Energy Conversion and Management 52 (2011) 1778–1789

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Recent advances in production of hydrogen from biomass

Elif Kırtay ⇑
Sila Science & Energy Company, University Mah, Trabzon, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this paper is to highlight various processes for the conversion of biomass into hydrogen gas.
Received 12 March 2010 Biomass energy has the potential to be ‘‘modernized’’ worldwide, i.e., produced and used efficiently and
Accepted 21 November 2010 cost competitively, generally in the more convenient forms of gases, liquids, or electricity. Biomass will
Available online 5 January 2011
play an important role in the future global energy infrastructure for the generation of power and heat, but
also for the production of chemicals and fuels. Biomass and biomass-derived fuels are can be used to pro-
Keywords: duce hydrogen sustainably. The methods available for the hydrogen production from biomass can be
Biomass
divided into two main categories: thermochemical and biological routes.
Hydrogen
Gasification
Ó 2010 Elsevier Ltd. All rights reserved.
Pyrolysis
Fermentation

1. Introduction is ideal for gradually replacing fossil fuels [12]. Since the energy
crises of the 1970s, many countries have become interest in bio-
The dramatic increase in the price of petroleum, the finite nat- mass as a fuel source to expand the development of domestic
ure of fossil fuels, increasing concerns regarding environmental and renewable energy sources and reduce the environmental im-
impact, especially related to greenhouse gas emissions, and health pacts of energy production. Biomass energy potential is addressed
and safety considerations are forcing the search for new energy to be the most promising among the renewable energy sources,
sources and alternative ways to power the world’s motor vehicles due to its spread and its availability worldwide [13]. Biomass
[1–3]. Hydrogen seems to be an ideal candidate, since hydrogen is and biomass-derived fuels are can be used to produce hydrogen
a cleaner source of energy [4]. It holds the promise as a dream fuel sustainably. Using biomass instead of fossil fuels to produce hydro-
of the future with many social, economic and environmental ben- gen reduces the net amount of CO2 released to the atmosphere,
efits to its credit [5]. since the CO2 released when the biomass is gasified was previously
About half of all the H2 as currently produced is obtained from absorbed from the atmosphere and fixed by photosynthesis in the
thermocatalytic and gasification processes using natural gas as a growing plants [14].
starting material, heavy oils and naphtha make up the next largest Hydrogen can be generated from biomass, but this technology
source, followed by coal, and only 4% is generated from water using urgently needs further development. The production of renewable
electricity [6]. Approximately 49% of hydrogen produced is used for hydrogen from biomass requires a co-product strategy to compete
the manufacture of ammonia, 37% for petroleum refining, 8% for with conventional production of hydrogen from the steam reform-
methanol production and about 6% for miscellaneous smaller-vol- ing of natural gas. The process of biomass to activated carbon is an
ume uses [7]. The future widespread use of hydrogen is likely to be alternative route to hydrogen with a valuable co-product that is
in the transportation sector, where it will help reduce pollution. practiced commercially [15]. The production of hydrogen from bio-
Vehicles can be powered with hydrogen fuel cells, which are three mass has several advantages and limitations compared to that of
times more efficient than a gasoline-powered engine [8,9]. fossil fuels, as shown in Table 1 [2].
All primary energy sources can be used in the hydrogen-
producing process [10]. The production of hydrogen from fossil
2. Overview of biomass
fuels causes the co-production of carbon dioxide (CO2), which is
assumed to be the main responsible for the so-called ‘‘greenhouse
The most important biomass energy sources are wood and
effect’’ [11]. Hydrogen produced through a range of renewable
wood wastes, agricultural crops and their waste byproducts, muni-
primary energy sources such as wind, biomass, and solar energy
cipal solid waste (MSW), animal wastes, waste from food process-
ing, and aquatic plants and algae [16]. Biomass is the name given
⇑ Tel.: +90 462 876 2079; fax: +90 462 871 3110. all the earth’s living matter. Biomass as the solar energy stored
E-mail address: [email protected] in chemical form in plant and animal materials is among the most

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.11.010
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1779

Table 1 Cellulose is a high-molecular-weight (106 or more) linear poly-

Main advantages and limitations of biomass to hydrogen. mer of b-(1 ? 4)-D-glucopyranose units in the 4C1 conformation.
Advantages Hemicellulose is a mixture of various polymerized monosaccha-
Use of biomass reduces CO2 emissions rides such as glucose, mannose, galactose, xylose, arabinose, 4-O-
Crop residues conversion increases the value of agricultural output methyl glucuronic acid and galacturonic acid residues. Hemicellu-
Replacing fossil fuels with sustainable biomass fuel
Costs of getting rid of municipal solid wastes
loses exhibit lower molecular weights than cellulose. The number
of repeating saccharide monomers is only 150, compared to the
Limitations
Seasonal availability and high costs of handling
number in cellulose (5000–10000) [29]. Lignin is an aromatic poly-
Non-total solid conversion (char formation) and tars production mer synthesised from phenylpropanoid precursors. The basic
Process limitations: corrosion, pressure resistance and hydrogen aging chemical phenylpropane units of lignin (primarily syringyl, guaia-
cyl and p-hydroxy phenol) are bonded together by a set of linkages
to form a very complex matrix [30].
Hardwoods have a higher proportion of cellulose, hemicellu-
precious and versatile resources on earth. It is composed mainly of loses, and extractives than softwoods, but softwoods have a higher
carbohydrate compounds, the building blocks of which are the ele- proportion of lignin. In general, hardwoods contain about 43% cel-
ments carbon, hydrogen, oxygen and nitrogen. All biomass is pro- lulose, 35% hemicelluloses, and 22% lignin while softwoods contain
duced by green plants converting CO2 in the air, water and sunlight about 43% cellulose, 28% hemicelluloses, and 29% lignin (on an
into plant material through photosynthesis [17]. Photosynthesis is extractive free basis) [31,32].
a carbon fixation reaction by reduction of CO2. The fixation or
reduction of CO2 is a light-independent process. 3. Hydrogen production from biomass

2.1. Importance of biomass The methods available for the hydrogen production from bio-
mass can be divided into two main categories: thermochemical
Biomass, mainly in the form of wood, is the oldest form of en- and biological routes. The major biomass-to-hydrogen pathways
ergy used by humans. Traditionally, biomass has been utilized by are shown in Fig. 1 [33].
humans through direct combustion, and this process is still widely Biomass can be thermally processed through pyrolysis [34,35]
used in many parts of the world [18]. Traditional biomass provides or gasification [36,37] to produce hydrogen. In the pyrolysis and
about 7–11% of the world’s energy supply [19]. The average major- gasification processes, water–gas shift is used to convert the re-
ity of biomass energy is produced from wood and wood wastes formed gas into hydrogen, and pressure swing adsorption is used
(64%), followed by MSW (24%), agricultural waste (5%), and landfill to purify the product [38]. The major disadvantage of these pro-
gases (5%) [20–22]. Biomass energy has the potential to be ‘‘mod- cesses is the decomposition of the biomass feed stock leading to
ernized’’ worldwide, i.e., produced and used efficiently and cost char and tar formation [39].
competitively, generally in the more convenient forms of gases, liq- Biological production of hydrogen (biohydrogen) as a byproduct
uids, or electricity [23]. The importance of biomass energy will in- of microorganism metabolism is an exciting new area of technol-
crease as national energy policy and strategy focuses more heavily ogy development that offers the potential production of usable
on renewable sources and conservation. Biomass appears to be an hydrogen from a variety of renewable resources [40]. Biohydrogen
attractive feedstock for three main reasons [24]: provides a feasible means for the sustainable supply of hydrogen
with low pollution and high efficiency, thereby being considered
– it is a renewable resource that could be sustainably developed a promising way of producing hydrogen [41]. Biotechnology of
in the future, hydrogen production might be a most important way for energy
– it appears to have formidably positive environmental properties production in the near future because of its characteristics of low
resulting in no net releases of CO2 and very low sulfur content, costs and regeneration [42].
– it appears to have significant economic potential provided that
fossil fuel prices increase in the future. 3.1. Thermochemical conversion of biomass to hydrogen

