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Hydrogen production from the thermochemical

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Cite this: DOI: 10.1039/c8se00535d

conversion of biomass: issues and challenges
Binlin Dou,*a Hua Zhang,a Yongchen Song,b Longfei Zhao,a Bo Jiang,b Mingxing He,a
Chenjie Ruan,a Haisheng Chen*c and Yujie Xuc

Received 3rd November 2018
Accepted 21st November 2018
DOI: 10.1039/c8se00535d
rsc.li/sustainable-energy
Hydrogen production from thermochemical conversion has been considered the most promising
technology for the use of biomass, and some novel methods are also being developed for low cost and
high efficiency. This review presents the recent progress in the studies on hydrogen production from
different kinds of biomass by pyrolysis, gasification and steam reforming without and/or with chemical-
looping technologies. Considering potential applications, the Ni-based catalysts made of cheap and
earth-abundant elements are especially important for the economically viable hydrogen production from
biomass by thermochemical conversion, and can also effectively be compensated for and modified, to
some extent, by using extremely low noble metal loading for retaining high catalytic activity, high coke
resistance and long-term stability. The catalyst modification strategies of adding other metals,
minimizing Ni particle sizes and improving the supports are highlighted. The sorption-enhanced steam
reforming (SESR) and chemical looping steam reforming (SE-CLSR) processes with in situ CO2 removal
using different reactors have been considered to change the normal equilibrium limits of the water–gas
shift (WGS) reaction, and thus increase feedstock conversion and process performances. The auto-
thermal operating conditions and CO2 capture during hydrogen production can be achieved by
chemical looping processes with cyclic oxidation–reduction of oxygen carriers (OCs). This paper
discusses the related issues, challenges and prospects, along with the possible solutions in order to help
in the development of efficient hydrogen production from the thermochemical conversion of biomass.

(2) Biomass hydrogen: This is either thermochemical or

1. Introduction
Up to 96% of the H2 production technologies is based on non-
renewable sources, with the most used processes being natural
gas (48%) and oil (30%) steam reforming, followed by coal
gasication with the water–gas shi (WGS) reaction (18%).1
Only 4% of the H2 produced is obtained by means of water
electrolysis. Consequently, in order to meet the fossil fuel
consumption and CO2 release reduction targets, new sustain-
able processes derived from renewable sources must be devel-
oped. Currently, several methods and technologies can be used
to produce renewable hydrogen.
(1) Electrolysis: This involves splitting water into hydrogen
and oxygen using electrical energy from one of the many
renewable sources.
a
School of Energy and Power Engineering, University of Shanghai for Science and
Technology, Shanghai, 200093, China. E-mail: bldou@usst.edu.cn; Tel: +86
2155272320
b
School of Energy and Power Engineering, Key Laboratory of Ocean Energy Utilization
and Energy Conservation of Ministry of Education, Dalian University of Technology,
Dalian, 116023, China
c
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190,
China. E-mail: chen_hs@mail.etp.ac.cn; Tel: +86 1082543148
biochemical conversion to produce hydrogen.
(3) Solar conversion: This is either thermal decomposition by
solar generated heat for hydrogen production or photolysis
using electrochemical systems for hydrogen production.
Indirect production of hydrogen from renewable resources
through electricity and electrolysis is also an option. However,
heavy efficiency penalties limit the electrolysis and it may only
be suitable for a large market if electricity costs are low enough.
The approaches of water splitting and photo-biological
production are still in the early stages so reliable statements
on the potential future commercial deployment are difficult to
make.2 If it were possible to develop a cost-effective and envi-
ronmentally friendly way to produce hydrogen for industrial
and commercial purposes from biomass, this would already be
one important step forward.
The basic categories of biomass materials as the feedstock to
provide low-cost and low-carbon hydrogen production can be
classied into several categories including lignocellulosic
biomass, agricultural residues, bio-wastes and energy crops, as
well as their products such as biogas, bio-oil and biochar. The
main issues to take into account in the selection of biomass as
a feedstock for hydrogen production are the spectrum of culti-
vars available in each country and the growth time, the different

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demands for each cultivar for other purposes, and harvesting,
transport and pre-treatment costs. Agricultural residues and
municipal bi-waste can viably provide cost-effective sources of
energy with low sulfur content. The promising energy crops are
a good choice for hydrogen production because they do not
have direct conicts with any food crops. Large-scale cultivation
of the energy crops in the contaminated lands is also needed for
remediation purposes as well as to fulll the bio-energy
demand. Different types of biomass, even the same types of
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biomass collected from different resources could present
diverse physicochemical characteristics and morphological
structures, and the differences and irregularity in biomass can
adversely affect the conversion efficiency and products. The low
bulk density, high oxygen content, and high inorganic
compounds such as potassium, calcium, sodium, silicon,
phosphorus, and chlorine compounds in raw biomass are
critical challenges to the thermochemical conversion process.
The potential for biomass-derived feedstock to hydrogen
production should also be related to environmental and health
issues. There should be an emphasis on the values of the
intrinsic metal salts in the biomass to promote pyrolysis and
gasication as catalytic effects.
Fig. 1 Hydrogen production processes from several typical kinds of biomass by different methods.
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Fig. 1 shows hydrogen production from different biomass-
derived feedstocks by different methods. Compared with
chemical and biochemical methods, the thermochemical
method gives a simpler route to the production of hydrogen and
usually needs no chemical addition, and can also convert
a variety of wet biomass and utilize the entire biomass-derived
feedstock. The enhanced hydrogen production by the thermo-
chemical process is mainly dependent on sorbent use for in situ
CO2 removal and studies have indicated that a further increase
in the amount of sorbent used, more than the critical value,
does not improve the intensication performance consider-
ably.3 Despite the various advantages of hydrogen production
from biomass, it is not being utilized at commercial levels due
to the existence of various challenges associated with the highly
distributed biomass-derived feedstock and the generic short-
comings of the thermochemical conversion technology. Thus,
in this paper, the issues, challenges and advances associated
with the types and properties of biomass and the thermo-
chemical conversion to hydrogen production in an environ-
mentally friendly way are highlighted and are expected to prove
useful to researchers, students, technology players, and
government authorities.
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2. Thermochemical conversion for
hydrogen production
2.1 Pyrolysis and gasication processes
To develop reliable hydrogen production from biomass, the
pyrolysis and gasication were rst studied as very low-cost
methods. Table 1 summarizes the methods for pyrolysis and
gasication of biomass using steam, air/oxygen, CO2, or catal-
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gaseous products from pyrolysis is still too low to be commer-
cially attractive. One of the methods to increase the hydrogen
yield is to apply catalytic pyrolysis. Watanabe et al. suggested
that the presence of basic sites in TiO2 is responsible for glucose
isomerization to fructose, whereas acid sites facilitate the
further dehydration to 5-hydroxymethylfurfural (5-HMF).20
Chen et al. studied the effect of catalysts on fast pyrolysis, and
Ca and Cr oxides seemed to perform the best.21 Duman and
Yanik studied hydrogen production from the steam pyrolysis of

