Renewable Energy 66 (2014) 570e579

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Renewable Energy
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Review

Hydrogen production from steam gasification of biomass: Influence of

process parameters on hydrogen yield e A review
Prakash Parthasarathy, K. Sheeba Narayanan*
Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli 620015, Tamil Nadu, India

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

Article history: Steam gasification is considered one of the most effective and efficient techniques of generating
Received 29 August 2013 hydrogen from biomass. Of all the thermochemical processes, steam gasification offers the highest
Accepted 26 December 2013 stoichiometric yield of hydrogen. There are several factors which influence the yield of hydrogen in
Available online 31 January 2014
steam gasification. Some of the prominent factors are: biomass type, biomass feed particle size, reaction
temperature, steam to biomass ratio, addition of catalyst, sorbent to biomass ratio. This review article
Keywords:
focuses on the hydrogen production from biomass via steam gasification and the influence of process
Hydrogen
parameters on hydrogen yield.
Biomass
Thermochemical method
Ó 2014 Elsevier Ltd. All rights reserved.
Steam gasification
Yield

1. Introduction Hydrogen is a staple feedstock in automobile industry used for

1.1. Hydrogen in energy sector
Hydrogen is the lightest of all elements in the world. It is the
most abundant chemical element comprising about 75% of the
earth’s elemental mass [1]. As hydrogen gas is lighter than air it is
not available freely in the earth [2]. Naturally occurring elemental
hydrogen is almost rare on earth. Even though hydrogen does not
exist by itself on earth, it can be produced from a wide variety of
sources viz. natural gas, coal, oil, water by using an array of modern
process technologies.
Hydrogen has the highest energy density of all fuels and energy
carriers. The energy yield of hydrogen is 122 kJ per kg, about 2.75
times greater than other hydrocarbon fuels [3]. Hydrogen is
believed to be an effective substitute for gasoline as 9.5 kg of
hydrogen is sufficient enough to replace 25 kg of gasoline [4]. In
spite of its highly packed energy density, hydrogen when com-
busted does not give away any emissions as its by-product being
only water. With regard to end-use, hydrogen can be used directly
and as an intermediate storage fuel. Hydrogen as such is finding its
application in fuel cell technology and in internal combustion en-
gines. While in the production of gasoline, methanol, ethanol and
other value chemicals, it acts as an intermediate storage fuel.
Depending on the application, hydrogen can be used as gas or as
liquid, thus making it as a versatile fuel.
the generation of gasoline and lubricants [5]. In fertilizer industry,
hydrogen is majorly used in the synthesis of ammonia. Hydrogen
finds its application in the food industry in the hydrogenation of
unsaturated oils of soyabeans, fish, peanut and coconut. In cos-
metics sector, hydrogen is employed for hydrogenating inedible oils
and greases for soap manufacturing. It is used in the glass industry
in making float glass and also in oxy-hydrogen cutting of glass.
Hydrogen plays a prominent role in the electronics industry in the
production and processing of silicon. It acts as an excellent refining
agent in metallurgical industry [6]. Hydrogen is going to be an
inevitable commodity in fuel cell manufacturing.
Though hydrogen is findings its applications in several sectors, it
is deemed to create a significant impact in the energy sector. It is
believed that if hydrogen enters transport sector, about 40 million
tonnes of hydrogen per year would be required [7]. Its property of
high energy density, rapid burning speed, high-octane number and
zero harming potential would make it as a first preferred fuel in the
near future. Hydrogen the future elixir of human life, thus offers a
potentially non-polluting, inexhaustible, efficient and cost attrac-
tive energy carrier. As is evidenced by several funded programs
from many national governmental agencies all over the world,
hydrogen is being promoted as the fuel for the future [8].
1.2. Hydrogen from biomass

* Corresponding author. Tel.: þ91 431 2503113; fax: þ91 431 2500133. The major share of hydrogen is produced from fossil fuels such
E-mail address: sheeba@nitt.edu (K.S. Narayanan). as natural gas, coal and oil. Only 4% of hydrogen is produced from