Biomass is burned by direct combustion to produce steam turns 3.1.1. Hydrogen from biomass via pyrolysis
a turbine and the turbine drives a generator, producing electricity. Pyrolysis of biomass is a promising route for the production of
Gasifiers are used to convert biomass into a combustible gas (bio- solid (char), liquid (tar and other organics), and gaseous products
gas). The biogas is then used to drive a high efficiency, combined as possible alternate sources of energy. The most interesting tem-
cycle gas turbine [25]. Heat is used to thermo-chemically convert perature range for the production of the pyrolysis products is be-
biomass into pyrolysis oil. Pyrolysis oil, which is easier to store tween 625 and 775 K [43,44].
and transport than solid biomass material, is then burned like Depending on the operating conditions, the pyrolysis process
petroleum to generate electricity [20]. can be divided into three subclasses: conventional (slow) pyrolysis,
fast pyrolysis and flash pyrolysis. Slow pyrolysis of biomass is asso-
ciated with high charcoal continent, but the fast pyrolysis is asso-
2.2. Components of biomass ciated with tar, at low temperature (675–775 K) [45], and/or gas, at
high temperature [46]. At present, the preferred technology is fast
The chemical structure and major organic components in bio- or flash pyrolysis at high temperatures with very short residence
mass are extremely important in the development of processes times [47]. Table 2 indicates the product distribution obtained
for producing derived fuels and chemicals [26]. The components from different processes of pyrolysis process [48].
of biomass include cellulose, hemicelluloses, lignin, extractives, Although most pyrolysis processes are designed for biofuel pro-
lipids, proteins, simple sugars, starches, water, hydrocarbons, ash, duction, hydrogen can be produced directly through fast or flash
and other compounds. Two larger carbohydrate categories that pyrolysis if high temperature and sufficient volatile phase resi-
have significant value are cellulose and hemicelluloses (holocellu- dence time are allowed as follows [49]:
lose). The lignin fraction consists of non-sugar type molecules
[27,28].
Biomass þ heat ! H2 þ CO þ CH4 þ other products ð1Þ
1780 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789

Fig. 1. Hydrogen and liquid fuels production from biomass sources. The waste CO2, H2O, and energy produced from these fuels can be utilized to produce further biomass.
Source: Ref. [33].

Table 2 – charcoal – a low temperature, low heating rate process,

Product distribution obtained from different processes of pyrolysis process.
– liquid products – a low temperature, high heating rate, short
Thermal Residence Upper Product yield (%) gas residence time process, and
degradation time (s) temperature (K) – fuel gas – a high temperature, low heating rate, long gas resi-
Char Liquid Gas
dence time process.
Slow pyrolysis 200 600 32–38 28–32 25–29
120 700 29–33 30–35 32–36
90 750 26–32 27–34 33–37 At 1023 K, the gaseous yield increases to around 45–50% com-
60 850 24–30 26–32 35–43 pared to the yield of 30–35% at 773 K, based on the dry biomass
30 950 22–28 23–29 40–48
feed [33]. Demirbas [51] investigated the yields of hydrogen-rich
Fast pyrolysis 5 700 22–27 53–59 12–16 gases via pyrolysis at different temperature ranges. He reported
4 750 17–23 58–64 13–18
that increasing the pyrolysis temperature resulted in an increase
3 800 14–19 65–72 14–20
2 850 11–17 68–76 15–21
in the hydrogen yield as a percentage of the total gases evolved.
1 950 9–13 64–71 17–24 The percent of hydrogen in gaseous products by pyrolysis from
Gasification 1500 1250 8–12 4–7 81–88
the samples of hazelnut shell, tea waste and spruce wood in-
creased from 36.8% to 43.5%, 41.0% to 53.9% and 40.0% to 51.5%
by volume, respectively, while the final pyrolysis temperature
was increased from 700 to 950 K. One of the methods to increase
Methane and other hydrocarbon vapors can be converted into the hydrogen yield is to apply catalytic pyrolysis. Three types of
hydrogen and carbon monoxide (CO) by steam reforming: biomass feedstocks, olive husk, cotton cocoon shell and tea waste
CH4 þ H2 O ! CO þ 3H2 ð2Þ were pyrolyzed at about 775–1025 K in the presence of ZnCl2
and catalyst-to-biomass ratios of 6.5–17 by weight [52]. The high-
A water–gas shift reaction can be applied in order to increase est yield of hydrogen-rich gas (70.3%) was achieved from olive
the hydrogen production: husk using about 13% ZnCl2 at about 1025 K temperature. This
study also investigated the effect of K2CO3 and Na2CO3 on yield
CO þ H2 O ! CO2 þ H2 ð3Þ
of gaseous products from various biomass species with pyrolysis.
Pyrolysis of biomass is complex functions of the experimental The effect of K2CO3 and Na2CO3 as catalysts on pyrolysis depends
conditions, under which the pyrolysis process proceeds. The most on the biomass species. The catalytic effect of Na2CO3 was greater
important factors, which affect the yield and composition of the than that of K2CO3 for the cotton cocoon shell and tea factory
volatile fraction liberated, are: biomass species, chemical and waste, but the catalytic effect of K2CO3 was greater for the olive
structural composition of biomass, particle size, temperature, heat- husk [52]. The study of Caglar and Demirbas [53] indicates that
ing rate, residence time, atmosphere, pressure and reactor config- the catalytic effect of Na2CO3 is greater than CaCO3 for rice straw
uration [50]. Yield of products resulting from biomass pyrolysis pyrolysis. The yields of hydrogen-rich gas from pyrolysis of agricul-
can be maximized as follows: tural residues at different temperatures in the presence of Na2CO3
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1781

were investigated by Demirbas [54]. Results of this study are In addition, thermal cracking that occurs parallel to reforming pro-
shown in Fig. 2. As indicted in Fig. 2, the highest yield of hydro- duces carbonaceous deposits [60].
gen-rich gas was obtained from the walnut shell sample. Among
the different metal oxides, Al2O3 and Cr2O3 exhibit better catalytic
3.1.2. Hydrogen from biomass via gasification
effect than the others [49]. The use of noble metals (Rh, Ru and Pt)
Gasification of biomass has been identified as a possible system
in large scale industrial steam reforming is not common because of
for producing renewable hydrogen, which is beneficial to exploit
their relative high cost [55].
biomass resources, to develop a highly efficient clean way for
Hydrogen can also be produced by catalytic steam reforming of
large-scale hydrogen production, and has less dependence on inse-
bio-oil or its fractions [56,57]. Hydrogen production from bio-oil
cure fossil energy sources [61]. In general, the gasification temper-
provides a new route for utilization of bio-oil. Hydrogen produc-
ature is higher than that of pyrolysis and the yield of hydrogen
tion from renewable bio-oil is an attractive idea for fuel, energy,
from the gasification is higher than that of the pyrolysis [35].
and agricultural applications. In recent years hydrogen production
Biomass gasification can be considered as a form of pyrolysis,
via steam reforming of bio-oil has attracted more and more atten-
which takes place in higher temperatures and produces a mixture
tion. But because of the complicated composition of bio-oil and
of gases with H2 content ranging 6–6.5% [37]. The synthetic gas
carbon deposition on catalyst surface in reaction process, currently
produced by the gasification of biomass is made up of H2, CO,
the studies mainly focus on the steam reforming of model com-
CH4, N2, CO2, O2, and tar. When gasifying biomass, tar that is
pounds in bio-oil and reforming catalysts [58]. The bio-oil can be
formed together with the synthetic gas is difficult to remove with
stored and shipped to a centralized facility where it is converted
a physical dust removal method [62]. The product distribution and
to hydrogen via catalytic steam reforming and shift conversion
gas composition depends on many factors including the gasifica-
[59]. Catalytic steam reforming of bio-oil at 1025–1125 K over a
tion temperature and the reactor type [63]. The most important
Ni-based catalyst is a two-step process that includes the shift reac-
gasifier types are fixed bed (updraft or downdraft fixed beds), flu-
tion [8]:
idized bed, and entrained flow gasifiers. All these gasifiers need to
Bio-oil þ H2 O ! CO þ H2 ð4Þ include significant gas conditioning along with the removal of tars
and inorganic impurities and the subsequent conversion of CO to
H2 by water gas shift reaction as discussed in the pyrolysis section.
CO þ H2 O ! CO2 þ H2 ð5Þ
Table 3 shows typical gas composition data as obtained from com-
The overall stoichiometry gives a maximum yield of 0.172 g H2/ mercial wood and charcoal downdraft gasifiers operated on low to
g bio-oil (11.2% based on wood) [8]. medium moisture content fuels [64].
Gasification technologies provide the opportunity to convert
CH1:9 O0:7 þ 1:26H2 O ! CO2 þ 2:21H2 ð6Þ renewable biomass feedstocks into clean fuel gases or synthesis
In reality, this yield will always be lower because both the gases. The synthesis gas includes mainly hydrogen and carbon
steam reforming and water–gas shift reactions are reversible, monoxide (H2 + CO) which is also called as bio-syngas [65,66].
resulting in the presence of some CO and CH4 in the product gas. Bio-syngas is a gas rich in CO and H2 obtained by gasification of
biomass. Table 4 shows the composition of bio-syngas from bio-
mass gasification [37]. Hydrogen production is the largest use of
syngas. Biomass can be converted to bio-syngas by non-catalytic
[67], catalytic [68], and steam gasification [69] processes.
Steam gasification is a promising technology for thermochemi-
cal hydrogen production from biomass. Hydrogen is produced from
the steam gasification of legume straw and pine sawdust [70],
hazelnut shell [71], paper, yellow pine woodchips [72], mosses, al-
gae [43], wood sawdust [73], wheat straw [74], and waste wood
[75].
Rabah and Eldighidy [76] studied the production of hydrogen
gas on a pilot scale by steam gasification of charred lignocellulosic
waste material. In the study, the hydrogen gas was freed from
moisture and CO2. They investigated the beneficial effect of some
inorganic salts such as chlorides, carbonates and chromates on
the reaction rate and production cost of the hydrogen gas. Steam
reforming C1–C5 hydrocarbons, nafta, gas oils, and simple aromat-
ics are commercially practiced, well-known processes. Steam
reforming of hydrocarbons; partial oxidation of heavy oil residues,
selected steam reforming of aromatic compounds, and gasification
of coals and solid wastes to yield a mixture of H2 and CO, followed
by water–gas shift conversion to produce H2 and CO2, are well-
established processes [77]. Steam reforming and so-called dry or
Fig. 2. Plots for yields of hydrogen-rich gas from pyrolysis of agricultural residues CO2 reforming occur according to the following reactions and are
versus temperature in the presence 30% Na2CO3. Source: Ref. [54]. usually promoted by the use of catalysts.

