The synthetic gas
from biomass gasification or so-called bio-syngas includes
mainly hydrogen and carbon monoxide. Hydrogen produc-
tion is the main goal of bio-syngas production by catalytic,
Biomass-based hydrogen production for renewable energy supply S. E. Hosseini et al.

noncatalytic and steam gasification processes. Among biomass for hydrogen production, especially SCWG, maps
these various technologies, steam gasification has emerged a promising future for hydrogen production. In this regard,
as a promising method for thermochemical biomass-based different biomass-based hydrogen production methods and
hydrogen production. It was stipulated that the system tem- various available biomass resources were developed in this
perature, as well as hydrogen yield from the process, is paper, considering Malaysia as a case study. Utilization of
higher in steam gasification compared with that in pyroly- biomass waste material especially POME (as a liquid
sis [145]. SCWG is mentioned as a promising method for waste) and PSR (as a solid waste) in hydrogen production
hydrogen production from biomass waste. Elimination of scenario of Malaysia is helpful to obtain waste-to-well
drying step (as a preliminary treatment in thermochemical strategy. The cost of hydrogen produced by SCWG of bio-
process of biomass) is one of the most important advan- mass is extremely lower than biomass pyrolysis method,
tages of this method. Highly moisturized biomass is eligi- wind-electrolysis systems and PV-electrolysis systems.
ble to be employed directly in SCWG without any high- Around 40% of the energy demand of Malaysia could be
cost drying process [146]. In SCWG, hydrogen is pro- supplied by SCWG of palm solid waste. Although bio-hy-
duced at high pressure, and thus, a small amount of energy drogen is expensive (because of low rates of hydrogen pro-
is required to pressurize hydrogen in the storage tank. duction and long time process), it has great capability to be
Moreover, tar and char formation decreases drastically in developed and emerges as a clean environmentally friendly
biomass SCWG method [147]. Compared with the other energy carrier.
biomass thermochemical gasification processes (like steam
or air gasification), the SCWG indicates high efficiency in NOMENCLATURE
lower temperatures [148]. Moreover, compared with the
other conventional hydrogen production processes, hydro- BP = British Petroleum
gen from SCWG of biomass is the most cost-effective pro- CPO = crude palm oil
cess [77]. Hong and Spritzer [149] pointed out that the cost COD = chemical oxygen demand
of hydrogen produced by SCWG of biomass is about US CO2 = carbon dioxide
$3/GJ (US$0.35/kg). EJ = exajoule
The chemical reaction of SCWG is categorized into EFB = empty fruit bunches
three following main reactions: GHG = greenhouse gas
Biomass þ H2 O → CO þ H2 steam reforming GW = global warming
(7) HFC = hydrogen fuel cell
MTOE = million tonnes of oil equivalent
CO þ H2 O →CO2 þH2 water gas-shift reaction NG = natural gas
(8) POME = palm oil mill effluent
PSR = palm solid residue
CO þ 3H2 →CH4 þ H2 O methanation reaction RSE = renewable and sustainable energy
(9) SCWG = supercritical water gasification
SMR = steam methane reforming
In reaction (7) (steam-reforming reaction), PSR reacts
with super-critical water to produce gaseous mixtures of
H2 and CO. The generated CO from reaction (7) partici-
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Int. J. Energy Res. (2015) © 2015 John Wiley & Sons, Ltd.
DOI: 10.1002/er