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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-


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

Copyright © 2015 John Wiley & Sons, Ltd.


S. E. Hosseini et al. Biomass-based hydrogen production for renewable energy supply

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

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 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 Malaysia, it has not been seriously taken into consideration
in the energy mix of the country [41].
Biomass is an advantageous RSE that can be employed as In Malaysia, the main produced agricultural crops are oil
a fuel to generate electricity and other forms of energy. palm, rubber, cocoa, rice and coconut. In terms of acreage,
Biomass feedstock is any organic matter available on a re- oil palm and rubber plantations are the major plantations in
newable basis for conversion to energy. Agricultural crops Malaysia. The Malaysian government has focused on using
and residues, farm animal wastes, industrial wood and log- renewable biomass from the oil palm industry, which in-
ging residues, food residues and the organic portion of mu- cludes empty fruit bunches, fibre and shells, to produce en-
nicipal waste are all types of biomass feedstock. Muis et al. ergy. Because Malaysia is one of the largest palm oil
[34] pointed out that biomass is a proven option for elec- producers in the world, around 85.5% of total available bio-
tricity generation in Malaysia. The economy of Malaysia mass in the country is palm oil waste (around 55.73 million
could be bolstered by biomass utilization in energy mix tonnes per year) [42]. Ong et al. [43] pointed out that ap-
of the country by providing job opportunities in rural areas. proximately 19 million tonnes per annum of biomass waste
Utilization of biomass can decrease the dependence on for- is produced in the form of empty fruit bunches, shells and fi-
eign energy sources, as is currently the case in many devel- bre in Malaysian palm oil mills. The cost of palm solid waste
oping countries. Deployment of biomass-based energy is estimated to be US$1772m per year [44].
generation can create various job opportunities for utility, After palm solid residue (PSR) and wood waste, rice
power equipment and agricultural equipment industries husk from rice mills is the third most important biomass re-
[35]. On the other hand, the increasing rate of total carbon source in Malaysia [45]. Moreover, biomass from paddy
dioxide (CO2) emissions from fossil fuels can be controlled straws has been named as an important source of biomass
by biomass-based energy utilization. in the country [36]. Other biomasses from cocoa, coconut
Besides CO2, other greenhouse gases such as methane and sugarcane cultivation are of minor importance because
(CH4), nitrogen oxide (NO) and sulfur oxide are generated of their lesser annual available quantities [39].
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 3. FEASIBILITY STUDY OF
the past 40 years, the value of CO2 emissions in metric tons HYDROGEN PRODUCTION IN
per capita in Malaysia has reached a maximum value of MALAYSIA
7.81 in 2008 and a minimum value of 1.34 in 1970 [37].
Because an abundance of renewable biomass resources The feasibility of hydrogen production in Malaysia can be
has been known in Malaysia, utilization of this alternative determined by taking into account several aspects such as
fuel could play an effective role in environmental protec- availability of feedstock, complexity and capability of cur-
tion of the country. Among all RSE resources, biomass rent production technologies and economic issues. As
has the highest potential to be employed as a renewable shown in Table III, there are various technologies that are
source of energy in Malaysia [38]. The total land area in available for hydrogen production in Malaysia. However,
Malaysia is 32.90 million ha, which includes 20.10 ha the selection of these technologies and the required feed-
(61%) under natural forest cultivation and 4.89 ha (14.9%) stock are restricted to the cost and economic issues.
agricultural sector [39]. Various types of available biomass The important parameters in choosing the best feed-
are listed in Table II [40]. 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 Because of the efficiency and economic benefits of
feedstock and the total cost of acquiring the feedstock. For steam-reforming method, many studies had been carried
instance, although coal is one of the most famous fossil out to improve this technology. Recently, better materials
fuel feedstock for hydrogen production [46], this feedstock for reformer tubes, better control and understanding of car-
is infeasible economically and technically for hydrogen bon limits and better catalysts and process concepts with
production in Malaysia. The cheapest and most abundantly high feedstock flexibility have been incorporated to steam
available fossil fuel is coal, and the Malaysia coal reserve reforming technology, contributing to less costly and more
is currently about 1712 million tons of various coals rang- efficient plants [49]. In Malaysia, the diversity of natural
ing from lignite to anthracite. Malaysia’s coal deposits are resources supported the government initiatives in promot-
mainly located in the rural and remote areas where infra- ing renewable energy development based on the 5th Fuel
structures are poor, and the development of infrastructures Policy. The renewable resources such as biomass are abun-
to transport these coals requires high cost. Furthermore, the dantly available in Malaysia. Biomass is a promising re-
majority of the coal deposits are located underground, newable resource to produce hydrogen. Malaysia is
which requires underground mining and consequently located in a strategic location and is blessed with a variety
higher cost. Because of the high cost of locally sourced of biomass such as residues from palm oil, rice, sugarcane
coal, 90% of the coal demands in Malaysia are fulfilled and the wood industry. However, issues regarding trans-
by importing coals from Australia, Indonesia, China and portation and preparation of biomass are the main chal-
South Africa [47]. As a result of high extraction cost of lo- lenges. The cost for transportation and preparation of
cal coals, the coal gasification technology is not feasible biomass is fundamentally very high. This results in the con-
for hydrogen production in Malaysia. The steam-reforming struction of small hydrogen plants without considering the
technology is the most feasible method in producing hy- economical aspect. One solution to this issue is by building
drogen in large scale. This is because the most feasible a hydrogen plant near the biomass resources as to minimize
feedstock available for hydrogen production remains to the transportation cost. Another challenge in biomass-based
be fossil fuels, although Malaysia has diverse renewable hydrogen production is that it requires better catalysts to im-
energy resources such as solar energy, wind energy and prove yields and selectivity, as bio-fuels are more difficult to
biofuels. When NG is not available, higher hydrocarbons reform because of its large composition of carbon atoms [50].
can be used as feedstock, taking advantage of the surplus Table IV shows the sources of biomass and the potential of
of various hydrocarbon streams in many refineries [48]. 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. Biomass-based hydrogen production for renewable energy supply