Table 3
Typical gas composition data as obtained from commercial wood and charcoal downdraft gasifiers operated on low to medium moisture content fuels (wood 20%, charcoal 7%).

Component H2 (%) CO2 (%) CH4 (%) CO (%) N2 (%) Heating value (MJ/m3)
Wood gas 12–20 9–15 2–3 17–22 50–54 5–5.9
Charcoal gas 4–10 1–3 0–2 28–32 55–65 4.5–5.6
1782 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789

Table 4 [85]. The study showed that with decreasing particle size, the dry
Composition of bio-syngas from biomass gasification. gas yield, carbon conversion efficiency and H2 yield increased,
Constituents % by volume (dry and nitrogen free) and the content of char and tar decreased.
Carbon monoxide (CO) 28–36
Hydrogen (H2) 22–32 3.1.3. Hydrogen from biomass via supercritical water (fluid–gas)
Carbon dioxide (CO2) 21–30 extraction
Methane (CH4) 8–11 The supercritical fluid extraction (SFE) is a separation technol-
Ethene (C2H4) 2–4
Benzene–Toluene–Xylene (BTX) 0.84–0.96
ogy that uses supercritical fluid solvent. Fluids cannot be liquefied
Ethane (C2H5) 0.16–0.22 above the critical temperature, regardless of the pressure applied
Tar 0.15–0.24 but may reach the density close to the liquid state. Every fluid is
Others (NH3, H2S, HCl, dust, ash etc.) <0.021 characterized by a critical point, which is defined in terms of the
critical temperature and critical pressure. Water is a supercritical
fluid above 647.2 K and 22.1 MPa [86,87].
Cn Hm þ nH2 O¡CO þ ðn þ m=2ÞH2 ð7Þ Supercritical water (SCW) possesses properties very different
from those of liquid water. The dielectric constant of SCW is much
lower, and the number of hydrogen bonds is much lower and their
Cn Hm þ nCO2 ¡ð2nÞCO þ ðm=2ÞH2 ð8Þ
strength is weaker. As a result, high-temperature water behaves
Modeling of biomass steam gasification to synthesis gas is a like many organic solvents so that organic compounds have com-
challenge because of the variability (composition, structure, reac- plete miscibility with SCW. Moreover, gases are also miscible in
tivity, physical properties, etc.) of the raw material and because SCW, thus a SCW reaction environment provides an opportunity
of the severe conditions (temperature, residence time, heating rate, to conduct chemistry in a single fluid phase that would otherwise
etc.) required [78]. occur in a multiphase system under conventional conditions [88].
The yield of H2 from steam gasification increases with increas- The biomass gasification in SCW is a complex process, but the
ing water-to-sample (W/S) ratio [79]. The yields of H2 from steam overall chemical conversion can be represented by the simplified
gasification increase with increasing of temperature. The yield of net reaction:
hydrogen-rich gaseous product in the gaseous products from the
CHx Oy þ ð2  yÞH2 O ! CO2 þ ð2  y þ x=2ÞH2 ð9Þ
black liquor steam gasification run (W/S = 1.9) increased from
38.0% to 50.3% with increasing temperature from 975 to 1325 K where x and y are the elemental molar ratios of H/C and O/C in bio-
[80]. The yields of H2 from steam gasification of hazelnut shell at mass, respectively. The reaction product is syngas whose quality de-
different temperatures were investigated by Demirbas [71]. Steam pends on x and y. The reaction (Eq. (9)) is an endothermic. It is
gasification runs were carried out over a temperature range from known from the reaction (Eq. (9)) that water is not only the solvent
925 to 1225 K. W/S ratios were 0.7 and 1.9 in steam gasification but also a reactant and the hydrogen in the water is released by the
runs. The highest H2 yield (59.5%) was obtained from the gasifica- gasification reaction [89].
tion run (W/S = 1.9) at 1225 K. Kriengsak et al. [72] investigated Compared with other biomass thermochemical gasifications,
high-temperature steam gasification of paper, yellow pine wood- such as air gasification or steam gasification, the SCW gasification
chips, and Pittsburgh bituminous coal in a batch-type flow reactor has high gasification efficiency at lower temperature and can deal
at temperatures in the range of 973–1473 K at two different ratios directly with wet biomass without drying [90]. Hydrogen produc-
of steam to feedstock molar ratios. Hydrogen yield of 54.7% for pa- tion by biomass gasification in SCW is a promising technology for
per, 60.2% for woodchips, and 57.8% for coal was achieved on a dry utilizing high moisture content biomass [89]. Another advantage of
basis, with a steam flow rate of 6.3 g/min at steam temperature of SCW reforming is that the H2 is produced at a high pressure’ which
1473 K. can be stored directly, thus avoiding the large energy expenditures
The effect of catalyst on gasification products is very important. associated with its compression [91]. The cost of hydrogen produc-
The use of the catalyst did not affect the gas yields, but the compo- tion from SCW gasification of wet biomass was several times high-
sition of the gases was strongly influenced. The content of H2 and er than the current price of hydrogen from steam methane
CO2 increased, while that of CO decreased; a drastic reduction in reforming. Biomass is gasified in supercritical water at a series of
the content of organic compounds could also be observed. Because temperatures and pressures during different resident times to form
the char yields remained almost constant compared to an equiva- a product gas composed of H2, CO2, CO, CH4, and a small amount of
lent no catalytic thermal run, the increase in the content of hydro- C2H4 and C2H6 [37,92]. SCW is a promising reforming media for the
gen was probably due to the influence of the catalyst on the water direct production of hydrogen at 875–1075 K temperatures with a
gas shift reaction [79]. Dolomite, Ni-based catalysts and alkaline short reaction time (2–6 s). As the temperature is increased from
metal oxides are widely used as gasification catalysts [49]. The 875 to 1075 K the H2 yield increases from 53% to 73% by volume,
yields of hydrogen from biomass with the use of dolomite in the respectively [91,92]. Only a small amount of hydrogen is formed
fluidized-bed gasifier and the use of nickel-based catalysts in the at low temperatures, indicating that direct reformation reaction
fixed bed reactor downstream from the gasifier were investigated of ethanol as a model compound in SCW is favored at high temper-
by Lv et al. [81]. They obtained a maximum hydrogen yield atures (>975 K) [91]. With an increase in the temperature, the
(130.28 g H2/kg biomass) over the temperature range of 925– hydrogen and carbon dioxide yields increase, while the methane
1125 K. Three types of catalysts were tested by Corte et al. [82]: yield decreases [89].
alumina, aluminosilicate material, and nickel-supported catalysts. Many researchers have investigated the aqueous conversion of
Minowa and Inoue [83] have carried out studies on the high-pres- whole biomass to hydrogen under low temperature but supercrit-
sure steam gasification of cellulose and lignocellulose materials ical conditions. The earliest report of SCW gasification of wood is
using a reduced metal catalyst. K2CO3 catalyst shows a destructive by Modell [93]. The author studied the effect of temperature and
effect on the organic compounds, and H2 and CO2 form at the end concentration on the gasification of glucose and maple sawdust
of the catalytic steam reforming process [84]. The catalytic steam in water, in the vicinity of its critical state (650 K and 22 MPa). Elli-
gasification of biomass in a lab-scale fixed bed reactor in order to ott and co-workers [94] from Pacific Northwest National Labora-
evaluate the effects of particle size at different bed temperatures tory (PNNL) investigated a variety of commercial catalysts and
on the gasification performance was carried out by Luo et al. support materials in hot liquid water at 20 MPa and 623 K to
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1783