0960-1481/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.renene.2013.12.025
 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579
other renewable sources [9]. As fossil fuels would be depleted by
2050, it is high time to look for alternative source of hydrogen
generation [10].
The various sources of hydrogen are illustrated in Fig. 1 [11].
The renewable sources of hydrogen include biomass, solar,
wind, hydel. Of them only biomass can generate hydrogen directly.
The rest of the renewable sources have to undergo electrolysis for
hydrogen production. Moreover, biomass is often dumped as such
or used directly whose energy density is very less. Therefore, if
biomass is utilised for hydrogen production, it not only safeguards
the environment, but also provides a sustainable source for
hydrogen. Biomass and biomass derived fuels are renewable energy
sources that can be used to produce hydrogen sustainably [12].
Biomass is a carbon neutral source which when coupled with CO2
sequestration can be claimed carbon negative emitter [13]. A wide
range of technologies exists for transforming the energy rich
biomass into hydrogen. The scope and potential for recovering
hydrogen from biomass is enormous. Hydrogen recovery from
biomass is quite enough to satisfy the present and future hydrogen
demands [14]. The economics of hydrogen generation from various
sources are given in Table 1 [15e18].
Efficiency is defined as the ratio of lower heating value of
hydrogen in product gas to total energy supplied to the process.
A lot of initiatives have been undertaken to promote hydrogen
production from biomass. Pertaining to that, in 2004 the Interna-
tional Energy Agency’s (IEA) program on the production and utili-
zation of hydrogen launched its new task to produce hydrogen from
carbon-containing materials [19]. All these initiatives emphasised
the world that biomass could be the solution for the near term for
hydrogen production, without a need for major scientific break-
through. Fig. 2 shows the commitment of nations towards the
hydrogen and fuel cells initiative [20].
Balat [21] enumerated the advantages and limitations of
biomass to hydrogen as presented in the Table 2.
Thus hydrogen energy is unavoidable. To meet out the growing
energy demand of the world, hydrogen production has to be from a
sustainable and renewable source. Biomass could be the ideal so-
lution for this. Considering the impact of hydrogen, this review
article is aimed at providing an insight into the basics of hydrogen
production from biomass for the upcoming researches to follow.
The scope of the work is to discuss about various thermochemical
methods of hydrogen production from biomass and to find out the
best suited method. The work further focuses on investigating the
effect of main process parameters on the hydrogen yield.
Other
alternative
sources
4%
Coal
18% Natural
gas
49%
Liquid
hydrocarbons
29%
Fig. 1. Hydrogen production from various sources.
571
2. Hydrogen production alternatives
2.1. Thermochemical route of generating hydrogen from biomass
Thermochemical and biochemical methods are the two modes
for hydrogen production from biomass. Though hydrogen from
biomass can be generated through bio-chemical route, thermo-
chemical methods have some significance over bio-chemical
methods. Biochemical methods require feed-stocks rich in starch
or sugar and cannot treat lignocellulosic stuffs [22]. In brief, bio-
chemical methods are very selective about feed-stocks whereas
thermochemical method allows an extensive range of feed stocks.
Despite the fact that, enzymatic or bio-chemical route are highly
developed, they are still being operated in batch process and time-
consuming. On the other hand, thermochemical methods are much
faster, but tend to be less selective producing a range of products.
Above all, overall efficiency (thermal to hydrogen) of thermo-
chemical process is higher (w52%) and production cost is lower
when compared to bio-chemical process [3]. These reasons
prompted researchers to work more on thermochemical route of
hydrogen production from biomass.
Thermochemical conversion of biomass is one of the leading
near term options for renewable hydrogen production [23]. Inter-
national Energy Agency (IEA) has [24] presented an extensive re-
view of research on thermochemical production of hydrogen from
biomass. Thermochemical processes such as combustion, gasifica-
tion, and pyrolysis are believed to be the most promising solution
for the production of second production fuels [25,26]. Present trend
of generating hydrogen from biomass is via thermochemical route
includes, fast pyrolysis followed by steam reforming of char, steam
critical water gasification and steam gasification.
2.1.1. Fast pyrolysis followed by steam reforming of char
Pyrolysis is the process of conversion of the biomass or any
carbonaceous feed stocks into convenient gas, liquid and solid fuels
or chemical feed stocks. Unlike combustion, pyrolysis takes place in
the total absence of oxygen, except in cases where partial com-
bustion is allowed to provide the thermal energy needed for the
process. Pyrolysis is categorized into torrefaction or mild pyrolysis,
slow pyrolysis and fast pyrolysis. Pyrolytic decomposition of
biomass can be given by the following equation
Pyrolysis of biomass / H2 þ CO þ CO2 þ HCgases þ Tar þ Char(1)
Fast pyrolysis is an advanced thermochemical process to convert
a significant fraction of biomass as a liquid. Fast pyrolysis followed
by steam reforming is one of the contemporary methods of
hydrogen production from biomass. In favour of gaseous products
especially hydrogen, high temperature, high heating rate and long
volatile phase residence time are the essential commodities [27].
Besides hydrogen recovered from gaseous products, the oily
products can also be processed for further hydrogen production
[28]. Based on water solubility the pyrolytic oil can be separated
into water soluble and water insoluble fractions. Hydrogen can be
generated from water soluble fraction while water insoluble frac-
tion can be used for adhesive formulation [29].
The main drawbacks of this method however, are low efficiency,
formation of tar and char. Generally fast pyrolysis is intended for
producing liquid products. The amount of gaseous products
generated from the process is low. This meagre amount of gaseous
product in turn leads for minimal hydrogen recovery. Formation of
tar is highly undesirable. Condensation of tar produces an oily
emulsion, which is very tedious to treat and causes subsequent
plugging problems in the downstream equipments. Presence of tar
in gaseous stream leads to unwanted secondary reactions which in
572 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579