[67]. The major pathways of biomass-based hydrogen pro- with the thermochemical biomass-based hydrogen production
duction are illustrated in Figure 2 [68]. processes, biohydrogen method displays less energy intensity
Gasification (steam gasification and SCWG), steam [72,73].
reforming of bio-oils and pyrolysis are the most well-
known thermochemical processes of biomass-based hydro- 5.1. Biophotolysis
gen production. Moreover, photo-fermentation, bio-pho-
tolysis of water using green algae and blue-green algae Splitting of water molecules (H2O) to form oxygen (O2)
(cyanobacteria), dark-fermentation and hybrid reactor sys- and hydrogen (H2) with light as a source of energy is
tem are the most important biological hydrogen production biophotolysis [74]. This process is categorized into two
processes. The high efficiency (thermal to hydrogen is up kinds: direct biophotolysis and indirect biophotolysis. Di-
to 52%) and low cost of biomass-based hydrogen produc- rect biophotolysis is a biological process that can produce
tion via thermochemical process are the most important hydrogen directly through energy conversion in the form
characteristics of this method [69]. 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
5. BIOLOGICAL BIOMASS-BASED to break water nonstop into O2 and H2. The main advan-
HYDROGEN PRODUCTION tage of this process is that water is used as the major
source, which is readily in abundance. Another merit for
Biohydrogen [67] production with anaerobic bacteria started this process is that even in low light, green algae and anaer-
in the 1980s. Because of special attention to sustainable de- obic conditions are still able to convert almost 22% of light
velopment and waste management, biohydrogen research energy by using hydrogen as an electron donor in the pro-
has significantly increased over the last decade [68,69]. cess of fixation of CO2. Production of oxygen by microor-
The most important technologies for biohydrogen produc- ganisms, in addition to hydrogen production, is a negative
tion include the following: water–gas shift hydrogen produc- point because when organisms sense oxygen, hydrogen
tion, direct photolysis hydrogen production from water by production is stopped [76]. Indeed, to prevent building up
cyanobacteria or green algae, photo-fermentative hydrogen of oxygen, the ratio of oxygen production (photosynthesis)
production, dark-fermentative hydrogen production process to oxygen consumption (respiration) should be changed
during the acidogenic phase of anaerobic digestion and [77]. Although it was found that addition of sulfate to the
two-stage dark/fermentative [70]. Photolysis and photo fer- solution is effective for depression of oxygen production,
mentation are light-dependent, while dark fermentation is the rate of hydrogen production also decreases [78]. Fur-
light-independent that takes place in the dark [71]. Compared thermore, because H2 and O2 are the main products of this