convert organic compounds to gaseous products rich in methane. 3.2. Biological process for hydrogen production
They reported that Ni-based catalyst showed an excellent activity
on the gasification. Schmieder et al. [95] found that real biomass Hydrogen produced from water, renewable organic wastes or
(wood as sawdust, straw) and wastes (sewage, sludge and lignin) biomass, either biologically (biophotolysis and fermentation) or
were completely gasified by addition of KOH or K2CO3 at 873 K photobiologically (photodecomposition), is termed ‘‘biohydrogen’’.
and 25 MPa, forming a H2-rich gas containing CO2 as the main car- Biological hydrogen production processes are found to be more
bon compound. Kruse and co-workers [96] studied the gasification environment friendly and less energy intensive as compared to
of pyrocatachol in SCW as part of a fundamental look at hydrogen thermochemical and electrochemical processes [98]. Researchers
production from high-moisture biomass and wastewater. In the have started to investigate hydrogen production with anaerobic
study, batch and tubular reactors were used. bacteria since 1980s [99–101]. The main advantages of different
biological hydrogen production processes are given in Table 6
3.1.4. Comparison of thermochemical processes [102].
In general, the gasification temperature is higher than that of The processes of biological hydrogen production can be broadly
pyrolysis and the yield of hydrogen from the gasification is higher classified into two distinct groups. One is light dependent and the
than that of the pyrolysis. The yield of hydrogen from conventional other is light-independent process [5]. Specific ways in which
pyrolysis of corncob increases from 33% to 40% with increasing of microorganisms can produce H2 are described below [103]:
temperature from 775 to 1025 K. The yields of hydrogen from
steam gasification increase from 29 to 45% for (W/S) = 1 and from – Biophotolysis of water using green algae and blue-green algae
29% to 47% for (W/S) = 2 with increasing of temperature from (cyanobacteria):
975 to 1225 K [74]. Hydrogen yields and energy contents, com-  Direct biophotolysis.
pared, with biomass energy contents obtained from processes with  Indirect biophotolysis.
biomass, are shown in Table 5 [97]. – Photo-fermentation.
Demirbas [74] investigated the yield of hydrogen from super- – Dark fermentation.
critical fluid extraction (SFE), pyrolysis and steam gasification of – Hybrid reactor system.
wheat straw and olive waste at different temperatures. The highest
yields (% dry and ash free basis) were obtained from the pyrolysis There are three types of microorganisms of biohydrogen genera-
(46%) and steam gasification (55%) of wheat straw while the lowest tion: cyanobacteria, anaerobic bacteria, and fermentative bacteria.
yields from olive waste. He also investigated the yield of hydrogen The cyanobacteria directly decompose water to biohydrogen and
from SFE, pyrolysis and steam gasification of beech wood at differ- oxygen in the presence of light energy by photosynthesis. Photo-
ent temperatures. Distilled water was used in the SFE (the critical synthetic bacteria use organic substrates like organic acids. Anaer-
temperature of pure water is 647.7 K). Results of this study are obic bacteria use organic substances as the sole source of electrons
shown in Fig. 3. From Fig. 3, the yield of hydrogen from SFE was and energy, converting them into biohydrogen. Biological hydro-
considerably high (49%) at lower temperatures. The pyrolysis was gen can be generated from plants by biophotolysis of water using
carried out at the moderate temperatures and steam gasification microalgae (green algae and cyanobacteria), fermentation of
at the highest temperatures. organic compounds, and photodecomposition of organic com-
pounds by photo-synthetic bacteria [99].All processes of biological
hydrogen production are fundamentally dependent upon the pres-
Table 5 ence of a hydrogen-producing enzyme. Hydrogenases and nitro-
Comparison of hydrogen yields were obtained by use of three different processes.
genases are the known enzymes which catalyze biological
Processes Hydrogen Hydrogen energy contents/ hydrogen production [104]. Hydrogenases are the key enzymes
yield (wt.%) biomass energy content for the biological hydrogen production, which can be classified as
Pyrolysis + catalytic reforming 12.6 91 uptake hydrogenases and reversible hydrogenases. Uptake hydrog-
Gasification + shift reaction 11.5 83 enases, such as Ni–Fe hydrogenases and Ni–Fe–Se hydrogenases,
Biomass + steam + except heat 17.1 124
act as important catalysts for hydrogen consumption as follows
(theoretical maximum)
[49]:

Fig. 3. Plots for yield of hydrogen from supercritical fluid extraction, pyrolysis and steam gasification [(W/S) = 2] of beech wood at different temperatures. Source: Ref. [74].
1784 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789

H2 ! 2e þ 2Hþ ð10Þ tosynthetic systems of microalgae to convert water into chemical
energy.
Reversible hydrogenases, as indicated by its name, have the ability
to produce H2 as well as consume H2 depending on the reaction 2H2 O þ Light energy ! 2H2 þ O2 ð12Þ
condition,
The solar energy is absorbed by the pigments at photosystem I
H2 $ 2e þ 2Hþ ð11Þ (PSI), or photosystem II (PSII) or both, which raises the energy level
of electrons from water oxidation when they are transferred from
Despite increasingly conspicuous diversity in many respects, PSI via PSII to ferredoxin [107]. The concept of ‘‘direct biophotoly-
hydrogenase can be classified broadly into three distinct classes: sis’’ envisions light-driven simultaneous O2 evolution on the oxi-
Ni–Fe hydrogenase, Fe-hydrogenase and metal-free hydrogenase dizing side of PSII and H2 production on the reducing side of PSI,
[105]. Classification of hydrogenases is given in Table 7. with a maximum H2:O2 (mol:mol) ratio of 2:1 [108].
Since hydrogenase is sensitive to oxygen, it is necessary to
3.2.1. Biophotolysis of water using microalgae maintain the oxygen content at a low level under 0.1% so that
Biophotolysis is the action of light on biological systems that re- hydrogen production can be sustained. This condition can be ob-
sults in the dissociation of a substrate usually water into molecular tained by the use of green algae Chlamydomonas reinhardtii that
hydrogen and oxygen. Photo-synthetic bacteria (e.g. Rhodobactor) can deplete oxygen during oxidative respiration [49,103]. Reported
can use broad organic substrates including lactic and acetic acids hydrogen production rates using this method are approximately
as the energy and carbon source under light irradiation. Photoauto- 0.07 mmol/h per liter [109,110].
trophic green algae and cyanobacteria use sunlight and carbon
dioxide as the sole sources for energy and carbon [92]. Based on 3.2.1.2. Indirect biophotolysis. In indirect biophotolysis, the problem
a preliminary engineering and economic analysis, biophotolysis of sensitivity of the hydrogen evolving process to oxygen is usually
processes must achieve close to an overall 10% solar energy con- circumvented by separating oxygen and hydrogen [110–112]. The
version efficiency to be competitive with alternatives sources of concept of indirect biophotolysis involves the following four steps
renewable hydrogen [106]. [49]: (1) biomass production by photosynthesis, (2) biomass con-
centration, (3) aerobic dark fermentation yielding 4 mol hydro-
3.2.1.1. Direct biophotolysis. Direct biophotolysis of hydrogen pro- gen/mol glucose in the algae cell, along with 2 mol of acetates,
duction is a biological process which utilizes light energy and pho- and (4) conversion of 2 mol of acetates into hydrogen. In a typical
indirect biophotolysis, cyanobacteria can synthesize and evolve
hydrogen through photosynthesis by following reactions:
Table 6
The main advantages of different biological hydrogen production processes. Source: 12H2 O þ 6CO2 þ Light energy ! C6 H12 O6 þ 6O2 ð13Þ
Ref. [102].

Process Advantages C6 H12 O6 þ 12H2 O þ Light energy ! 12H2 þ 6CO2 ð14Þ

Direct biophotolysis It can produce H2 directly from water
and sunlight
Hydrogen production by cyanobacteria has been studied for
Solar conversion energy increased by 10- over three decades and has revealed that efficient photoconversion
folds as compared to tress, crops of H2O to H2 is influenced by many factors [102]. Rates of H2 pro-
Indirect biophotolysis It can produce H2 from water duction by non-nitrogen-fixing Cyanobacteria range from
Has the ability to fix N2 from atmosphere 0.02 lmol H2/mg chl a/h (Synechococcus PCC 6307) to 0.40 lmol
Photo-fermentation A wide spectral light energy can be used H2/mg chl a/h (Aphanocapsa montana) [113].
by these bacteria
It can use different waste materials like
3.2.2. Photo-fermentation
distillery effluents, waste, etc.
Purple non-sulfur bacteria evolve molecular hydrogen catalyzed
Dark fermentation It can produce H2 all day long without
by nitrogenase under nitrogen-deficient conditions using light en-
light
A variety of carbon sources can be used ergy and reduced compounds (organic acids) [114]. These bacteria
as substrates themselves are not powerful enough to split water. However, un-
It produces valuable metabolites such as der anaerobic conditions, these bacteria are able to use simple or-
butyric, lactic, and acetic acids as by ganic acids, like acetic acid, or even hydrogen disulfide as electron
products
donor. These electrons are transported to the nitrogenase by ferre-
It is anaerobic process, so there is no O2
limitation problem doxin using energy in the form of adenosine triphosphate (ATP).
Hybrid reactor system (combined Two stage fermentation can improve the
When nitrogen is not present, this nitrogenase enzyme can reduce
dark and photo-fermentation) overall yield of hydrogen proton into hydrogen gas again using extra energy in the form of
ATP [110]. The reaction can be given as

Table 7
Classification of hydrogenases. Source: Ref. [105].