Table 1
Cost analysis of hydrogen production methods.

Method Energy efficiency H2 production cost Production scale Major advantages Major disadvantage
size/current trend

Steam methane reforming 83% $0.75/kg (without CO2 Large/currently Proven technology, High CO2 by-product, Limited
(SMR) sequestration) available Efficiency, Economical methane supply, Global
warming, dependence
of fossil fuel
Partial oxidation 70e80% $1.39/kg (residual oil) Large/available Established, cost-effective CO2 by-product, Lower
efficiency than SMR,
Global warming
Autothermal reforming 71e74% $1.93/kg Large/currently Proven technology, Less CO2 by-product, Limited
available capital costs methane supply, Less
efficient efficiency
than SMR
Coal gasification 63% $0.92/kg (without CO2 Large/currently Established, cost-efficient CO2 by-product, Low
sequestration) available quality hydrogen
Biomass gasification 40e50% $1.21e2.42/kg Mid-size/currently Renewable, indigenous Seasonal availability,
available operational difficulties,
Transportation problems,
Varying H2 content
Biomass pyrolysis 56% $1.21e2.19/kg Mid-size/currently Renewable, indigenous Seasonal availability,
available operational difficulties,
Transportation problems,
Varying H2 content
Electrolysis 25% Electrical $2.56e2.97/kg (Nuclear Small/currently Proven technology, Low overall efficiency,
efficiency included source) available Emission free High cost
Thermo-chemical 42% (850  C) $2.01/kg (SulphureIodine Under research Emission free, alternate High capital costs, extreme
cycle) source operating conditions, Highly
corrosive
Photocatalytic 10e14% (theoretical) $4.98/kg Under research Renewable, alternate source Pricy, Low efficiency
Biological 24% (speculative) $5.52/kg Under research Renewable, alternate source Low efficiency, High
capital cost
Bio-photolysis of water Under research Renewable, sustainable, Strong inhibition effect
by algae CO2 consumed of generated oxygen on
hydrogenase enzyme,
Low H2 production, No
waste utilization
Dark fermentative Under research Renewable, simultaneous Low energy conversion
hydrogen production waste treatment and efficiency
generation of H2
Photo fermentative Under research High theoretical conversion Uses nitrogenase enzyme
hydrogen production yield, absence of oxygen which with high-energy demand,
reduces the potential for low solar energy conversion
inhibition (Biological efficiency, accommodates
Processes for Hydrogen large areas for the
Production from Biomass) anaerobic photo bioreactors

turn reduces gaseous stream quantity. Similarly the presence of
char in gaseous stream catalyses secondary cracking leading to
unwanted products. Though particulate removal systems are
employed in downstream to remove char particles, complete
removal of char is impossible. Thus, unwanted secondary cracking
of gas is unavoidable in this method. These issues reduce the po-
tential of hydrogen recovery from the biomass.
2.1.2. Steam critical water gasification
Steam critical water gasification is another thermochemical
method of hydrogen production. It is known that, water exists in
three states under normal conditions: solid, liquid, and gas [30].
When the pressure and temperature of water is subjected to super
critical state (22.1 MPa and 374  C), its gas and liquid phase be-
comes miscible [31] At this point water becomes oxidant and when
biomass reacts with super critical water the oxygen molecules of
water are transferred to carbon atoms of biomass. The so formed CO
reacts with steam to produce CO2 and hydrogen by water gas re-
action. The hydrogen atoms of water and biomass are set free [32].
Thus, hydrogen is generated.
The above method is a promising one to produce hydrogen from
biomass [33]. But this method has some drawbacks. This method is
particularly suited for high moisture content biomass. Further, the
cost of hydrogen production from supercritical water gasification of
wet biomass is many folds higher than the current price of
hydrogen from steam methane reforming. Though this method is
believed to yield higher efficiency in terms of hydrogen production,
this technology is still under development and involves a lot of
research to make it proven.
2.1.3. Steam gasification
To start with, gasification is a chemical process that converts
carbonaceous materials like biomass into useful gaseous fuels or
chemical feedstock. Gasification takes place in an oxygen-
deficient environment requiring heat. It requires a medium for
reaction, which can be air, oxygen, subcritical steam, or a
mixture of these. Table 3 compares different gasification pro-
cesses [8].
There are three major motivations for carrying out gasification:
to increase the heating value of the fuel by removing non-
combustible components like nitrogen and water, to remove
sulphur and nitrogen from the fuel and preventing them to let into
the atmosphere, to reduce the carbon-to-hydrogen (C/H) mass ratio
in the fuel. During gasification process, biomass undergoes drying,
pyrolysis (devolatilization), reduction and combustion reactions.
Drying liberates moisture; pyrolysis removes volatiles in the form
 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579 573