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 S. E. Hosseini et al.

technique, significant safety is required. Low efficiency microalgae in water, and hydrogen is produced through en-
and non-continuous process of hydrogen production are ergy conversion from sunlight to chemical energy using dif-
the main tremendous challenges [79]. ferent approaches of light and no-light approaches such as
dark aerobic fermentation, biomass production by photosyn-
5.2. Hydrogenase and nitrogenase enzymes thesis and biomass concentration. Water and CO2 are the
major inputs involved in the growth of microalgae and
Hydrogenase enzymes are biological enzymes divided into cyanobacteria using hydrogenase enzyme as catalytic bacte-
two types: iron–iron (fe–fe) and nickel–iron (Ni–Fe) enzymes ria for the production of hydrogen [86]. Water is the donor in
[76,77]. Iron and nickel are metals that are easy to obtain and the hydrogen production; thus, biophotolysis does not re-
cheap. Fe–Fe is mostly used because it is more efficient than quire any substrate as nutrients. The method of hydrogen pro-
Ni–Fe [80]. This enzyme is commonly found in microorgan- duction using cynanobacteria and microalgae is of advantage
isms like cyanobacteria green algae. Therefore, hydrogen is because of the fact that it uses light as energy source and wa-
obtained through conversion of protons with production of ox- ter as a substrate; if appropriately utilized, the hydrogen pro-
ygen. Hence, this enzyme is sensitive to oxygen change [81]. duced could be used in fuel cell to generate electricity [87].
Nitrogenase enzymes convert nitrogen molecules to pro-
duce hydrogen in anaerobic condition [82]. Cyanobacteria
5.3. Photo fermentation
is the only microorganism tested to contain this type of en-
zyme in biohydrogen production [83]. It is divided into nitro- In photo fermentation or so-called photosynthetic bacterial
gen fixation (which requires ATP) and non-nitrogen fixation. hydrogen production, the nitrogenase characteristic of pur-
Figure 3 demonstrates how a heterocyst prepares an oxy- ple non-sulfur bacteria plays a crucial role to evolve H2. In
gen-free condition to the oxygen-sensitive nitrogenase that order to scavenge transferred light energy to membrane
decreases molecular nitrogen into NH3 and protons into hy- reaction centres, light-harvesting pigments such as
drogen based on reaction (1) [84]. In an N2-containing envi- phycobilins, carotenoids and chlorophylls are employed.
ronment (such as air), N2 fixation is the dominant reaction, Water is converted into electrons, protons and oxygen by
while hydrogen is a minor byproduct. Based on reaction sunlight energy. By utilization of nitrogenase catalyst in
(2), higher rates of H2 could be constituted in the absence the process, the protons and electrons react with nitrogen
of molecular N2. The required energy for hydrogen evolu- and ATP to make ADP, H2 and ammonia [88]. The process
tion is provided by neighbour cells or derived from the en- is performed in the lack of nitrogen circumstance
ergy-rich carbohydrate (CH2O). The efficiency of energy employing primarily infrared light energy. One of the most
conversion from light to H2 by nitrogenase is low (<1%) be- advantages of this technique is that oxygen does not inhibit
cause of the high energy demand (four ATP per hydrogen) the process. Furthermore, the bacteria (which use the hy-
[85]. drogen byproduct to reinvigorate other energy-requiring
processes via the uptake hydrogenase enzyme) can be used
N2 þ 8Hþ þ 8eþ 16 ATP → 2NH3 þ H2 in various circumstances (such as polyurethane foam, po-
þ16 ADP þ 16 Pi nitrogen fixation reaction rous glass or continuous cultures) [12]. Nevertheless, some
(1) important parameters such as high amount of required en-
ergy for the process, re-oxidation of hydrogen, slow nitro-
8Hþþ 8e- þ 16 ATP→4H2 þ 16 ADP (2) genase enzyme and limited availability of organic are
þ16 Pi non-nitrogen fixation reaction named as disadvantages of this process [76]. By engineer-
ing the ratio of carbon to nitrogen nutrients, the required
Indirect biophotolysis process uses cyanobacteria and energy for the process decreases and the activity of

Figure 3. Nitrogenase-mediated hydrogen evaluation in a heterocyst of nitrogen-fixing heterocystous cyanobacteria.