Classification Occurrence/source Structure Features

Localization Function
Ni–Fe Anaerobic, photo-synthetic bacteria, Heterodimeric, multimeric Membrane-bound, cytoplasmic, Uptake of hydrogen
cyanobacteria periplasmic
Ni–Fe–Se Sulphate-reducing bacteria, Oligomeric Membrane-bound, cytoplasmic Oxidation of hydrogen
methanogenes
Fe Photo-synthetic bacteria, anaerobic Monomeric, heteromeric Cytoplasmic, mambrane- bound, Production of hydrogen
fermentative bacteria, cyanobacteria, periplasmic chloroplast, hydrogenosomes
green algae, protozoan
Metal-free Methanogens Monomeric Cytoplasmic Formation of hydrogen
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1785

C6 H12 O6 þ 12H2 O þ Light energy ! 12H2 þ 6CO2 ð15Þ C6 H12 O6 þ 2H2 O ! 2CH3 COOH þ 2CO2 þ 4H2 ð16Þ
Among the various bioprocesses capable of hydrogen produc-
C6 H12 O6 ! CH3 CH2 COOH þ 2CO2 þ 2H2 ð17Þ
tion, photo-fermentation is favored due to relatively higher sub-
strate-to-hydrogen yields and, its ability to trap energy under a Thus, the highest theoretical yields of H2 are associated with
wide range of the light spectrum and versatility in sources of met- acetate as the fermentation end-product. In practice, however,
abolic substrates with promise for waste stabilization [115]. In high H2 yields are usually associated with a mixture of acetate
photo-fermentation processes, the yield of the order of 80% has and butyrate fermentation products, and low H2 yields are with
been achieved [110]. However, these processes have three main associated propionate and reduced end-products (alcohols, lactic
drawbacks [49]: (1) use of nitrogenase enzyme with high-energy acid). Clostridium pasteurianum, Clostridium butyricum, and Clostrid-
demand, (2) low solar energy conversion efficiency and (3) demand ium beijerinkii are high H2 producers, while Clostridium propionicum
for elaborate anaerobic photobioreactors covering large areas. is a poor H2 producer [113,118,119].
The amount of hydrogen production by dark fermentation
highly depends on the pH value, hydraulic retention time (HRT)
3.2.3. Dark fermentation and gas partial pressure. For the optimal hydrogen production,
Hydrogen can be produced by anaerobic bacteria, grown in the pH should be maintained between 5 and 6 [49]. Hydrogen produc-
dark on carbohydrate-rich substrates. Dark fermentation of carbo- tion from the bacterial fermentation of sugars has been examined
hydrate-rich substrates as biomass presents a promising route of in a variety of reactor systems. Hexose concentration has a greater
biological hydrogen production, compared with photosynthetic effect on H2 yields than the HRT. Flocculation also was an impor-
routes [116]. Anaerobic hydrogen fermenting bacteria can produce tant factor in the performance of the reactor [66,99]. The hydrogen
hydrogen continuously without the need for photoenergy [117]. yield from sucrose by dark-fermentation could be difficult to in-
Dark hydrogen fermentation can be performed at different temper- crease above 2.5-mol/mol hexose, owing to the formation of fatty
atures: mesophilic (298–313 K), thermophilic (313–338 K), ex- acids during the fermentation process [120].
treme-thermophilic (338–353 K) or hyperthermophilic (>353 K)
temperatures. While direct and indirect photolysis systems pro- 3.2.4. Two-stage process (integration of dark- and photo-
duce pure H2, dark-fermentation processes produce a mixed biogas fermentation)
containing primarily H2 and CO2, but which may also contain lesser A combination of dark and photo-fermentation in a two-stage
amounts of methane (CH4), CO, and/or hydrogen sulfide (H2S) hybrid system could be expected to reach as close to the theoreti-
[113]. Glucose yield different amount of hydrogen depending on cal maximum production of 12 mol of H2 (mol glucose)1 equiva-
the fermentation pathways and liquid end-products. A maximum lent as possible, according to the following reactions [5]:
of 4 mol hydrogen is theoretically produced from 1 mol of glucose
with acetic acid as the end-product, while a maximum of 2 mol i. Stage I – dark fermentation (facultative anaerobes)
hydrogen is theoretically produced from 1 mol of glucose with
butyrate as the end-product [117]: C6 H12 O6 þ 2H2 O ! 2CH3 COOH þ 2CO2 þ 4H2 ð18Þ

Cellulose and starch containing wastes

Grinding

Pretreatment including delignication

Hydrolysis

Wastewater
Glucose syrup

Pretreatment Dark fermentation Organic acids

H2 + CO2 Photo-fermentation

H2 separation Treated wastewater

CO2

H2
Fig. 4. A schematic diagram for biohydrogen production from cellulose/starch containing agricultural wastes and food industry wastewaters. Source: Ref. [123].
1786 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789

Fig. 5. (A) Global production of hydrogen by sources and (B) global use of hydrogen by sector.

ii. Stage II – photo-fermentation (photo-synthetic bacteria) duced from fossil fuels, the CO2 generated must be captured and
sequestered for there to be significant reductions in GHG emissions
2CH3 COOH þ 4H2 O ! 8H2 þ 4CO2 ð19Þ versus conventional transportation fuels used with advanced vehi-
cle technologies [133].
In the first step biomass is fermented to acetate, carbon dioxide, Presently, 48% H2 is produced from natural gas, 30% from heavy
and hydrogen by thermophilic dark fermentation, while in the sec- oils and naphtha, 18% from coal, and 4% from electrolysis (Fig. 5A)
ond step, acetate is converted to hydrogen and carbon dioxide [134]. H2 can be used either as the fuel for direct combustion in an
[121,122]. internal combustion engine or as the fuel for a fuel cell [5].
Starch, cellulose or hemicellulose content of wastes, carbohy- However, the largest users of H2 are the fertilizer and petroleum
drate rich food industry effluents or waste biological sludge can industries with, respectively, 49% and 37% (Fig. 5B) [7]. Present uti-
be further processed to convert the carbohydrates to organic acids lization of hydrogen is equivalent to 3% of the energy consumption
and then to hydrogen gas by using proper bioprocessing technolo- and with a growth rate estimated at 5–10% per year [6].
gies. Fig. 4 shows schematic diagram for biohydrogen production Hydrogen is currently more expensive than conventional en-
from food industry wastewaters and agricultural wastes by two ergy sources. In the longer-term renewables will become the most
stage, anaerobic dark and photo-fermentations [123]. important source for the production of hydrogen. Hydrogen will
play an important role in a future energy economy mainly as a
storage and transportation medium for renewable energy sources.
4. Present scenario and future prospects Renewable shares of 69% on the total energy demand will lead to
hydrogen shares of 34% in 2050 (Table 8) [135].
Energy demand has grown strongly and will continue to in- Many experts think that hydrogen has a major role to play as an
crease, particularly in developing countries where energy is energy carrier in future energy supply [136–138]. There are many
needed for economic growth and poverty alleviation [124]. Accord- conventional methods for producing hydrogen, like thermochemi-
ing to the International Energy Agency (IEA) estimates [125], world cal process, catalytic reforming of hydrocarbons and electrolysis of
energy demand will increase by half again between now and 2030, water, but these methods are not economical and are mostly non-
with more than two-thirds of this increase coming from develop- renewable [4]. Production of hydrogen from renewable biomass
ing and emerging countries. At the present time primary energy has several advantages compared to that of fossil fuels [8]. Biolog-
sources are dominated by fossil fuels, with nearly 80% of global en- ical production of hydrogen as a byproduct of microorganism
ergy demand supplied from crude oil, natural gas, and coal [126]. metabolism is an exciting new area of technology development
In 1985, total worldwide petroleum consumption was 2807 that offers the potential production of usable hydrogen from a vari-
million tons, but in 2008, the figure reached 3928 million tons, ety of renewable resources [113]. Biological production of hydro-
with an average annual growth rate of almost 1.5% [127]. Today, gen provides a feasible means for the sustainable supply of
the transportation sector worldwide is almost entirely dependent hydrogen with low pollution and high efficiency, thereby being
on petroleum-derived fuels. One-fifth of global CO2 emissions are considered a promising way of producing hydrogen, and it had
created by the transport sector, which accounts for some 60% of got special attention in the last decade [139].
global oil consumption [127]. The dramatic increase in the price Biomass will play an important role in the future global energy
of petroleum, the finite nature of fossil fuels, increasing concerns infrastructure for the generation of power and heat, but also for the
regarding environmental impact, especially related to GHG emis-
sions, and health and safety considerations are forcing the search Table 8
for new energy sources and alternative ways to power the world’s Share of individual primary energy sources in meeting final energy needs (%). Source:
motor vehicles [3128,129]. Environmental, economical and politi- Ref. [135].
cal concerns are generating a growing interest in biofuels. Biofuels Source of energy 1998 2025 2050
include energy security reasons, environmental concerns, foreign
Fossil fuels 88 62 29
exchange savings, and socioeconomic issues related to the rural Nuclear energy 10 2 2
sectors of all countries in the world. Biofuels are environmentally Hydrogen from solar energy – 7 31
friendly alternatives automotive fuel that can be used in an inter- Electricity from solar energy – 11 16
nal combustion engine [130–132]. Heat from solar energy – 18 22
Energy from solar energy 2 25 35
Hydrogen can help reduce carbon emissions, if produced from
Hydrogen – 11 34
renewable energy sources and nuclear energy. If hydrogen is pro-
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1787