Table 3
Comparison between different gasification processes.

Air gasification Oxygen Steam gasification

gasification

Product heating Low 4e6 High 10e15 High 15e20

value, MJ/Nm3
Products CO, H2, CO, H2, HC, H2, CO, CO2,
Water, CO2 CH4 light HC, tar
CO2,
HC, Tar, N2
Average product H2  15%, H2  40%, H2  40%, CO  25%,
gas composition CO  20%, CO  40%, CH4  8%, CO2  25%,
CH4  2%, CO2  20%, N2: 2%, H2:CO: 1
CO2  15%, H2:CO: 1
N2  48%,
H2:CO: 0.75
Reactor temperature, 900e1100 1000e1400 700e1200

C
Cost Cheap Costly Medium

Fig. 2. Commitment of nations towards the hydrogen and fuel cells initiative.

reactions. Steam gasification technology is suitable for biomass

of gaseous CO, CO2, light hydrocarbons and tar. A series of reactions
between drying and pyrolysis products occurs in reduction stage.
Lastly in combustion zone char further decomposed to produce
more gaseous products [34].
Gasification can be illustrated by a simple reaction.
Biomass þ Air / H2 þ CO2 þ CO þ N2 þ CH4 þ Light and heavy
HC þ Tar þ H2O þ Char (2)
Biomass steam gasification converts carbonaceous material to
permanent gases (H2, CO, CO2, CH4 and light HC), char and tar.
Biomass steam gasification can be given by a simplified reaction
equation.
having moisture content less than 35% [39]. By and large all
biomass have moisture close to 35% and hence steam gasification is
best suited for dealing biomass. Steam gasification technology is a
well proven and well established one. Some of the advantages of
steam gasification are: provides an effective means of renewable
hydrogen production, contribute for the highest yield of hydrogen
from biomass, offers cleaner product with minimal environmental
impact.
Many researches have been carried out in steam gasification
[40e43]. Nipattummakul et al. [40] presented that steam gasifica-
tion increased the hydrogen yield thrice as compared to air gasifi-
cation. Franco et al. [41] reported that the use of pure steam is more

Biomass þ Steam / H2 þ CO þ CO2 þ CH4 þ Light and heavy Table 4

The sequence of reactions occurring during steam gasification.
HC þ Tar þ Char (3)
Reactions DH Type Equation
The sequence of reactions occurring during steam gasification is (kJ/mol)
given in Table 4 [35e37]. Primary devolatization
Steam gasification is another thermochemical method of Biomass / CO, CO2, CH4, (4)
hydrogen production. In fact, it is believed to be an effective mode C2H4, H2O, Carbon,
Primary Tar(CHxOy)
of producing renewable hydrogen without leaving any carbon
footprint in the environment [38]. The drawbacks of earlier Tar cracking and reforming
Primary tar / CO, CO2, (5)
methods of hydrogen production could be overcome by steam
CH4, C2H4, H2,
gasification. The yield of hydrogen in steam gasification is far better Secondary Tar
than fast pyrolysis followed by steam reforming of char. But as of
Homogenous gas-phase reactions
now, no effective comparison could be drawn between steam
Secondary Tars / C, CO, H2 (6)
gasification and steam critical water gasification in terms of H2 þ 0.5O2 / H2O 242 Combustion (7)
hydrogen yield. Only lesser amounts of char and tar are produced (oxidation)
during steam gasification since steam initiates more water gas CO þ 0.5O2 / CO2 283 Combustion (8)
(oxidation)
CH4 þ 0.5O2 / CO þ 2H2 110 Combustion (9)
(oxidation)
Table 2 CH4 þ CO2 / 2CO þ 2H2 þ247 Dry reforming (10)
Main advantages and limitations of biomass to hydrogen. reaction
CH4 þ H2O / CO þ 3H2 þ206 Steam reforming (11)
Advantages reaction
Reduces the dependence on fossil fuels CO þ H2O / CO2 þ H2 40.9 Water gaseshift (12)
Provides a sustainable energy source reaction
Reduces green house gas emissions
Heterogeneous reactions
Increases the value of agricultural products
C þ O2 / CO2 393.5 Oxidation of (13)
Reduces the agricultural and municipal waste residues
Carbon
Limitations C þ 0.5O2 / CO 123.1 Partial oxidation (14)
Less energy density C þ CO2 / 2CO þ159.9 Boudouard reaction (15)
Bulkiness and high moisture content C þ H2O / CO þ H2 þ118.5 Water gas reaction (16)
Intensive labour involved in collection, handling and transportation (steam reforming)
Seasonal availability C þ 2H2 / CH4 87.5 Methane production (17)
Formation of tar and char reaction
574 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579