ysis by different devices.4–15 In order to save energy and

demonstrate the feasibility using solar energy, biomass
conversion was carried out under real solar irradiation condi-
tions, and experimental temperatures were up to 1000–
1400
C.19
2.1.1 Pyrolysis of biomass. Generally, the pyrolysis of
biomass is the main sub-process in the thermochemical
hydrogen production and gasication and has also been
proposed as a key technology in the bio-renery process to
produce chemicals and fuels. The detailed fundamentals and
reaction kinetics of biomass pyrolysis have been studied and
reviewed.16,17 The studies have demonstrated that gaseous
products can be obtained from the pyrolysis of biomass at high
temperatures.18,19 However, the hydrogen concentration in
olive pomace in a two-stage xed bed reactor using different
char-based catalysts, and the results showed that the steam had
no inuence on hydrogen production, and Ni-impregnated and
non-impregnated biomass char catalysts can enhance hydrogen
production.22 If the purpose of pyrolysis is to maximize the
hydrogen yield, then process conditions of high temperature
and long residence time should be selected, and consideration
should be given to the catalyst used.
2.1.2 Gasication of biomass. The potential of various
gasication technologies to produce hydrogen should be
emphasized to exhibit abundance, low cost, and diverse appli-
cations in numerous industries for biomass conversion.
Recently, several review papers concerning biomass gasication

Table 1 Summary of several studies on biomass pyrolysis and gasification

Technology Feeding Reactor Process condition Product yield Reference

Fast pyrolysis Lignocellulosic, wood waste Circulating uidized Atmospheric pressure, 400– 72% bio-oil, 12% gases and 4
bed reactor 550
C, residence time of 1 s, 16% char
small particle sizes <0.5 mm
Flash pyrolysis Wood sawdust Conical spouted bed 425–525
C Bio-oil and gases 5
reactor
Slow pyrolysis Algal biomass TGA and Py-GC/MS Low heating rate, 350– 45–55% liquids, 25–35% 7
750
C, atmospheric gases, and 15–25 char
pressure, long residence
time
Air gasication Pine sawdust Fluidized bed reactor 700–900
C, ambient, air High temperature favored H2 8
with steam mixture and gas yields
Steam gasication Olivine particles Fluidized bed gasier 770
C and a steam/biomass 19.4–42.6% H2 9
ratio of 1 with calcined
dolomite
Steam–oxygen Woody biomass and Circulating uidized 800–820
C, steam to 20–25% H2, 20–25% CO, 35– 10
gasication agriculture residue bed gasier biomass ratios of 1.1–1.51; 40% CO2
oxygen to biomass
stoichiometric ratios (ER) of
0.36–0.4
Steam–air Wood waste Fixed bed downdra Max. bed temp.: 900–1050
C 25–30% H2, 40–45% CO, 20– 11
gasication gasier and exit temp.: 700
C; 25% CO2
equivalence ratios of 0.2–0.3
Steam–air Wood pellets Fixed bed updra Max. bed temp. of 950– 25–35% H2, 30–40% CO, 20– 12
gasication gasier 1150
C and exit temp. of 30% CO2, 5–10% CH4
150–400
C, and equivalence
ratios of 0.24–0.35
Supercritical water Lignin, cellulose and waste Tubular batch reactor Fixed heating rate of 30–40% H2 13
gasication biomass 30
C min1 to 650
C and
50 min residence time, with
K2CO3 and 20NiA0.36Ce/
Al2O3 catalyst
Chemical looping Biomass char Fix-bed reactor 850
C with natural iron ore H2, CO 14
gasication
Solar gasication Pine and spruce wood Tubular reactor with 1000–1400
C 35–45% H2, high carbon 15
solar energy conversion rate of 93.5%