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

nitrogenase enhances. Indeed, to reduce the nitrogenase via acetate fermentative metabolism, and the second step
dependent on the high levels of nitrogen nutrients, enzyme is conversion of resultant acetate to hydrogen by photosyn-
engineering should be maintained. thetic bacteria in another reactor. Twofold hydrogen yield
is reported by Tao et al. [99] in comparison with that using
5.4. Dark fermentation only dark-fermentation. It was claimed that by utilization
of two-step photo-fermentation, the total hydrogen produc-
Dark fermentation is requiring complex organic com- tion increases from 3.6 to 6.63 mol H2/mol sucrose.
pounds; it appears to be favourable among the methods Rittmann et al. [100] stipulated that the discontinuous
of hydrogen production, and it operates in anaerobic condi- monitoring of culture parameters and the emergence of un-
tion (without oxygen). Hydrogen is produced at high rate stable culture circumstances due to sample removal and/or
and low cost with various organic substrate and wastewa- inhibition of biohydogen production by buildup of liquid
ters enriched with carbohydrates. Three types of bioreac- and gaseous metabolic products are the most important
tors could be used to yield hydrogen in dark fermentation drawbacks of dark fermentation technique. Manipulation
process. In fermentative hydrogen production, many feed- to the culture needs to disrupt at least one physical factor,
stocks were used, which includes biomass, agricultural which results in non-continuous cultivation conditions
waste, food processing waste, sewage sludge and livestock and making the application of closed batch technique
effluents [89]. Dark fermentation under anaerobic is con- rather unattractive [101]. In dark fermentation, beside pure
sidered more encouraging, given that the hydrogen pro- hydrogen, a mixed biogas containing primarily H2, CO2
duced is optimum with little cost using wastewaters and lesser amounts of CH4, CO and hydrogen sulfide
carbohydrate-based substrate [90]. Based on temperature (H2S) is generated [102].
distribution, dark fermentation processes are classified into
low (mesophiles), medium (thermopiles) and high 5.4.1. Factors that influence dark fermentation
(Hyperthermophiles) temperature process. Aerobes mi- 5.4.1.1. Organic loading Rate. Organic loading rate
crobes, anaerobes organisms and facultative anaerobes were (OLR) affects the rate of biohydrogen production. Studies
tested using different temperature ranges. Ferchichi et al. have shown this effect using different types of substrate
[91] found that Clostridium saccharoperbutylacetonicum loading when wastewater was used as a substrate. Microor-
ATCC 27021 grown on pure carbohydrate (disaccharides) ganism acts on organic substrate to yield hydrogen. OLR is
and hydrogen yield was more than twice 2.81 mol-H2/mol evaluated using two quantities: hydraulic retention time
sugars greater than monosaccharide 1.29 mol-H2/mol hex- (HRT) and chemical oxygen demand (COD). Glucose
ose. It was claimed that the rate of production of hydrogen sugar was used, and the OLR was measured in g/L day,
with monosaccharide is much higher than disaccharides which is equivalent to the extent of the COD (g/L) fed at
[92]. Because carbohydrates are the main source of hydrogen, a certain period of time. Thus, the high OLR does not nec-
complex carbohydrates, biomass rich in sugars and sewages essary result in higher hydrogen production. However, it is
may appear to be suitable for biohydrogen production [93]. significant to consider certain range of the OLR due to the
In dark fermentation, hydrogen is usually produced by microbial growth and hydrogen production [103]. In an ex-
pyruvate. Pyruvate is produced through Embden–Meyer- perimental investigation of hydrogen production via dark
hof–Parnas (EMP) pathway, which is divided into acetyl- fermentation process, implemented by Mariakakis et al.
CoA and formate by PFL (pyruvate formate lyase) under [104], it was found that the maximum hydrogen production
anaerobic conditions [94]. The substrate can be exogenic reaches to 1.72 mol H2/mol hexose for HRT equal to 1.6 d
or endogenic. Hydrogen is obtained through conversion and OLR of 20 g sucrose/(L∙d), while no hydrogen gas pro-
of pyruvate dark condition. The pyruvate disintegration is duction could be established for OLRs lower than 10 g su-
controlled by two enzymes, namely, PFL and pyruvate crose/(L∙d), a value that can be considered as threshold.
ferridoxin oxido-reductase [95]. Oxygen is not produced
in dark fermentation. Dark fermentation-based hydrogen 5.4.1.2. Temperature. Temperature is an environ-
is not competitive with the commercialized hydrogen pro- mental factor that affects the biological hydrogen produc-
duction processes (from fossil fuels) in terms of reliability, tion. There are three ranges of temperatures that acted on
efficiency and cost. The efficiency of fermentation hydro- the bacteria during biohydrogen production: psychrophilic
gen is about 1–5%, which shows that the process needs 0–20 °C, mesophilic bacteria 20–42 °C and thermophilic
to advance in terms of efficiency [96]. bacteria 42–75 °C [105]. Reports have shown how the tem-
Although anaerobic digestion of organic waste includ- perature effects proportionally on the production rate of hy-
ing agricultural and municipal waste and wastewater drogen. Hydrogen production rate using thermopiles was
sludge has illustrated its sustainability for H2 production, observed to be higher than that in mesophilic bacteria
the low yields of hydrogen realized from the fermentation [103]. However, no standard was observed yet regarding
of even the simplest sugars restrict current H2 production the exact temperature to be used in biological hydrogen pro-
[97]. Kotay et al. [98] pointed out that a combination of duction. The best possible temperature to be used in dark fer-
dark and photo-fermentation in a two-stage hybrid system mentation depends on the type of biocatalyst and the type of
ameliorates the overall yield of hydrogen. The first step is employed substrate and carbon source. Both mesophilic and
decomposition of starch or glucose by anaerobic bacteria thermophilic temperatures were applied to be optimal for