Table 5 steam-to-biomass ratio, and smaller biomass particle size

Parameters and its effects on hydrogen yield of steam gasification. contribute for more hydrogen production. The findings of previous
Parameter Description Effects researches are given in Table 6 [41,43,54e65].
Biomass types Different plant species Product composition
wastes largely depends of 3.1. Biomass types
inherent nature of
parent biomass All biomass are mainly composed of cellulose, hemi-cellulose
Feed particle Biomass feed particles Feed size influences
and lignin and their composition differs from biomass to biomass.
size dimension heat and mass
transfer conditions These components play a major role in the decomposition of
which in turn biomass [65]. Generally, larger composition of cellulose and lignin
products constituents yield more gaseous products. This in turn increases the potential of
and composition
hydrogen recovery from biomass. Thus the hydrogen production
Process Gasifier temperature Low temperatures
temperature is considered after favours char yield and
from biomass is based on the intrinsic nature, moisture content and
pyrolysis zone methane production. alkali content [39]. Brown [66] gave a simplified representation for
Optimal temperatures biomass pyrolysis which is illustrated in Fig. 3.
for hydrogen Many biomass species have been tried out so far to generate
generation 800e900  C.
hydrogen from biomass through steam gasification. Some of them
Steam-biomass Mass of steam/mass Low S/B e methane
ratio of biomass and char, High S/B e syngas are: coir pith [67], pine saw dust [68], almond shell [69], black li-
Process pressure Gasification occurs at Chemical equilibrium quor [70], coffee husk [71], ceedar wood [72], waste water sludge
constant pressure in indicates that gasification [62], palm oil waste [73], municipal solid waste [74], paper [64],
the gasifier is favoured by low beech wood, wheat straw, corn cob [57], saw dust [75], hazel nut,
pressures and high
temperatures. However,
tea waste, spruce wood [76], yellow pine woodchips [56], moses,
no substantial gain is algae [77], wood saw dust [78], waste wood [79], lignocellulosic
obtained if the process char [80].
runs in vacuum.
Catalyst Small quantity of No catalyst-less gas
3.2. Biomass feed particle size
materials added to yield and tar formation
the process to speed
up the reaction rate The effect of biomass particle size on hydrogen production is
Sorbent to Materials of small Removal of CO2 increases significant. Some researchers have worked on the effect of biomass
biomass ratio amount added to syngas yield particle size [59,81e85].
adsorb CO2 developed
during the process
Actually smaller particles provide larger surface area per unit
mass. This larger surface area improves heat and mass transfer
between the particles. Due to effective heat transfer, the gasifica-
tion reaction (Boudouard reaction, water gas reaction, carbon
economical and favours more hydrogen yield compared to other
conversion reactions) efficiencies improve significantly. The
conventional gasifying agents. Umeki et al. [42] and Wei et al. [43]
improved effectiveness of gasification reactions eventually aug-
reported water-gas shift reaction vital for hydrogen production
ments for better H2 and CO production but in the expense of
which could be enhanced by steam gasification.
decrease in CO2 content. Production of tar and char also gets
reduced.
3. Factors influencing hydrogen yield in steam gasification Lv et al. [81] reported that larger particles possess greater heat
transfer resistance which result in incomplete pyrolysis leading to
There are some vital process parameters which influence the more amount of residual char. Luo et al. [59] in his work demon-
yield of hydrogen generated in steam gasification. They are biomass strated that decrease in particle size improved carbon conversion
types; biomass feed particle size, temperature, steam to biomass efficiency and hydrogen yield. Reed [82] presented that smaller
ratio, addition of catalysts, sorbent to biomass ratio etc. The pa- particles facilitate water gas reaction; carbon gasification reaction,
rameters and its effects on hydrogen yield of steam gasification are secondary cracking reactions and boudouard reaction which in turn
provided in Table 5 [44]. increases hydrogen and CO content in the product. Jand et al.,
The steam gasification of biomass has been investigated by Rapagna et al. and Hernandez et al. [83e85] found that reduction in
many researchers in order to evaluate the influence of operating particle size greatly improved gasification properties by increasing
parameters (i.e. temperature, residence time, steam to biomass producer gas efficiency and by reducing the tar amount.
ratio and particle size, etc) and type of biomass on the gasification
performance [45e50]. Bridgwater [51] in his work stated that 3.3. Temperature
relative yields of gas, liquid and char depend mostly on the rate of
heating and the final temperature. The researcher further asserted Temperature is the most influential factor in the hydrogen
gas composition is influenced by many factors such as feed production during steam gasification. Effect of temperature on
composition, water content, reaction temperature, and the extent hydrogen production was studied by many researchers
of oxidation of the pyrolysis products. The work by Rapagna and [39,59,74,76,81,86e88].
Latif [52] showed that the catalysts enhance the decomposition of Generally, increase in temperature increases the heating rate
tar and consequently increase the production of permanent gases among the particles. This leads to effective destruction of the par-
like hydrogen. Experiments carried out by the same researcher ticles and proceeds for complete gasification reactions (Combus-
revealed at same operating temperatures the smallest particles tion, Boudouard, Water gas, methane formation, CO shift, and
produce more gas per kg of biomass than biggest particles. steam methane reforming reactions). As a result, yield of gaseous
This establish the fact that, powdered biomass is most suitable products increases contributed by the increase in hydrogen, CO and
for hydrogen production. Lv et al. [53] is of the view that the methane content. Increase in temperature proceeds for completion
higher reactor temperature, proper equivalence ratio, proper in gasification reactions and only a small amount of char is left
 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579 575