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have been published, but few of the papers focused on the
generic shortcomings and process intensication perfor-
mance.23–25 It is estimated that a typical route for biomass
gasication and steam reforming (and/or WGS) with a pressure
swing adsorber system (PSA) requires 2.4 TJ of primary energy
input per TJ of hydrogen,26 and for a plant with an expected
hydrogen output of 139 700 kg per day and cost of biomass in
the range of $46–80 per dry-ton, the hydrogen production cost is
expected to be $1.77–2.05 per kg.27
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Biomass gasication occurs through a sequence of complex
thermochemical reactions and hence, it is unrealistic to split
the gasier into different zones carrying out many gasication
reactions simultaneously. As can be seen in Fig. 2, the various
stages and temperature changes involved in the gasication
process are as follows: drying, pyrolysis, combustion and
reduction zones. The gaseous product is a mixture of the
combustible gases including CO, H2, and CH4 and non-
combustible gas such as CO2 and N2. For hydrogen produc-
tion, good quality gas from the gasier should have high
hydrogen and low tar content. The quality of gas from biomass
gasication can be affected by some parameters including
temperature, pressure, residence time, equivalence ratio,
biomass characteristics and gasier design. Air gasication of
biomass only produces syngas with a low H2 content and low
heating. In steam gasication, the hydrogen yield is far better
than pyrolysis and air gasication while the overall conversion
efficiency of thermal energy-to-hydrogen can also reach up to
52%.
Biomass oxygen-rich air gasication is one effective method
for producing medium heating value gas, but it needs a large
investment for oxygen production and this disadvantage
impedes its popularization. The experimental studies reported
in previous literature28 showed that the steam-gasication
processes based on the uidized-bed reactor with or without
added O2 are also capable of producing MHV of 10–16 MJ N1
m3 gas with a 30–60 vol% H2 content. This is due to the fact
that no nitrogen from air gasication is present in the products,
and in addition, a homogeneous WGS reaction is possible in the
Fig. 2 Biomass gasification process with main chemical reactions and temperature descriptions.
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early stages of the gasication process to increase hydrogen
production. However, this technology requires a steam
temperature of over 700
C, and there is the added cost of steam
generators with good performance.
2.1.3 Reactor congurations. A further complexity in the
pyrolysis and gasication operations is the type of reactors. The
design of a reactor depends mainly on biomass availability, size,
shape, ash content and moisture content. The xed-bed reactor
has been reported as suitable for small-scale heat and power
generation applications and can also be classied as downdra,
updra and cross dra. The uidized bed reactor (FBR), which
is exible in terms of biomass materials, has a superior heat
transfer rate, however, some difficulties are induced by the
presence of the heat carrier solid and the separation from the
products. The microwave and electromagnetic heating for
different reactors can be considered largely advantageous for
environmental applications in the processing of sludge or
radioactive and toxic wastes including hospital waste, tyres and
some biomass. The pyrolysis and gasication can also be
affected by tars, HCl, alkali metal and dust particles produced
from the various biomass-derived feedstocks, which not only
reduce the quality of product gases but also lead to the mal-
functioning of the equipment.29,30
For the design of pyrolysis and gasication devices and their
scale-up, the process characteristics and raw materials should
be thoroughly understood for the optimal operation and control
of the thermochemical treatment. Additionally, a high-
efficiency hydrogen production process should be developed
by improving the operating conditions through the introduc-
tion of contaminant-control technology. In most cases, the
interactions of various compounds during the combined
removal of various contaminants is complex and not well
understood. In our previous studies, the experiment was
designed for the simultaneous or combined removal of various
contaminants from pyrolysis and gasication gas and the
results indicate that the simultaneous or combined removal
process for HCl, alkali metal vapor, etc. with high efficiency is
feasible.30
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2.1.4 Supercritical water gasication. The interest in the
supercritical water gasication of agricultural wastes, leather
wastes, switchgrass, sewage sludge, algae, manure, olive mill
wastewater and black liquor has increased in the last 10 years,
and the main product components of H2, CH4, CO2, and CO
content are very low due to CO reacting further by the WGS and
methanation reaction. Jin et al. reported that supercritical water
gasication is an efficient and clean conversion of biomass due
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to the unique chemical and physical properties, and anthracene
and furfural were the key intermediates; some microscopic
reaction mechanisms may provide information for reactor
design and operating condition selection.31
The studies demonstrated that an almost total conversion in
supercritical water gasication of corn silage and clover grass
can be achieved at temperatures higher than 700
C, and
hydrogen content ranging from 26% to 57% was obtained.32
Chen et al. studied hydrogen production by sewage sludge
gasication in supercritical water with a uidized bed reactor,
and more than 40% carbon gasication efficiency at a temper-
ature of 540
C and pressure of 25 MPa for a 2 wt% sewage
sludge with 2 wt% sodium carboxymethyl cellulose feedstock
was achieved.33
The use of catalysts such as Ni, Ru, Pt and some alkali metal-
based materials in supercritical water gasication can reduce
the temperature and pressure, and thus decrease the equip-
ment and operating costs.34 Hydrogen production from the
supercritical water gasication of oleic acid with Ru/Al2O3
catalyst was conducted at the temperatures of 400–500
C and
a pressure of 280 bar, and high biomass conversion and high
hydrogen yields were obtained; without the catalyst, most of the
oleic acid remained unconverted.35 Pinecone biomass was
gasied in subcritical water, near-critical water and supercrit-
ical water to investigate hydrogen yields, and the results
demonstrated that in the non-catalytic gasication of the
pinecone, the highest hydrogen concentration of 1.42 mmol g1
with the heating value of 488 kJ N1 m3 of the gas products was
obtained in supercritical water. At 30 wt% catalyst loading, the
highest hydrogen yield was increased to 3.26 mmol g1.36
The attempts to industrialize the supercritical water gasi-
cation of wet biomass were carried out with a capacity of 50 kg
h1 in a uidized bed reactor by the TU Del/Gensos semi-pilot
scale setup, and the results indicated that the temperature and
the residence time played signicant roles in the conversion
efficiencies.37 Correa and Kruse reviewed supercritical water
gasication of biomass for hydrogen production; high oper-
ating costs and high energy demands for high temperature and
high-pressure process were found to be crucial problems in the
supercritical water gasication of biomass.38 Corrosion of the
reactor is another challenge that needs to be addressed.
Implication of catalysts in the supercritical water gasication of
biomass can reduce the temperature and pressure with
enhanced H2 production. The poisoning and deactivation of the
catalysts during supercritical water gasication of biomass
increases the process costs. Supercritical water gasication may
represent one of the possible future options for hydrogen
production. Due to the complexity and interplay of the system,
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designing an efficient and low-cost supercritical water gasi-
cation process for biomass is still underway.
2.1.5 Chemical looping gasication. Chemical looping
gasication (CLG) using an oxygen carrier (OC) to replace the
gasication agent (O2) is a novel technology with low cost for
converting biomass feedstock into syngas. First, the oxygen of
OC is applied as an oxygen source for combustion and gasi-
cation, and then the reduced OC can be regenerated in the air
reactor. Huang et al. used the natural iron ore as an OC for the
CLG of biomass char in a xed-bed reactor and steam was used
in order to improve the CLG conversion of biomass; the results
showed that the char gasication rate of 80% was obtained by
the mixture of iron ore and steam with redox reactions.39
The CLG mechanism of redox reactions between biomass
and OCs was also discussed by Wang et al., and the thermo-
dynamic analysis of the CLG of biomass by Mn2O3 OC for
syngas production was performed by Gibbs free energy mini-
mization methods.40 The optimal conditions were suggested
and the total dry concentration of CO and H2 was about 98.8%,
and high carbon conversion was also obtained.40 Chen et al.
studied the multi-functional iron-based OC for H2-rich syngas
production by gasication from bauxite residue in the uidized
bed reactor and the feasibility of auto-thermal CLG was evalu-
ated based on the functions of OCs as oxygen and heat
carriers.41 Syngas production with calcium ferrite and barium
ferrite by solid–solid reactions in a xed-bed ow reactor was
studied by Siriwardane et al., and the results indicated that the
BaFe2O4 and CaFe2O4 OCs are excellent for the CLG of solid
fuels.42
A 25 kWth prototype for the CLG of biomass using natural
hematite as OC was studied.55 The effects of temperature, the
ratio of steam to biomass and hematite mass percentage were
determined and 860
C was the optimal gasication tempera-
ture corresponding to high carbon conversion and syngas
yields.43 The study on the CLG of biomass in a xed-bed reactor
showed that CO was generated faster than other components
because carbon was partially oxidized and H2 was quickly
reacted and consumed by the lattice oxygen [O] in the OC.44
CLG based on one kind of carbonaceous material process for
H2-rich syngas production and CO2 capture can be seen in
Fig. 3. In general, the hydrodynamic, chemical reaction
kinetics, and the transfer of heat and mass in this process are
quite different from that of a commercial gasication system.
Wang et al. analyzed the feasibility of H2 production by CLP
based on coal gasication in a transport reactor, and the effects
of temperature, pressure, the ratio of steam to carbon on the
reactor hydrodynamics, chemical reaction rates, steam/power
consumption and products were given and discussed.45 Wei
et al. studied the steam gasication of biomass for hydrogen
production in an external circulating concurrent moving-bed
system with CaO as the CO2 sorbent.46 In this system, steam
gasication, in situ CO2 capture, char combustion, and CaCO3
calcination occurred simultaneously. The experimental results
showed that enhanced H2 production was achieved by in situ
CO2 removal and H2 concentration of 60–70 mol% in dry gas
was obtained.
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Fig. 3 Biomass gasification with the Ca-chemical looping process.
Hydrogen production from agricultural biomass using steam
as the gasifying agent by CLG with in situ CO2 capture was
studied in two uidized-bed reactors. The work reported 71%
concentration of H2 and nearly 0% concentration of CO2 in the
product gas were obtained. CaCO3 of 40% could be regenerated
to CaO at the temperature of 800
C.47 In these studies, the use
of a CLG for the production of hydrogen from biomass gasi-
cation takes place in two uidized bed reactors connected by
solid CaO ow. In the rst carbonator, the gasication and WGS
reaction can be enhanced and improved by in situ CO2 removal
using CaO-based sorbent and the tar may be decreased. In the
second regenerator, the captured CO2 is released and collected.
Armbrust et al. presented a continuously operated 20 kWth
CLG using dual uidized-bed reactors.48 The effects of the main
parameters including temperature, looping ratio (LR), and
space-time on the H2 production were investigated and the
results showed that the H2 concentration of 84.4 vol% and a CO
conversion of 76.4% were achieved. The experimental investi-
gation on biomass gasication for high-purity hydrogen
production by CLP over a range of temperatures between 650
and 900
C and pressures up to 20 atm was performed by
Moghtaderi et al. The results conrmed that CO2 capture effi-
ciencies of 56.4% and high purity hydrogen can be achieved,
and concrete and demolition waste could be used as a source of
sorbent for in situ CO2 removal.49
2.2 Steam reforming process
2.2.1 Steam reforming of biomass-derived feedstock.
Biomass can be transferred to bio-oil or syngas by pyrolysis and
gasication and the products are usually used as low-quality
fuels because of their complex compositions, and hydrogen
concentration is very low. High hydrogen yield can be obtained
using several reforming technologies over catalysts such as
steam reforming, dry reforming, auto-thermal reforming,
partial oxidation and chemical looping reforming. Table 2
depicts a schematic representation of the hydrogen production
from biomass via different reforming processes.50–54 Steam
reforming represents the most developed industrial process
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and gives the lowest operating cost and the highest hydrogen
yield. Due to the difficulties in hydrogen transportation and
storage, the in situ hydrogen production by the steam reforming
of liquid biomass-derived feedstock as the hydrogen carrier may
have a promising future. Among all the carriers, methanol,
ethanol and glycerol are some attractive hydrogen sources and
possess relatively high H/C ratios. The endothermic steam
reforming reactions can operate in the gas or aqueous phases
and present more challenges and opportunities for future use.
Recently, research related to the steam reforming of
biomass-derived feedstock using different kinds of materials in
Table 3 has taken new steps toward improving it as the main
pathway to obtaining renewable hydrogen as an efficient
candidate in the future global energy scenario.55–72 From ther-
modynamic studies, hydrogen production from the steam
reforming of biomass-derived feedstock at temperatures higher
than 400
C has been proved, and some studies have shown that
the increment of temperature and steam used favors the
hydrogen production, while high pressure considerably reduces
hydrogen yield, and low-cost Ni-based catalysts were extensively
used.70–72 The use of high temperature in steam reforming has
two effects: one is that WGS can be shied toward CO and H2O,
which decreases the H2 yield, and the other one is that the
conversion of biomass-derived feedstock is increased due to
decomposition.56 The ratio of steam and carbon (S/C) in steam
reforming is an important parameter because increasing this
ratio will increase the conversion and also reduce carbon
formation. The steam gasication of carbon might be enhanced
at a high partial pressure of steam. However, a high ratio of S/C
increases energy consumption. The steam reforming of hydro-
carbons occurs rst through different adsorbed species on the
catalyst to form CxHy* and OH* species. The OH* and CxHy*
can then react to form CO and H2, and H2 and CO2 are formed
from the WGS, and the following radical reactions may be
included:73
CH4(g) + 2* # CH3* + H*
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Table 2 Summary of several reforming technologies for biomass conversion