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.

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

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]

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

municipal solid waste [113], starch effluent [114], food-pro- with a POME concentration of 20 g COD/l in the feed,
cessing wastewater [115], rice wastewater [116], distillery the suspended-cell-containing reactor was able to produce
and molasses-based wastewater [117] and domestic waste- hydrogen at an optimal rate of 0.348 L H2/(L POME h) at
water [118] were experimented by various researchers. 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
6. HYDROGEN PRODUCTION FROM immobilized-cell-containing reactor was scaled up to 5 L,
PALM OIL MILL EFFLUENT 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-
Palm oil mill waste is categorized into liquid, solid and ment of POME for 1 h at 60 °C, the rate increases to 0.632
gasses waste. Hydrogen production from palm oil gasses L H2/(L POME hour) at HRT of 2 h. The main soluble me-
waste has not been developed properly yet. When looking tabolites were butyric acid and acetic acid, followed by
into liquid waste, it is definite that the waste will be re- propionic acid and ethanol. Successful researches in hydro-
leased to the river or water stream system as it the most gen production from POME indicate that utilization of
economic manner to manage the waste. Palm oil mill efflu- POME (as material to produce hydrogen through various
ent (POME) is the water waste that is being discharged methods) will be implemented in large-scale hydrogen pro-
from the sterilization process of oil palm fruit, crude oil duction in the future.
clarification process and cracked mixture separation pro-
cess [119]. Discharging POME to the environment is
harmful to the aquatic ecosystem because of creating 7. HYDROGEN FROM BIOMASS
highly acidic environments or causing algal growth, which PYROLYSIS
occurs on the surface of the water because of the COD and
biological oxygen demand. Hence, an alternative way to Biomass pyrolysis is a route of gaseous, liquid (tar and
make POME become useful and harmless to the environment other organics) and solid (char) production for generation
is to produce hydrogen from POME. Several discussions of alternate sources of energy [125]. The required temper-
were made based on POME waste to produce hydrogen. Atif ature for pyrolysis is between 352 and 502 °C, and the re-
et al. [120] discussed about anaerobic production of hydro- lated pressure is 0.1–0.5 MP in the absence of air [126].
gen from POME by anaerobic microflora in 5-1 bioreactor Because of the operating system, the pyrolysis process is
at 60 °C and pH 5.5. They found that in a fed batch reactor, known as fast pyrolysis and slow pyrolysis. High-tempera-
hydrogen yields a total of 4.708 l H2/1 POME. In 2006, ture gas and low-temperature tar is produced in biomass
POME was adopted as supplementary substrate in the anaer- fast pyrolysis, while high charcoal continent is generated
obic contact filter system under mesophilic conditions by in slow pyrolysis [127]. High-temperature fast pyrolysis
Vijayaraghavan and Ahmad [121], signifying a cumulative in very short residence times yields higher rates of hydro-
gas generation of 11.8 l/week (56% hydrogen) corresponding gen [128]. Because the major product of slow pyrolysis
to COD removal of 67%. Figure 4 shows the schematic is charcoal, this process is not taken into account for hydro-
diagram of up-flow anaerobic contact filter for hydrogen gen- gen production. In the fast pyrolysis process, the biomass
eration. In this experiment, the mixed type reactor unit in- feedstock is heated quickly in the absence of air to form va-
cludes acrylic column (100 ID × 1200 mm height), and 40- pour and condense to a dark brown mobile bio-liquid. The
mm diameter rigid circular porous plastic balls are employed products of fast pyrolysis include gaseous products (CH4,
as a packing material. The openings in porous ball were H2, CO, CO2 and other gases based on the organic nature
3 mm with a cross fluted at every one-fourth of the ball of the biomass feedstock); liquid products (tar and oils
diameter [121]. such as acetic acid and acetone, which are liquid at room
Prasertsan et al. [122] optimized hydrogen production temperature); and solid products (composed of char and
from POME by thermoplilic fermentative process. The pure carbon plus other inert materials). Although pyrolysis
waste sample was held in a constructed bioreactor for processes are applied for biofuel production, biomass-
2 days at 60 °C to increase the yield of hydrogen. A maxi- based hydrogen can be generated directly through fast py-
mum hydrogen yield of 0.27 l H2 g/COD was reported by rolysis in high-temperature circumstance and sufficient
the authors. A 50 L of continuous stirred tank reactor was volatile phase residence time (reaction 3).
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 Biomass þ heat→ CH4 þ CO þ H2 (3)
to pilot plant. The rate of hydrogen yield was obtained at þ other products
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- To raise the rate of hydrogen production from fast py-
bilization techniques to produce hydrogen using rolysis mechanism, steam reformation of methane and
immobilized anaerobic sludge as the seed culture. POME other produced hydrocarbon vapours is carried out based
was used as the substrate carbon source. They found that on reaction (4).