Table 6
Findings of earlier literatures.

Biomass Reactor Particle size Steam Temperature Catalyst Sorbent to Findings References
(mm) ( C) biomass
ratio

Refuse plastic fuel Steam flow 700e1000 K2CO3 Raise in temperature enhances [54]
0e0.25 g/min H2 yield. Steam and K2CO3
catalyst increases H2
concentration dramatically.
Pine saw dust External circulating 0.10e0.20 S/B 0.38e0.59 650e800 CaO Higher temperatures favours [55]
concurrent moving increase in H2 content in dry
bed gas. CO2 absorbent increases
the extent of the water-gas
shift reaction and improves
the yield of H2
Paper, yellow pine Batch type flow Steam 700e1200 Yield of both the hydrogen and [56]
woodchips reactor flow 6.3 g/min carbon monoxide increases
while carbon dioxide and
methane decreases with the
increase in gasification
temperature.
Beech wood, olive Horizontal S/B 1, 2 500e950 Wheat straw produces more [57]
waste, wheat cylindrical reactor H2 yield. The yield from steam
straw and corn gasification increases with
cob increasing S/B ratio. The yields
of hydrogen from the pyrolysis
and the steam gasification
increases with increase of
temperature
Wood saw dust S/B 0.17e0.51 675e1225 Increase in S/B ratio increases [58]
H2 yield.
Pine saw dust Gasification Below 0.075 mm, 600e900 Natural Decrease in particle size brought [59]
reactor 0.075e0.15 mm, dolomite increase in the dry gas yield,
0.15e0.3 mm, carbon conversion efficiency, H2
0.3e0.6 mm, yield and decrease in char,
06e1.2 mm tar yield. Hydrogen and carbon
monoxide contents in the
produced gas increases with
decreasing particle size.
Pine saw dust Gasifier 02e0.4 mm 1.05e2.53 800e950 With the increasing gasifier [60]
temperature varying from
800 to 950  C, hydrogen yield
increased from 49.97 to 79.91 g
H2/kg biomass. Steam/biomass
ratio of 2.05 seemed to be
optimal in all steam-gasification
runs.
Legume straw, Free fall reactor 0.0e1.0 750e850 Limestone, Increase in temperature increased [43]
pine saw dust olivine and gas yields, H2 content in the gas
dolomite but decreased tar, char, CO and
CH4 yield. The presence of steam
increased the gas yields and
reduced the tar and char yields.
Dolomite catalyst showed
better performance.
Saw dust Stainless steel 0.425e0.5 mm 0.58e1.58 600, 670, 710 0, 1, 1.5, 2 Maximum hydrogen production [61]
cylinder tube of 54.96% obtained at S/B of 0.83.
reactor Increase in temperature increases
hydrogen yield till 670  C then
on showed a decreasing trend.
Addition of CaO/biomass increases
hydrogen yield and concentration.
Maximum hydrogen yield and
concentration observed at
CaO/biomass of 2.
Waste water Semi-batch 35 g Steam to carbon 900 Steam gasification generates [62]
sludge type reactor ratio 3.05, 5.62 more syngas, hydrogen, energy
and 7.38 and higher apparent thermal
efficiency than pyrolysis. Peak
value of syngas yield, energy
yield and hydrogen obtained
at 5.62.
Palm residual Semi-batch 35 g Steam flow 600e900 Heating value and energy yield [63]
branches type reactor rate 3.10 g/min ratio increases with increasing
temperature. Slow reaction rate
is found below 700  C.
(continued on next page)
576 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579