Technology Advantage Disadvantage Reference

Steam reforming Most developed industrial process, High water and energy 50
no oxygen requirement, lowest consumptions and CO2 emissions
operating temperature, best H2/CO
ratio
Dry reforming Environmental potentials for CO2 Low H2/CO ratio, high operating 51
emission temperature, and limited
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Autothermal reforming
Partial oxidation reforming
Chemical looping reforming
commercial experience
Lower process temperature than Limited commercial experience 52
partial oxidation and low methane
slip
Reduced desulfurization Low H2/CO ratio, high operating 53
requirement, no catalyst temperatures and complex
requirement and low methane slip handling process
High carbon capture and less Limited commercial experience 54
energy consumption

CH3* + * # CH2* + H* 2H* # H2(g) + 2*

CH2* + * # CH* + H* The active metal particles in the catalyst can be covered by
carbon formed during steam reforming, and carbon can also
CH* + * # C* + H* cause disintegration of the support material. The different
carbon formation reactions may include CO reduction and CxHy
H2O(g) + 2* # HO* + H* decomposition as follows:74
CO reduction:
OH* + * # O* + H*
CO + H2 # Cs + H2O
C* + O* # CO* + *

CO* # CO(g) + *

Table 3 Hydrogen production from steam reforming of different biomass-derived feedstocks

Reactor and process

Feeding Catalyst conditions Products Reference

Biomass-derived syngas or
gasication gas
Biomass-derived ethanol
Biodiesel
Biodiesel byproduct glycerol
Sunower oils
Waste cook oils
Biomass-derived pyrolysis
oils or models
Biomass tars or models
Biomass-derived organics
mixtures (ethanol, phenol,
naphthalene, methanol)
Ni-based catalyst, IrNi
catalyst
Ni-based, Pt/Al2O3, Rh/Al2O3,
RhPt/CeO2, Co3O4/CeO2
Pt/Al2O3 monoliths, Ni-
based catalysts, Ni/Ce–Zr
Ni-based catalysts
Ni-based catalyst
Ni-based catalyst with CaO
sorbent
Ni/Al2O3, NiCo/MgO,
LaKMnO3, Fe/olivine
Ni/Al2O3, CoFe/Al2O3, Ni/
TiO2, Y-zeolite
Ni/Al2O3
Fixed-bed reactor at 800– H2, CO2 55
950
C, 1 bar, 114 000 h1
Fixed-bed reactor with H2, CO2, CO, CH4, carbon 56–59
atmospheric pressure and conversion > 95%
500–800
C
a tube reactor heated by an H2O, H2, CO, CO2, CH4 60 and 61
electrical oven or xed-bed
reactor with atmospheric
pressure 500–850
C, S/C ¼
2–5
Fixed bed reactor, 500– H2, CO2, CO, CH4 62 and 63
850
C, S/C ¼ 3
Bench-scale unmixed steam H2, CO2, CO, CH4 64
reformer, 600–800
C
Packed bed reactor, 600
C H2 (>95%) 65
Plug ow reactor under near H2, CO2, CO, CH4, carbon 66 and 67
atmospheric pressure (1.07 conversion > 90%
bar), a residence time of
0.68 s and 400–1000
C
Fixed-bed reactor, gliding H2O, H2, CO2, CO, CH4, 68–71
arc reactor, uidized-bed carbon conversion > 90%
reactor
Fixed-bed reactor at 773– H2O, H2, CO2, CO, CH4 72
1073 K