Fig. 6. (A) Evolution of global market shares of different final-energy carriers and (B) global hydrogen supply mix for the period 2000–2100 in the B1–H2 scenario. Source: Ref.
[142].

production of chemicals and fuels. The dominant biomass conver- References

sion technology will be gasification, as the gases from biomass gas-
ification are intermediates in the high-efficient power production [1] Demirbas A. New liquid biofuels from vegetable oils via catalytic pyrolysis.
Energy Educ Sci Technol 2008;21:1–59.
or the synthesis from chemicals and fuels [140]. Biomass gasifica- [2] Balat M, Balat M. Political, economic and environmental impacts of biomass-
tion offers the earliest and most economical route for the produc- based hydrogen. Int J Hydrogen Energy 2009;34:3589–603.
tion of renewable hydrogen [34]. IIASA’s Environmentally [3] Sigar CP, Soni SL, Mathur J, Sharma D. Performance and emission
characteristics of vegetable oil as diesel fuel extender. Energy Source A
Compatible Energy Strategies (ECS) project has developed a long- 2009;31:139–48.
term hydrogen-based scenario (B1–H2) of the global energy system [4] Behera BK, Balasundaram R, Gadgil K, Sharma DK. Photobiological production
to examine the future perspectives of fuel cells [141]. The scenario of hydrogen from Spirulina for fueling fuel cells. Energy Source A
2007;29:761–7.
illustrates the key role of hydrogen in a long-term transition to-
[5] Kotay SM, Das D. Biohydrogen as a renewable energy resource – prospects
wards a clean and sustainable energy future. Fig. 6 is redrawn from and potentials. Int J Hydrogen Energy 2008;33:258–63.
the B1–H2 scenario in order to show trends in global market shares [6] Mohan SV, Bhaskar YV, Sarma PN. Biohydrogen production from chemical
of different final-energy carriers and in global hydrogen supply as a wastewater treatment in biofilm configured reactor operated in periodic
discontinuous batch mode by selectively enriched anaerobic mixed consortia.
standard. Hydrogen, in particular, driven by the penetration of effi- Water Res 2007;41:2652–64.
cient end-use technologies, increases its share dramatically, [7] Konieczny A, Mondal K, Wiltowski T, Dydo P. Catalyst development for
accounting for approximately 49% of the global final consumption thermocatalytic decomposition of methane to hydrogen. Int J Hydrogen
Energy 2008;33:264–72.
by the end of the 21st century, and becomes the main final-energy [8] Nath K, Das D. Hydrogen from biomass. Curr Sci 2003;85:265–71.
carrier (Fig. 6A). Biomass gasification will become a dominant [9] Momirlan M, Veziroglu T. The properties of hydrogen as fuel tomorrow in
technology in the future (Fig. 6B) [142]. sustainable energy system for a cleaner planet. Int J Hydrogen Energy
2005;30:795–802.
[10] Veziroglu T. Hydrogen energy, part A. New York (NY): Plenum Press; 1975.
[11] Resini C, Arrighi L, Delgado MCH, Vargas MAL, Alemany LJ, Riani P, et al.
5. Conclusion Production of hydrogen by steam reforming of C3 organics over Pd–Cu/c-
Al2O3 catalyst. Int J Hydrogen Energy 2006;31:13–9.
Hydrogen produced from biorenewables is a sustainable energy [12] Yolcular S. Hydrogen production for energy use in European Union countries
and Turkey. Energy Source A 2009;31:1329–37.
carrier for promising alternative to fossil fuels. Biomass-based [13] Demirbas A. Biofuels sources, biofuel policy, biofuel economy and global
hydrogen includes energy security reasons, environmental con- biofuel projections. Energy Convers Manage 2008;49:2106–16.
cerns, foreign exchange savings, and socioeconomic issues related [14] Larsen H, Feidenhans’l R, Petersen, LS. Hydrogen and its competitors. Risø
energy report 3, Risø National Laboratory, Roskilde, Denmark; November,
to the rural sectors of all countries in the world. Due to its environ- 2004.
mental merits, the share of hydrogen from biomass in the automo- [15] Demirbas A. Production of combustible gas from triglycerides via pyrolysis.
tive fuel market will grow fast in the next decade.Hydrogen is Energy Source A 2009;31:870–5.
[16] Demirbas MF, Balat M, Balat H. Potential contribution of biomass to the
currently more expensive than conventional energy sources. In sustainable energy development. Energy Convers Manage 2009;50:1746–60.
the longer-term renewables will become the most important [17] Tuncel F, Gercel HF. Production and characterization of pyrolysis oils from
source for the production of hydrogen. Thermochemical (pyrolysis Euphorbia macroclada. Energy Source A 2004;26:761–70.
[18] Balat M. Mechanisms of thermochemical biomass conversion processes. Part
and gasification) and biological (biophotolysis, photo-fermentation
3: reactions of liquefaction. Energy Source A 2008;30:649–59.
and dark fermentation) processes can be practically applied to pro- [19] Balat M. Development of worldwide green electricity in the past decade.
duce hydrogen. Biomass gasification offers the earliest and most Energy Source B 2009;4:17–33.
economical route for the production of renewable hydrogen. Steam [20] Demirbas A. Biomass resource facilities and biomass conversion processing
for fuels and chemicals. Energy Convers Manage 2001;42:1357–78.
reforming of natural gas and gasification of biomass will become [21] Demirbas A. Modernization of biomass energy conversion facilities. Energy
the dominant technologies by the end of the 21st century. Source B 2007;2:227–35.
1788 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789