Table 6 (continued )

Biomass Reactor Particle size Steam Temperature Catalyst Sorbent to Findings References
(mm) ( C) biomass
ratio

Paper, yellow pine Batch type 30 g Steam flow 700e1200 Yield of H2 and CO increased with [56]
woodchips and flow reactor rate 3.3e6.3 g/min increasing temperature while CH4
Pittsburgh and CO2 decreased. 10 fold
bituminous coal reduction in tar observed at high
gasification temperatures.
Pinus pinaster Atmospheric 5.7e11.5 g/min 0.4e0.85 700e900 Optimal temperature 830  C, [41]
(softwood), fluidised bed optimal S/B 0.7e0.8. Biomass
Eucalyptus reactor species influences gasification
globulus and process generating varying gas
holm-oak compositions. Water gas shift
(hardwood) reactions dominant upto 830  C.
After 830e900  C water gas and
boudouard reaction prevails
Paper 35 g 8 g/min 600e900 Char gasification reactions slower [64]
than pyrolysis reactions. Char
gasification more sensitive to
reactor temperature than
pyrolysis reactions.

behind. Moreover significant increase in temperature effectively
thermally decomposes the tar molecules which again chip in for
more gaseous products.
de Lasa et al. [39] was of the opinion that with increase in
temperature, combustible gas content, gas yield, hydrogen, and
heating value all increased significantly, while the tar content
decreased sharply. He et al. [74] confirmed that temperature rise
attributes for better decomposition of char and tar through bou-
douard and thermal cracking reactions. Demirbas [76] ascertained
that increase in temperature not only increases the hydrogen yield
but also decreases tar yield. Luo et al. [59] reported that higher
heating rate produced more light gases as well as less char and
condensate. Lv et al. [81] and Kumar et al. [86] through their work
have substantiated increase in temperature has resulted an in-
crease in hydrogen and methane content. Li et al. [87] concluded
that temperature is the most important factor in gasification pro-
cess; contributing to higher hydrogen production and syngas yield.
Inayat et al. [88] in his experiments observed decrease in methane
and CO2 concentration with increase in temperature.
Some works emphasised on the effect of steam to biomass ratio
[2,39,88].
At low values of steam to biomass, solid carbon and methane are
formed. As more steam is supplied, carbon and methane are
reformed to carbon-mono-oxide and hydrogen. When steam is
supplied more than the biomass content, solid carbon and methane
reduces further whereas hydrogen and CO2 yield increases mono-
tonically. CO on the other hand reduces monotonically as water gas
and reforming reactions of hydrocarbons are promoted by steam.
Thus, increase of steam significantly promotes hydrogen formation
in biomass gasification. But presence of excess steam is found to
have a negative impact as reduction in temperature favours large
quantities of tar. Hence an optimised steam biomass ratio is ideal.
Kalinci et al. [2] reported that increase in steam promotes water
gas and reforming reactions of hydrocarbons. de Lasa et al. [39]
reported that increase in steam to biomass ratio induces reactions
such as char, methane steam reforming and water gas shift etc.
Inayat et al. [88] is of the view that methane forming and water gas
shift are highly dependent of steam flow rate.