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.

Figure 4. Schematic of up-flow anaerobic contact filter for hydrogen production.

type demonstrates higher heating rates, and thus, it seems


CH4 þ H2 O →CO þ 3H2 (4) to be the promising reactor type for pyrolysis biomass-
based hydrogen production [129].
Moreover, water–gas shift reaction (reaction 5) is ap- Because gasification of tar is difficult, extensive studies
plied to enhance the rate of hydrogen production. have been carried out on the catalytic effect of inexpensive
dolomite and CaO on the decomposition of hydrocarbon
CO þ H2 O→CO2 þ H2 (5) compounds in tar [126,127].
The catalytic effects of Ni-based catalysts [131],
Based on water solubility, the oily byproducts of pyrol- K2CO3, Na2CO3 and CaCO3 [132], Y-type zeolite [133]
ysis are separated into two fractions. The water-soluble and various metal oxides (Al2O3, SiO2, ZrO2, TiO2 [134]
byproducts are applied for hydrogen production, while and Cr2O3 [132]) have been studied by various researchers.
the water-insoluble byproducts are used for adhesive pro- It was found that among the various metal oxides, Al2O3
duction. Type of catalyst, temperature, heating rate and and Cr2O3 demonstrate better catalytic effect than the
residence time are the most important parameters that con- others. Among the catalysts, Na2CO3 is better than
trol hydrogen yield from pyrolysis biomass process. The K2CO3 and CaCO3. Noble metals Ru and Rh are more ef-
adjusting of these parameters is implemented by the selec- fective than Ni catalyst and less susceptible to carbon for-
tion of reactor type and heat transfer modes, such as solid– mation; however, they are not commonly used because of
solid conductive heat transfer and gas–solid convective their high costs [135].
heat transfer [129]. In pyrolysis biomass hydrogen produc- Hydrogen production from pyrolysis of various bio-
tion, high temperature, high heating rate and long volatile mass feedstock such as peanut shell; post-consumer wastes
phase residence time are crucial [130]. The yield of hydro- like plastics, trap grease, mixed biomass and synthetic
gen from pyrolysis of biomass is augmented significantly polymers [136], rapeseed [137]; and agricultural residue
when Ni-based catalyst is employed. Further, hydrogen [138] was experimented by different researchers. Czernik
could be produced by using additional steam reforming et al. [136] pointed out that hydrogen could be efficiently
and water–gas shift reaction [77]. The heat transfer modes generated from plastics where 34 g hydrogen was achieved
and features of various reactors are listed in Table VI. from 100 g of polypropylene, which is 80% of the stoichio-
From this table, it can be found that fluidized bed reactor metric potential. Abedi et al. [138] stipulated that the rate