[22] Balat M. Gasification of biomass to produce gaseous products. Energy Source [58] Wu C, Yan Y, Li T, Qi W. Preparation of hydrogen through catalytic steam
A 2009;31:516–26. reforming of bio-oil. Chin J Process Eng 2007;7:1114–9.
[23] Larson ED, Kartha S. Expanding roles for modernized biomass energy. Energy [59] Evans RJ, Chornet E, Czernik S, Feik C, French R, Phillips S, et al. Renewable
Sustain Develop 2000;4:15–25. hydrogen production by catalytic steam reforming of peanut shells pyrolysis
[24] Demirbas A. Emission characteristics of gasohol and diesohol. Energy Source products. ACS Div Fuel Chem 2003;48:594–5.
A 2009;31:1099–104. [60] Turner J, Sverdrup G, Mann MK, Maness PC, Kroposki B, Ghirardi M, et al.
[25] Balat M, Ayar G. Biomass energy in the world, use of biomass and potential Renewable hydrogen production. Int J Energy Res 2008;32:379–407.
trends. Energy Source A 2005;27:931–40. [61] Demirbas MF. Technological options for producing hydrogen from renewable
[26] Yaman S. Pyrolysis of biomass to produce fuels and chemical feedstocks. resources. Energy Source A 2006;28:1215–23.
Energy Convers Manage 2004;45:651–71. [62] Yoon SJ, Choi YC, Lee JG. Hydrogen production from biomass tar by catalytic
[27] Demirbas A. Pyrolysis mechanisms of biomass materials. Energy Source A steam reforming. Energy Convers Manage 2010;51:42–7.
2009;31:1186–93. [63] Stevens DJ. Hot gas conditioning: recent progress with larger-scale biomass
[28] Demirbas A. Pyrolysis of biomass for fuels and chemicals. Energy Source A gasification systems. NREL subcontractor report: NREL/SR-510-29952,
2009;31:1028–37. Golden, Colorado; August, 2001.
[29] Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: a [64] Stassen HEM, Knoef HAM. Small scale gasification systems. The Netherlands:
critical review. Energy Fuels 2006;20:848–89. Biomass Technology Group, University of Twente; 1993.
[30] Balat M, Balat M, Kırtay E, Balat H. Main routes for the thermo-conversion of [65] Balat M. Sustainable transportation fuels from biomass materials. Energy
biomass into fuels and chemicals. Part 1: pyrolysis systems. Energy Convers Educ Sci Technol 2006;17:83–103.
Manage 2009;50:3147–57. [66] Demirbas A. Converting biomass derived synthetic gas to fuels via Fisher–
[31] Balat M. Mechanisms of thermochemical biomass conversion processes. Part Tropsch synthesis. Energy Source A 2007;29:1507–12.
1: reactions of pyrolysis. Energy Source A 2008;30:620–35. [67] Cobb JT. Production of synthesis gas by biomass gasification. In: Proceedings
[32] Demirbas A. Mechanisms of thermal degradation of wood in alkaline glycerol. of the 2007 spring national AIChE meeting, Houston, Texas; April 22–26,
Energy Source A 2009;31:1294–9. 2007.
[33] Tanksale A, Beltramini JN, Lu GM. A review of catalytic hydrogen production [68] Lv P, Yuan Y, Wu C, Ma L, Chen Y, Tsubaki N. Bio-syngas production from
processes from biomass. Renew Sustain Energy Rev 2010;14:166–82. biomass catalytic gasification. Energy Convers Manage 2007;48:
[34] Caglar A, Demirbas A. Conversion of cotton cocoon shell to hydrogen rich 1132–9.
gaseous products by pyrolysis. Energy Convers Manage 2002;43:489–97. [69] Chaudhari ST, Dalai AK, Bakhshi NN. Production of hydrogen and/or syngas
[35] Balat M. Hydrogen-rich gas production from biomass via pyrolysis and (H2 + CO) via steam gasification of biomass-derived chars. Energy Fuels
gasification processes and effects of catalyst on hydrogen yield. Energy 2003;17:1062–7.
Source A 2008;30:552–64. [70] Wei L, Xu S, Zhang L, Liu C, Zhu H, Liu S. Steam gasification of biomass for
[36] Yan Q, Lu Y. Thermodynamic analysis of hydrogen production from biomass hydrogen-rich gas in a free-fall reactor. Int J Hydrogen Energy 2007;32:
gasification in supercritical water. Energy Convers Manage 2006;47:1515–28. 24–31.
[37] Demirbas A. Hydrogen production from carbonaceous solid wastes by steam [71] Demirbas A. Thermochemical conversion of hazelnut shell to gaseous
reforming. Energy Source A 2008;30:924–31. products for production of hydrogen. Energy Source A 2005;27:339–47.
[38] Balat M, Balat M, Kırtay E, Balat H. Main routes for the thermo-conversion of [72] Kriengsak SN, Buczynski R, Gmurczyk J, Gupta AK. Hydrogen production by
biomass into fuels and chemicals. Part 2: gasification systems. Energy high-temperature steam gasification of biomass and coal. Environ Eng Sci
Convers Manage 2009;50:3158–68. 2009;26:739–44.
[39] Swami SM, Chaudhari V, Kim DS, Sim SJ, Abraham MA. Production of [73] Demirbas MF. Producing hydrogen from biomass via non-conventional
hydrogen from glucose as a biomass simulant: integrated biological and processes. Energy Explor Exploit 2004;22:225–33.
thermochemical approach. Ind Eng Chem Res 2008;47:3645–51. [74] Demirbas MF. Hydrogen from various biomass species via pyrolysis and
[40] Cheong DY, Hansen CL. Bacterial stress enrichment enhances anaerobic steam gasification processes. Energy Source A 2006;28:245–52.
hydrogen production in cattle manure sludge. Appl Microbiol Biotechnol [75] Wu W, Kawamoto K, Kuramochi H. Hydrogen-rich synthesis gas production
2006;72:635–43. from waste wood via gasification and reforming technology for fuel cell
[41] Wu K, Chang JS. Batch and continuous fermentative production of hydrogen application. J Mater Cycles Waste Manage 2006;8:70–7.
with anaerobic sludge entrapped in a composite polymeric matrix. Process [76] Rabah MA, Eldighidy SM. Low cost hydrogen production from waste. Int J
Biochem 2007;42:279–84. Hydrogen Energy 1989;14:221–7.
[42] Ming L, Nanqi R, Aijie W. Hydrogen production efficiency of mixed-culturing [77] Demirbas A. Hydrogen production from biomass by gasification process.
bacteria with non-immobilized technology in a hydrogen-producing Energy Source A 2002;24:59–68.
bioreactor. In: VII. Latin American workshop and symposium on anaerobic [78] Dupont C, Boissonnet G, Seiler JM, Gauthier P, Schweich D. Study about the
digestion, Merida, Mexico; October 22–25, 2002. kinetic processes of biomass steam gasification. Fuel 2007;86:32–40.
[43] Demirbas A. Thermochemical conversion of mosses and algae to gaseous [79] Maschio G, Lucchesi A, Stoppato G. Production of syngas from biomass.
products. Energy Source A 2009;31:746–53. Bioresour Technol 1994;48:119–26.
[44] Balat H. Prospects of biofuels for a sustainable energy future: a critical [80] Demirbas A. Pyrolysis and steam gasification processes of black liquor. Energy
assessment. Energy Educ Sci Technol A 2010;24:85–111. Convers Manage 2002;43:877–84.
[45] Bridgwater AV. Renewable fuels and chemicals by thermal processing of [81] Lv P, Chang J, Wang T, Fu Y, Chen Y. Hydrogen-rich gas production from
biomass. Chem Eng J 2003;91:87–102. biomass catalytic gasification. Energy Fuels 2004;18:228–33.
[46] Encinar JM, Beltran FJ, Ramiro A, Gonzalez JF. Pyrolysis/gasification of [82] Corte P, Lacoste C, Traverse JP. Gasification and catalytic conversion of
agricultural residues by carbon dioxide in the presence of different biomass by flash pyrolysis. J Anal Appl Pyrolysis 1985;7:23–35.
additives: influence of variables. Fuel Process Technol 1998;55:219–33. [83] Minowa T, Inoue S. Hydrogen production from biomass by catalytic
[47] Elliot DC, Beckman D, Bridgewater AV, Diebold JB, Gevert SB, Solantausta Y. gasification in hot compressed water. Renew Energy 1999;16:1114–7.
Developments in direct thermochemical liquefaction of biomass: 1983–1990. [84] Demirbas A, Caglar A. Catalytic steam reforming of biomass and heavy oil
Energy Fuels 1991;5:399–410. residues to hydrogen. Energy Educ Sci Technol 1998;1:45–52.
[48] Balat M. New biofuel production technologies. Energy Educ Sci Technol A [85] Luo S, Xiao B, Guo X, Hu Z, Liu S, He M. Hydrogen-rich gas from
2009;22:147–61. catalytic steam gasification of biomass in a fixed bed reactor: influence of
[49] Ni M, Leung DYC, Leung MKH, Sumathy K. An overview of hydrogen particle size on gasification performance. Int J Hydrogen Energy 2009;34:
production from biomass. Fuel Process Technol 2006;87:461–72. 1260–4.
[50] Demirbas A. Partial hydrogenation effect of moisture contents on the [86] Demirbas A. Characterization of products from two lignite samples by
combustion oils from biomass pyrolysis. Energy Source A 2008;30:508–15. supercritical fluid extraction. Energy Source A 2004;26:933–9.
[51] Demirbas A. Hydrogen-rich gases from biomass via pyrolysis and air–steam [87] Demirbas A. Diesel-like fuel from tallow by pyrolysis and supercritical water
gasification. Energy Source A 2009;31:1728–36. liquefaction. Energy Source A 2009;31:824–30.
[52] Demirbas A. Gaseous products from biomass by pyrolysis and gasification: [88] Lu YJ, Guo LJ, Ji CM, Zhang XM, Hao XH, Yan QH. Hydrogen production by
effects of catalyst on hydrogen yield. Energy Convers Manage 2002;43: biomass gasification in supercritical water: a parametric study. Int J
897–909. Hydrogen Energy 2006;31:822–31.
[53] Caglar A, Demirbas A. Hydrogen-rich gas mixture from olive husk via [89] Guo LJ, Lu YJ, Zhang XM, Ji CM, Guan Y, Pei AX. Hydrogen production by
pyrolysis. Energy Convers Manage 2002;43:109–17. biomass gasification in supercritical water: a systematic experimental and
[54] Demirbas A. Hydrogen production via pyrolytic degradation of agricultural analytical study. Catal Today 2007;129:275–86.
residues. Energy Source A 2005;27:769–75. [90] Yan Q, Guo L, Lu Y. Thermodynamic analysis of hydrogen production from
[55] Berman A, Karn RK, Epstein M. Kinetics of steam reforming of methane biomass gasification in supercritical water. Energy Convers Manage
on Ru/Al2O3 catalyst promoted with Mn oxides. Appl Catal A: Gen 2005;282: 2006;47:1515–28.
73–83. [91] Demirbas A. Biorefineries: current activities and future developments. Energy
[56] Galdamez JM, Garcia L, Bilbao R. Hydrogen production by steam reforming of Convers Manage 2009;50:2782–801.
bio-oil using coprecipitated Ni–Al catalysts. Acetic acid as a model [92] Demirbas A. Biohydrogen: for future engine fuel demands. London: Springer-
compound. Energy Fuels 2005;19:1133–42. Verlag; 2009.
[57] Vagia EC, Lemonidou AA. Thermodynamic analysis of hydrogen production [93] Modell M. Gasification and liquefaction of forest products in supercritical
via steam reforming of selected components of aqueous bio-oil fraction. Int J water. In: Overend RP, Milne TA, editors. Fundamentals of thermochemical
Hydrogen Energy 2007;32:212–23. biomass conversion. Elsevier Applied Science; 1985. p. 95–119.
 E. Kırtay / Energy Conversion and Management 52 (2011) 1778–1789 1789