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CH4 decomposition:
CH4 # Cs + 2H2
CH decomposition:
CnHm # nCs + m/2H2
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2.2.2 Catalysts for the steam reforming process
(1) Ni-based catalysts. The commercial Ni-based catalyst for
the steam reforming process is effective, and can also run under
a wide range of conditions with operating temperatures from
approximately 500 to 950
C and pressures from 10 to 25 atm.
Table 4 gives some typical Ni-based catalysts used in steam
reforming processes.75–109 Hu and Lu investigated the inuence
of different promoter metals including Li, Na, K, Mg, Fe, Co, Zn,
Zr, La, and Ce on the performance of a Ni/Al2O3 catalyst in the
steam reforming of acetic acid, and found that the K addition
gave the largest improvement in the catalytic performance in
terms of both activity and stability, and the addition of Co, Fe,
or Zn decreased feeding conversion.78
The use of Ni-based reforming catalyst during hydrogen
production from steam reforming has four major issues:
activity, poisoning, carbon deposition, and sintering. The
studies have demonstrated that the catalytic activity and the
species of products were affected by Ni content, the type of
support and structure. Various supports were included such as
zeolites, dolomite, olivine and some metal oxides such as La, Fe,
CeO2, SiO2, ZrO2, TiO2, MgO, ZnO, and Al2O3, etc.
The different Ni-based catalysts have been prepared by the
co-precipitation method with the rising pH technique for
renewable hydrogen production from glycerol steam reforming
in a continuous ow xed-bed reactor under atmospheric
pressure at certain temperatures, and the Ni/Mg/Al, Ni/Cu/Al,
Ni/Cu, and Ni/Mg catalysts with very low cost were found to
have good performance at relatively low temperatures of 500–
600
C.110–112 Świerczyński et al. studied the steam reforming of
biomass tar using toluene as a model compound via the Ni/
olivine catalyst and found that the Ni/olivine catalyst exhibi-
ted low carbon deposition, high activity and selectivity for H2
production.113 Zhang et al. studied Ni/olivine catalysts doped
with CeO2, and found that the doping of CeO2 in the catalysts
presented a particular effectiveness for coking resistance and
catalytic activity during the steam reforming of biomass tar.114
The promoting effect of CeO2 on the catalyst is probably
through a redox mechanism from Ce0 to Ce4+.
The synergistic effect of the combination of two active
elements of Ni and Co has been studied and the results indi-
cated that Ni should be more suitable than Co in the steam
reforming of hydrocarbons.115,116 However, the supported Co
catalyst was more effective for the steam reforming of oxygen-
ates than the supported Ni catalyst.116 Some results indicated
that the performance of the Ni–Co/Al2O3 catalyst for the resis-
tance to coke formation and life was much higher than the
corresponding monometallic Ni and Co catalysts in the steam
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reforming of biomass tar, and this is due to the synergy between
Ni and Co atoms on the Ni–Co alloy surface.117–119 The catalyst
support has also been known to signicantly improve the
catalytic property of metals by altering the electronic structure.
Some studies have indicated that oxygen ions can be trans-
ported through metal oxide supports such CeO2 or ZrO2 and
also help to burn out the deposited coke.120
(2) Non-Ni-based catalysts. For non-Ni-based catalysts,
Tomishige et al. studied the catalytic activity of noble metal
catalysts supported on CeO2/SiO2 for the steam reforming of
biomass tar as compared with Ni-based catalysts.121 They found
that noble metal catalysts had better performance than the
commercial Ni catalysts, and among the noble metals, Rh was
found to be signicantly more active than others with a selec-
tivity order of Rh, Pt, Pd, Ru, and Ni. Kolb et al. found that Pt/
In2O3/Al2O3 catalysts exhibited 10 times higher activity as
compared to the common Cu-based catalysts.122,123 Iwasa et al.
reported that noble metal catalyst containing the PdZn alloy
phase was an alternative to a copper catalyst for hydrogen
production from steam reforming.124,125 However, the perfor-
mance of bimetallic PdZn catalysts is also highly sensitive to the
preparation procedure, always bearing the risk of metallic Pd
formation, resulting in the formation of large quantities of
undesired CO under practical operating conditions. Studies
have been carried out on the steam reforming of the biodiesel
byproduct glycerol by different noble metal catalysts including
Ir, Rh, Ru, Pt, and Pd, and the results showed that the Rh and
Ru catalysts exhibited high H2 selectivity and glycerol conver-
sion, and the reaction process was also affected by carbon
formation and deposition.126
Different non-Ni-based catalysts used in the steam reforming
process are given in Table 5.127–148 As is known, the noble metal
catalysts have very high catalytic activity with high coke resis-
tance and long terms ability. However, one of the major chal-
lenges in implementing these catalysts for hydrogen production
from the steam reforming of biomass-derived feedstock is the
high cost associated with the current catalyst formulations,
which features prohibitively high noble metal loadings (typi-
cally ranging from 5.0 to 15 wt%). The penalty incurred by using
noble metal catalysts can be compensated for, to some extent,
by reducing the loading amount of noble metals while retaining
the high catalytic activity. Currently, systematic studies on the
catalytic performance of noble metals and Ni-based catalysts
with extremely low noble metal-loading over a wide range of
operating conditions are unexplored. All noble metals added to
Ni-based catalysts are less prone to carbon deposition and
formation, and are thus effective for enhancing the stability of
catalysts.
2.2.3 Effective catalyst modication strategies. A good
catalyst for the steam reforming of biomass-derived feedstock
cannot fully eliminate carbon formation; however, it may favor
the formation of reactive intermediate species for the enhanced
decomposition of heavy hydrocarbon, tar and aromatic
compounds. Under these circumstances, the modication of
the catalyst has been investigated to help to decrease the
support acidity and also improve the prohibition of carbon
formation on the surface. Three strategies may be considered:
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Table 4 Different typical Ni-based catalysts used in the steam reforming process