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 VI. Pyrolysis reactor types, heat transfer modes and typical features

Reactor type Mode of heat transfer (%) Typical features

Ablative 95 conduction Accepts large size feedstock


4 convection Very high mechanical char abrasion from biomass
1 radiation Compact design
Heat supply problematical
Heat transfer gas not required
Particulate transport gas not always required
Fluidized bed 90 conduction High heat transfer rates
9 convection Heat supply to fluidizing gas or to bed directly
1 radiation Limited char abrasion
Very good solids mixing
Particle size limit <2 mm in smallest dimension
Simple reactor configuration
Circulating fluidized bed 80 conduction High char abrasion from biomass and char erosion
19 convection Leading to high char in product
1 radiation 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
Entrained flow 4 conduction Low heat transfer rates
95 convection Particle size limit <2 mm
1 radiation Limited gas/solid mixing

of hydrogen production from pyrolysis process would be generated. The combination of final produced gases in
5–7% higher when the reforming is followed by water– the gasification process (reaction 6) is influenced by the
gas shift processing of carbon monoxide in the product composition of biomass feedstock, the gasifying agent
gas. To improve the process of hydrogen production from and the gasification process.
biomass pyrolysis, fluidized catalyst beds are applied to
overcome the problem of reduced reforming performance Biomass þO2 ðor H2 OÞ→H2 O ; CO ; CO2 ; CH4 ; H2 (6)
caused by coke and char deposition on the catalyst surface þother CHs þ char þ tar þ ash
and in the bed itself [139]. An economic study about bio-
mass pyrolysis process for hydrogen production performed Thermochemical decomposition of the cellulose, hemi-
by Padró and Putsche [140] demonstrated that the cost of celluloses and lignin compounds with production of vola-
hydrogen production by biomass pyrolysis is significantly tiles and char is the first step of the biomass gasification
lower than hydrogen production by wind-electrolysis sys- process [141]. Further, the char gasification and some other
tems and photovoltaic (PV) electrolysis systems. It was es- equilibrium reactions take place. Compared with biomass
timated the hydrogen production cost of biomass pyrolysis pyrolysis, biomass gasification is performed in higher tem-
to be in the range of US$8.86/GJ to US$15.52/GJ; how- peratures, resulting in a mixture of gases with H2 content
ever, hydrogen production by wind-electrolysis systems ranging from 6 to 6.5% [142]. A combination of O2, N2,
and PV-electrolysis systems is US$20.2/GJ and US$41.8/ CO, CO2, CH4 called synthetic gas and tar are produced
GJ, respectively [140]. 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
8. HYDROGEN FROM BIOMASS been stipulated that the type of reactor (downdraft fixed
GASIFICATION beds, fluidized bed and entrained flow gasifier) and process
temperature effect on the composition of synthetic gas
Gasification consists of combustion and pyrolysis pro- from biomass gasification [144]. In order to increase the
cesses to prepare heat for the endothermic pyrolysis reac- performance of gasifier, tars and inorganic impurities
tions. Gasification is usually performed at high should be removed and water–gas shift reaction should
temperatures to increase the rate of gas production. Ther- be implemented to convert CO to H2. The synthetic gas
mal decomposition of solid biomass takes place at temper- from biomass gasification or so-called bio-syngas includes
atures around 602–1002 °C. At the end of gasification mainly hydrogen and carbon monoxide. Hydrogen produc-
process, a combination of H2, CH4, CO, N2 and CO2 is tion is the main goal of bio-syngas production by catalytic,

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.

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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