3.5. Catalyst
3.4. Steam to biomass ratio

It is enthralling to study about the effects of catalyst in hydrogen

Like temperature, steam to biomass ratio has a strong influence
on both product gas composition and energy input. Researchers
have reported steam gasification has promoted hydrogen yield.
Fig. 3. The simplified representation of biomass pyrolysis.
production of biomass. Few works throw light on the effect of
catalyst on hydrogen production [11,29,43,75,89e93].
Several catalysts have been attempted by researchers till date in
steam gasification of biomass. Some of the attempted catalysts are
dolomite; Ni based catalyst, alkaline metal, alumina, alumina sili-
cate, K2CO2, Na2CO3, K2CO3 and ZnCl2.
Catalyst facilitates effective heat and mass transfer between
particles. This in turn improves the efficiency of the gasification
reactions (combustion, Boudouard, water gas, methane formation,
CO shift, steam methane reforming). Increase in efficiency of water
gas, CO shift and steam methane reforming reaction contribute for
the rise in hydrogen and carbon-moo-oxide yield. Catalysts not
only provoke the gasification reactions but also help in the
destruction of tar. The destruction of tar too contributes for
hydrogen production. Thus overall hydrogen yield is improved by
means of increase in efficiency of gasification reactions and also by
tar destruction.
Ni et al. [29] reported that dolomite, Ni-based catalysts and
alkaline metal oxides catalysts are best for gasification reactions.
Balat [11] found out that use of catalyst is not affecting gas yield but
 P. Parthasarathy, K.S. Narayanan / Renewable Energy 66 (2014) 570e579
strongly controls gas composition. Corte et al. [89] employed
alumina, alumino-silicate material, and Ni-based catalysts in their
studies. They found alumino silicate catalysts are more active for
carbon gasification and nickel catalysts suitable for lighter hydro-
carbon. Wei et al. [43] observed that catalysts are employed in
gasification processes to boost up the yield and quality of product
gas and also to destruct tar.
Still extensive research is underway to develop a highly stable,
efficient, cheap and highly reactive catalyst for biomass gasification
to promote hydrogen yield [75,89e93]. However developing an
optimum catalyst is complicated as it involves comprehensive un-
derstanding of gasification kinetics and reaction mechanisms.
3.6. Sorbent to biomass ratio
Biomass is regarded as carbon neutral emitter fuel. It could be
claimed as carbon negative emitter if carbon dioxide produced in
system is captured and not allowed to let into the environment
[93]. Several researchers have endeavoured to study the effect of
sorbent on hydrogen yield [61,94e107]. Some of the sorbents
attempted in gasification processes are: rhodium, aluminium oxide,
nickel based sorbent, dolomites, metal based sorbent.
The fundamental idea is that the removal of CO2 from the
gasification system alters the equilibrium composition of the
product gas promoting the production of hydrogen-rich gas.
Acharya et al. [61] and Alvarez et al. [94] in their work has reported
that solid based sorbent has better efficiency than liquid based
sorbent. Feng et al. [104], Gupta and Fan [105], Rao and Rubin [106]
have recommended for CaO as sorbent.
4. Conclusions
Steam gasification offers an effective and economical route of
hydrogen production from biomass leaving minimal environmental
footprint. It provides a promising option for sustainable hydrogen
production since biomass is plentiful throughout the world. The
influence of biomass types, biomass feed particle size, temperature,
steam to biomass ratio, addition of catalysts, sorbent to biomass
ratio on hydrogen yield from steam gasification of biomass was
reviewed. The following conclusion can be drawn from the above
discussion.
Yield of hydrogen varies from biomass to biomass which de-
pends on inherent composition of the species. Decrease in particle
size increases hydrogen yield providing larger surface areas facili-
tating faster heat and gasification rates. Reduction in particle size
also increases dry syngas yield and carbon conversion efficiency. By
and large, gasification temperature is higher than that of pyrolysis
and yield of hydrogen from the gasification is higher than that of
pyrolysis. Yield of hydrogen increases with increase in temperature.
This is due to the fact that increase in temperature increases the
efficiency of gasification reactions and helps in the destruction of
tar effectively promoting further gas yield. Steam to biomass ratio
like temperature has a strong influence on both product gas
composition and energy input. Thus, increase of steam significantly
promotes hydrogen formation as steam influences water gas, CO
shift and methane formation reactions. Addition of catalyst im-
proves hydrogen yield due to the influence of catalyst towards shift
reaction. Entrapping CO2 increases the hydrogen yield as the water
gas shift reaction is shifted forward when CO2 is removed from the
system.
Acknowledgements
The authors wish to thank DST, India for the financial support for
this study under the grant no. SR/FTP/ETA-69/2009.
577
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