Catalyst Description T (
C) S/C ratio X (C, %) Reference

Ni/Al2O3 Glycerol steam reforming in the xed-bed 550–650 3 62–90 75–77

reactor
Ni–Na/Al2O3 Catalyst with K addition presents high 400 7.5 Na: 93.8 78
Ni–K/Al2O3 activity for steam reforming of acetic acid K: 100
Ni–Mg/Al2O3 Mg: 47.8
Ni/Al High activity for acetic acid steam 650 4.35 100 79
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reforming
Ni/Zn/Al Coprecipitation method with low coke 600 2 — 80
formation of <3.2%, CO selectivity of 99%
Ni/Al/Zn Catalyst (8 wt% Ni and 20 wt% Zn) had 500 1.4 100 81
best activity
Ni/B/Al Boron improved stability and conversion 800 1 61 82
Ni/Mg/Al Hydrotalcite used for preparation, high 800 0.75 30 83
coke resistance
NiSiO2/Al2O3 Sol–gel method with 10% Ni has high 700 3.5 95.7 84
activity
Ni@SiO2 Core–shell structure with Si core and 750 1.3 85 85
11% Ni
Ni/MgO Nanocrystalline MgO support for catalyst 700 1 77 86
with 7% Ni and coke resistant and stable
to 50 h for steam reforming of CH4
Ni/MgO/Al2O3 High activity for steam reforming of 650 1.5 95 87
acetic acid
Ni/La2O3 High activity and selectivity toward H2 for 800 2 100 88
steam reforming of biomass-derived
ethanol
Ni–La/Al2O3 Perovskite structured Ni/La with high 850 1.24 100 89
stability
Ni/TiO2 High activity for steam reforming of tar 550–650 H2O 9.2% 65–76 90
derived from the pyrolysis of wood
biomass
Ni/ZrO2 High activity for steam reforming of tar 550–650 H2O 9.2% 68–81 91
derived from the pyrolysis of wood
biomass
Ni/La/Ca Perovskite-derived catalyst for glycerol 550 3 100 92
steam reforming
Ni/Al/Mo Catalyst with Ni2AlO4 and/or Ni2O3 and 700 4 85 93
MoO42 on the surface, Ni/Al ratio of 3
and 0.05 wt% Mo
Ni/MgOAl2O3 Core–shell structure, 10% Ni, good 750 2 97 94
stability over rst 50 h
Mg/Ni/Al Coprecipitation method for catalyst with 600 3 90 95
low coke formation
Pt/Ni/Mg/Al Good startup/shutdown activity of 700 2 95 96
catalyst with 0.5% Pt
Ni/Rh/Al2O3 Catalyst with 1 wt% Rh and 10 wt% Ni, 675 2 99 97
good activity of WGS
Ni/Ce–ZrO2 CO selectivity of 67%, good stability of 750 3 97 98 and 99
WGS
Ni/Si/Al/Ce Low carbon formation, even at lower S/C 800 1.3 70 100
ratios
Ni/Cu/Zr/Ce Catalyst with 1% Cu and 10% Ni for 400 10 43 101
ethanol steam reforming
Pt/Ni/Ce Catalyst with 2.8% Pt and 9.8% Ni for 350 3 100 102
ethanol reforming with high carbon
deposition and high byproduct
formation
Ni/Ca/Zr Ethanol reforming and Ca deter coking 500 3 100 103
Ni–Co/La2O3 High activity and selectivity for acetic 550 9 100 104
acid steam reforming
Ni/Ce/Zr High activity for acetic acid steam 650 3:1 100 105
reforming

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Table 4 (Contd. )

Catalyst Description T (
C) S/C ratio X (C, %) Reference

Ni/olivine–CeO2 3.0% NiO/olivine doped with 1.0% CeO2 700–830 5:1 60–75 106 and 107
for steam reforming of biomass tar with
resistance to coking
Ni–Co/HT Co and Ni in hydrotalcite (HT)-like 500–650 3–9 — 108
materials for high activity for ethanol
steam reforming
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Ni/dolomite High activity for steam reforming of 600–800 2–10 70–80 109
biomass tar

(1) A method for the catalyst developed is based on an
inexpensive non-noble metal by adding a small amount of
noble and/or other non-noble metals to enhance the catalytic
properties. Palma et al. studied the performance of CeO2
supported Pt–Ni and Pt–Co catalysts in ethanol steam
reforming at low temperature, and the results indicated that
the Pt/Ni/CeO2 catalyst presented high activity and the
product distribution was very close to the equilibrium calcu-
lation.149 In addition, the Pt–Co catalysts also appeared very
attractive with high hydrogen selectivity and low coking
tendency.145 The bimetallic and trimetallic catalysts can lead
to high catalytic performances. Nevertheless, noble–noble
bimetallic catalysts are not viable candidates for the steam
reforming of biomass-derived feedstock due to scarcity and
price concerns.
(2) One of the most popular methods for catalyst improve-
ment is to minimize the Ni particle sizes on the surface during
the preparation process. Carbon formation and deposition on
a Ni surface of the catalyst has been known to necessitate Ni
ensembles, and large Ni particles on the catalyst could cause
more severe carbon deposits. Small Ni particles with high
specic surface area are usually considered more advantageous.
However, because the steam reforming reaction typically occurs
at high temperature, the initially small Ni particles on the
catalyst may be sintered during the reaction and heavy carbon
deposition could be formed on the large Ni particles of the
catalyst surface size. Strong metal–support interactions and
addition of the metal are oen used to increase the dispersion
and maintain the small size of the Ni particles at high
temperature. When strong interactions of the Ni particles and
their supports occur, the size of the Ni particles during the
synthesis can be decreased and also contribute to minimizing
the aggregation because the support tends to retain Ni particles.
Han et al. studied uncoupling the size and support effects of Ni
catalysts for reforming, and the effects of Ni particle size and
support in the catalyst were separately observed.150 The decrease
in the particle size of catalysts could result in enhanced metal–
support interaction for the high activity of the catalyst for
hydrogen production from the steam reforming process.151
Thus, the small Ni nanoparticles would denitely be more

Table 5 Different typical non-Ni-based catalysts used in the steam reforming process