[94] Elliott DC, Sealock J, Baker EG. Chemical processing in high-pressure aqueous [117] Ren N, Li J, Li B, Wang Y, Liu S. Biohydrogen production from molasses by
environments. 2. Development of catalysts for gasification. Ind Eng Chem Res anaerobic fermentation with a pilot-scale bioreactor system. Int J Hydrogen
1993;32:1542–8. Energy 2006;31:2147–57.
[95] Schmieder H, Abeln J, Boukis N, Dinjus E, Kruse A, Kluth M, et al. [118] Hawkes FR, Dinsdale R, Hawkes DL, Hussy I. Sustainable fermentative
Hydrothermal gasification of biomass and organic wastes. J Supercrit Fluids hydrogen production: challenges for process optimisation. Int J Hydrogen
2000;17:145–53. Energy 2002;27:1339–47.
[96] Kruse A, Meier D, Rimbrecht P, Shacht M. Gasification of pyrocatachol in [119] Nath K, Das D. Improvement of fermentative hydrogen production: various
supercritical water in the presence of potassium hydroxide. Ind Eng Chem Res approaches. Appl Microbiol Biotechnol 2004;65:520–9.
2000;39:4842–8. [120] Tao Y, Chen Y, Wu Y, He Y, Zhou Z. High hydrogen yield from a two-step
[97] Wang D, Czernik S, Montane D, Mann M, Chornet E. Biomass to hydrogen via process of dark- and photo-fermentation of sucrose. Int J Hydrogen Energy
fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its 2007;32:200–6.
fractions. Ind Eng Chem Res 1997;36:1507–18. [121] Özgür E, Uyar B, Öztürk Y, Yücel M, Gündüz U, Eroğlu I. Biohydrogen
[98] Das D, Veziroglu TN. Hydrogen production by biological processes: a survey production by Rhodobacter capsulatus on acetate at fluctuating temperatures.
of literature. Int J Hydrogen Energy 2001;26:13–28. Resour Conservat Recycl 2010;54:310–4.
[99] Demirbas A. Biohydrogen generation from organic waste. Energy Source A [122] Nath K, Muthukumar M, Kumar A, Das D. Kinetics of two-stage fermentation
2008;30:475–82. process for the production of hydrogen. Int J Hydrogen Energy 2008;33:
[100] Li J, Li B, Zhu G, Ren N, Bo L, He J. Hydrogen production from diluted molasses 1195–203.
by anaerobic hydrogen producing bacteria in an anaerobic baffled reactor [123] Kapdan IK, Kargi F. Bio-hydrogen production from waste materials. Enzym
(ABR). Int J Hydrogen Energy 2007;32:3274–83. Microb Technol 2006;38:569–82.
[101] Zhi X, Yang H, Yuan Z, Shen J. Bio-hydrogen production of anaerobic [124] Balat M. Coal in the global energy scene. Energy Source B 2010;5:50–62.
bacteria in reverse micellar media. Int J Hydrogen Energy 2008;33: [125] International Energy Agency (IEA). World energy outlook 2006. OECD/IEA,
4747–54. Paris; November, 2006.
[102] Nath K, Das D. Biohydrogen production as a potential energy resource – [126] Kırtay E. The role of renewable energy sources in meeting Turkey’s electrical
present state-of-art. J Sci Ind Res 2004;63:729–38. energy demand. Energy Educ Sci Technol A 2009;23:15–30.
[103] Das D, Khanna N, Veziroglu TN. Recent developments in biological hydrogen [127] Balat M, Balat H. Progress in biodiesel processing. Appl Energy
production processes. Chem Ind Chem Eng Q 2008;14:57–67. 2010;87:1815–35.
[104] Loubette N, Junker M. State of the art of biological hydrogen production [128] Dincer K. Lower emissions from biodiesel combustion. Energy Source A
processes. In: Proceedings of 16th world hydrogen energy conference, Lyon, 2008;30:963–8.
France; June 13–16, 2006. [129] Balat H, Oz C. Challenges and opportunities for bio-diesel production in
[105] Das D, Dutta T, Nath K, Kotay SM, Das AK, Veziroglu TN. Role of Fe- Turkey. Energy Explor Exploit 2008;28:327–46.
hydrogenase in biological hydrogen production. Curr Sci 2006;90: [130] Demirbas A. Global renewable energy projections. Energy Source B
1627–37. 2009;4:212–24.
[106] Benemann JR. Hydrogen production by microalgae. J Appl Phycol 2000;12: [131] Demirbas C. The global climate challenge: recent trends in CO2 emissions
291–300. from fuel combustion. Energy Educ Sci Technol A 2009;22:179–86.
[107] Yu J, Takahashi P. Biophotolysis-based hydrogen production by cyanobacteria [132] Hacisalihoglu S. Ethanol–gasoline and ethanol–diesel fuel blends. Energy
and green microalgae. In: Mendez-Vilas A, editor. Communicating current Educ Sci Technol A 2009;22:133–46.
research and educational topics and trends in applied in [133] Greene DL. Climate change policy for transportation while waiting for H2. In:
microbiology. Badajoz: Formatex Publishing; 2007. p. 79–89. Proceedings of the 10–50 solution: technologies and policies for a low-carbon
[108] Melis A, Zhang L, Forestier M, Ghirardi ML, Seibert M. Sustained future, Pew Center on Global Climate Change and the National Commission
photobiological hydrogen gas production upon reversible inactivation of on Energy Policy, Washington, DC; March 25–26, 2004.
oxygen evolution in the green alga Chlamydomonas reinhardtii. Plant Physiol [134] Balat M, Kırtay E. Major technical barriers to a ‘‘hydrogen economy’’. Energy
2000;122:127–36. Source A 2010;32:863–76.
[109] Resnick RJ. The economics of biological methods of hydrogen production. [135] Demirbas A. Biohydrogen for future engine fuel demands. London
Master thesis, Massachusetts Institute of Technology, Sloan School of (England): Springer-Verlag; 2009.
Management, Management of Technology Program; 2004. [136] Veziroglu TN, Sümer S ß . 21st Century’s energy: hydrogen energy system.
[110] Manish S, Banerjee R. Comparison of biohydrogen production processes. Int J Energy Convers Manage 2008;49:1820–31.
Hydrogen Energy 2008;33:279–86. [137] Balat M. Potential importance of hydrogen as a future solution to
[111] Hallenbeck PC, Benemann JR. Biological hydrogen production; environmental and transportation problems. Int J Hydrogen Energy
fundamentals and limiting processes. Int J Hydrogen Energy 2002;27: 2008;33:4013–29.
1185–93. [138] Eggertson B. Polarising views: the role of hydrogen as the world’s future
[112] Balat M. Production of hydrogen via biological processes. Energy Source A energy carrier. Refocus 2004;5:56–7.
2009;31:1802–12. [139] Li Z, Wang H, Tang Z, Wang X, Bai J. Effects of pH value and substrate
[113] Levin DB, Pitt L, Love M. Biohydrogen production: prospects and limitations concentration on hydrogen production from the anaerobic fermentation of
to practical application. Int J Hydrogen Energy 2004;29:173–85. glucose. Int J Hydrogen Energy 2008;33:7413–8.
[114] Fedorov AS, Tsygankov AA, Rao KK, Hall DO. Hydrogen photoproduction by [140] Boerrigter H, Rauch R. Review of applications of gases from biomass
Rhodobacter sphaeroides immobilised on polyurethane foam. Biotechnol Lett gasification. In: Knoef HAM, editor. Handbook biomass gasification. The
1998;20:1007–9. Netherlands: Biomass Technology Group (BTG); 2005. p. 211–30.
[115] Gadhamshetty V, Sukumaran A, Nirmalakhandan N, Myint MT. [141] Barreto L, Makihira A, Riahi K. Medium and long-term demand and supply
Photofermentation of malate for biohydrogen production – a modeling prospects for fuel cells: the hydrogen economy and perspectives for the 21st
approach. Int J Hydrogen Energy 2008;33:2138–46. century, International Institute for Applied Systems Analysis, Final report on
[116] O-Thong S, Prasertsan P, Karakashev D, Angelidaki I. Thermophilic the TEPCO-IIASA collaborative study, IIASA contract no. 00-101, Laxenburg,
fermentative hydrogen production by the newly isolated Austria; 2002.
Thermoanaerobacterium thermosaccharolyticum PSU-2. Int J Hydrogen [142] Barreto L, Makihira A, Riahi K. The hydrogen economy in the 21st century: a
Energy 2008;33:1204–14. sustainable development scenario. Int J Hydrogen Energy 2003;28:267–84.