Catalyst Description T (
C) S/C ratio X (C, %) Reference

Ru/MgO/Al2O3 Catalyst with 5 wt% Ru for steam reforming of acetic acid 650 1.5 99 127
Co/La/Al2O3 Catalyst with 18 wt% Co for steam reforming of acetic acid 400 1 85 128
Rh/CeO2–ZrO2 Catalyst with 0.5 wt% Rh and high activity and selectivity 650 3 90 129
Ru/SrO–Al2O3 Superior catalytic activity for steam reforming of biomass tar 600 2.0 80 130
Rh/CeZrMgO 0.5 wt% Rh/Ce0.14Zr0.81Mg0.05O2 with high activity for steam reforming of phenol 450–550 — 70–80 131
Co/MgO 12 wt% Co/MgO catalyst for biomass tar steam reforming 900 0.6 23 132
Zn/TiO2 96% selectivity and high hydrogen yield 450 1.1 100 133
Pd/ZnO Methanol SR. Low CO selectivity of 2% 300 1.8 100 134
Pt/Ce/C High activity and selectivity and decreased deactivation 350 0.5 90 135
Pt/C Nanotubes, promoted by Na, high conversion at high S/C 400 5 >95 136
Pt/Mo/C Higher activity than traditional catalysts at reaction conditions 295 5.5 30 137
Ir/CeO2 2 wt% Ir catalyst presents high activity for the steam reforming of bio-ethanol 650 1.5 99 138
Pt/Al2O3 0.5 wt% Pt high activity and low carbon formation 340 1.5 98 139
Rh/Sr/Al 1% Rh on Sr-hexaaluminate presents high stability 740 1.4 45 140
Rh/CeO2 2 wt% Rh catalyst for ethanol steam reforming 450–650 8 100 141
Rh/Zr/Ce High conversion at lower temperature with low S/C ratio 700 4 95.2 142
Gd/Ce Good for high temperatures, resistant to carbon deposition 900 5.5 80 143
Pt/CeO2–La2O3–Al2O3 High activity and stability 500 3 — 144
Pt/Co/CeO2 High activity and selectivity for bioethanol steam reforming 350 3 100 145
Pt/In2O3/Al2O3 15 wt% Pt catalyst presents highest activity 600–800 3 100 146
Cu/Ce 70% Cu catalyst for minor deactivation stabilized aer 20 h 300 1.5 100 147
Cu/Zn/Zr High activity for methanol steam reforming 260 1.2 100 148

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advantageous for ensuring the high activity of reforming and
the interaction of Ni particles and support can maximize the
activity. In fact, the Ni particle size effect on catalytic activity is
limited, and most Ni particles on the catalyst inevitably become
larger aer the long reforming reaction. Baudouin et al. studied
that the turnover frequency in the reforming reaction, which is
the activity per available surface Ni atom per unit time, is
independent of Ni particle size for the reforming at 500
C.152
They argued, however, that the Ni particle size on the catalyst
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was signicantly increased aer the reaction despite a relatively
low reaction temperature being used and this increase in Ni
particle size also precluded the proper evaluation of the particle
size effects.152
(3) For a given active metal, an appropriate support can
enhance the metal and support interaction, thus leading to
a reduction in metal sintering, while too strong interactions of
metal and support will decrease the catalyst reducibility to low
catalytic activity. In that case, the adequate doping of the
support with another species can ensure that the metal–support
interaction is strong enough to avoid catalyst sintering and
weak enough to ensure the reducibility (such as MgO doping of
NiO/Al2O3). Moreover, mesoporous and composite structures
can perform better than reducible and irreducible metal oxides
due to their peculiar properties. Although these general guide-
lines for the inuence of the metal, support and promoter are
generally valid, different studies have reported varying degrees
of catalyst development success based on a given metal, support
or promoter. This can be attributed to complex mechanisms of
steam reforming reaction and the inuence of operating
parameters, and thus the validity of the aforementioned factors
is extremely dependent on the process method and catalyst
involved. On the other hand, some studies have shown that
perovskite-type catalysts can also exhibit very good selectivity
and conversion to hydrogen production.153
2.2.4 Chemical looping steam reforming. The concept of
chemical looping reforming (CLR) is based on chemical looping
combustion (CLC) in Fig. 4(a), where an oxygen carrier (OC)
catalyst performs the task of bringing oxygen from the air to the
fuel without contact between fuel and air.154 In the case of CLR,
the system included two reactors, namely, a fuel reactor (FR)
and an air reactor (AR). The OC constantly circulates between
the FR and AR. In the FR, the OC particles are reduced by the
fuels, and the fuels are rst oxidized to form CO2 and H2O
products, and then reforming and the WGS with steam occur. In
the AR, the OC is oxidized to its initial state with O2. As can be
seen in Fig. 4(b) and (c), The CLR processes can be classied as
follows: (1) chemical looping reforming for syngas CLR(a); (2)
chemical looping reforming integrated with water oxidation for
pure hydrogen and syngas (CLR(w)); (3) steam reforming inte-
grated with chemical looping combustion for hydrogen, which
is also called chemical looping steam reforming (CLSR).
CLR(a) in its most basic form can be described as a combi-
nation process of the partial oxidation and reforming of fuels.
The partial oxidation process of fuels is exothermic, but the
reforming process is highly endothermic. To keep the
exothermic status, the ratio of the reforming to the partial
oxidation should be carefully adjusted and kept at a low value.
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The auto-thermal operating conditions for CLR(a) were studied
using Ni-based oxygen carriers by Ortiz et al.154 and the mass
and heat balances to determine the maximum H2 production
were analyzed. The results have shown that the molar ratio of
oxygen and methane should be higher than 1.2 to reach auto-
thermal conditions and the maximum H2 yield of about
2.75 mol H2 per mol CH4 was obtained. The main advantages of
CLR(a) as compared to steam reforming are (1) no external heat
to the reactor; (2) no CO2 emissions from external combustion;
(3) less steam to syngas production; (4) less catalyst required per
unit fuel feed; (5) high reaction rate; (6) less concern about
carbon formation, and etc.155 Besides the advantages mentioned
above, CLR(a) is also an interesting alternative technology for
syngas production for methanol and for Fischer–Tropsch
synthesis, which are important industrial processes where
synthesis gas with a (H2/CO) ratio of 2 is wanted. Such syngas
cannot be directly produced from steam methanol reforming.
CLR(w) technology could simultaneously generate pure
hydrogen and syngas separately. Similar to CLR(a), fuels are
partially oxidized by oxygen carrier in the FR to produce syngas,
but the reduced oxygen carrier is not oxidized by air in AR but by
steam to recover lattice oxygen and produce hydrogen in the
steam reactor (SR).156 Pure hydrogen can be obtained from the
steam reforming exit without any additional gas treatments
required by cooling and condensing the steam. However, the
oxygen carrier screening and performance optimization are
challenging. The reactions of CLR(w) can be illustrated as
follows:
Fuel reduction:
MmOn + CxHyOz ¼ MmOnk + H2 + CO
Steam oxidation:
MmOnk + H2O ¼ MmOnk+1 + H2
Air oxidation:
MmOnk+1 + O2 ¼ MmOn
where MmOn is an oxygen carrier, MmOnk and MmOnk+1 are the
corresponding reduced oxygen carriers with different reduction
degrees.
Hydrogen can be produced by a CLSR (Fig. 4(d)). The fuels
are partially oxidized by OC in the FR, but the reduced oxygen
carrier is not oxidized by air in AR but catalyzes fuels and steam
to produce hydrogen in the fuel and steam reactor. An AR using
air is completely added to oxidize the reduced OC. In this
process, the steam reforming process does not differ from the
conventional steam reforming in the way that the reactions take
place inside reactor by the reduced OC and the main products
are H2 and CO2.157
Protasova and Snijkers reviewed recent developments in OC
materials for hydrogen production by chemical looping
processes, and more than 900 materials have been investigated
as possible OCs candidates.158 A suitable OC for hydrogen
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Fig. 4 Chemical looping processes, AR: air reactor; FR: fuel reactor: (a) CLC; (b) CLR(a); (c) CLR(w); (d) CLSR.
production of CLSR includes the following characteristics: (1)
high oxygen transport capacity; (2) high reactivity with fuels to
CO2 and H2O; (3) stability of multi-cycle redox reactions; (4)
high resistance to agglomeration and sintering; (5), high
mechanical strength; (6) environmentally friendly and other
some characteristics such as low cost.
Table 6 lists different metal oxides such as Ni, Ce, Fe and Mn
oxides as OCs.159–179 NiO appears to be the most promising for
hydrogen production from the CLSR process due to its excellent
catalytic reforming and WGS reaction. However, pure NiO
presents very poor performance in multiple reductions and re-
oxidation due to nickel agglomeration. Therefore, the pure
NiO is commonly supported on some supports for high
stability. Diego et al. studied the reduction and oxidation of Ni-
based OCs in the CLSR processes, and the results showed that
NiO/NiAl2O4 in the oxidized state was active for oxygen trans-
fer.160 Once NiO is reduced, the reduced Ni presents excellent
catalytic properties for hydrogen production from steam
reforming. The Fe-based OCs have been studied as candidates
for hydrogen production in different reactor types. Luo et al.
reviewed the properties of different metal oxide particles
considering oxygen carrying capacity, reaction kinetics, ther-
modynamic properties, melting points, physical strength, and
environmental effects for chemical looping processes.54
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The studies have indicated that the incorporation of CeO2
into NiO–MCM-41 can effectively enhance the metal–support
interaction and promote the homogeneous distribution of Ni
and Ce to achieve a large Ce–Ni interface, and TEM images of
Ni-based OCs with Ce are displayed in Fig. 5.170 The hexagonal
structure can be clearly observed in Fig. 5 and the Ce promoter
was successfully embedded in the wall of the pores together
with Ni, and the results for the CLSR of ethanol demonstrated
that CeO2 has remarkable redox reactions and oxygen storage–
release capability by altering the state between Ce3+ and Ce4+,
and the mesoporous MCM-41 support improves the oxygen
transfer.170
The CLSR to produce hydrogen includes different reactions
such as OC reduction, steam reforming (SR), WGS and re-
oxidation of the reduced OC, and these reactions can be
accomplished in different types of reactors including the
alternating xed-bed reactor, dual uidized-bed reactors and
moving-bed reactors.180–182 The practical experiences have indi-
cated substantial operational and design challenges for the
uidized-bed and moving-bed reactors. Firstly, the scaling up of
the interconnected different systems of fuel and air reactors is
very complex, especially under the pressurized conditions
required for hydrogen production with high efficiency and
energy balance. Secondly, the external circulation of the OCs
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Table 6 Different typical OCs used in the chemical looping reforming process

Oxygen carrier Preparation method Fuel Reactor Reference

NiO/Al2O3 Coprecipitation Waste cooking vegetable oil Fixed bed 159–165

Wet impregnation Pyrolysis oil, glycerol Fluidized bed
Acetic acid
Ethanol/bio-oil aqueous fraction
NiO/NiAl2O4 Coprecipitation Glycerol Moving bed reactor 166
NiO/MgO–ZrO2 Freeze granulation Kerosene (biomass tar) Fluidized bed 167
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NiO/montmorillonite Ultrasound assisted cation exchange Bio-ethanol Fixed bed 168

NiO/SBA Wet impregnation Bio-ethanol Fixed bed 169
NiO/MCM-41 Wet impregnation Glycerol Fixed bed 170
NiO–CeO2/Al2O3 Wet impregnation Bio-ethanol Fluidized bed 171
CeO2/Al2O3 Wet impregnation CH4 TGA, xed bed 172
CeO2/LaFeO3 Deposition–precipitation CH4 Fixed bed 173
CeO2/ZrO2 Coprecipitation CH4 TPR 174
CeO2–Fe2O3 Coprecipitation CH4 TGA, xed bed 175–177
Mn3O4/MgZrO3 Freeze granulation Biomass gases Fluidized bed 178
LaFeO3 Hydrothermal synthesis CH4, bio-ethanol Fluidized bed 179

particles by cyclones and loop seals also increases the costs and
imposes operational limits. These challenges have led to the
development of alternative xed-bed reactors to avoid the need
to circulate OCs between different interconnected reactors.183,184
The alternating xed-bed reactor evaluated by our studies,185
which was used for CLSR, is a periodic cyclic two-step process
consisting of alternating feeds of fuels/steam and air. The main
advantages can allow much more compact system design and
simplify the process operation at the same time; the complex
redox reactions using different OCs for the CLSR process can be
easily evaluated. For this system, the gas products from the
CLSR of bio-ethanol using NiO/Al2O3, NiO/MMT, NiO/MCM-41,
and NiO/SBA-15 are shown in Fig. 6.185 Hydrogen production
was stable aer 240 s for all OCs. In the initial stage of the CLSR,
the CO2 product was dominant as compared to H2, CH4 and CO
products. Three different stages can be observed in the fuel
step: (1) OC reduction: in this stage, fuel was oxidized, the CO2
formation was dominant and the negative steam conversion
resulting from H2O formation was observed. (2) Coexisting
reactions of OC reduction, steam reforming and WGS: the
hydrogen product started to increase with time in this stage due
to the increase in the reduced OC. (3) Steam reforming and WGS
reactions: OCs have been totally reduced in this stage and
hydrogen and CO2 are mainly produced.

TEM profiles of fresh OCs for the CLSR of bio-ethanol (a) Ni@Al–MCM-41; (b) Ni/Al–MCM-41; (c) CeNi/Al–MCM-41; (d) HRTEM of CeNi/
Fig. 5
Al–MCM-41.

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As mentioned above, OCs undergo different phase transi- CO + H2O 4 CO2 + H2

tions during the reduction and re-oxidation of the CLSR
process. Since the reduction rate of OCs in the oxidation by fuels
is much slower than the rate of air oxidation of the reduced OC, CO2 sorption:
the designed residence time of the OC in the fuel step should be
longer than that in the air step. This sets constraints on reactor MeO + CO2 / MeCO3 (Me: CaO, Li2ZrO3, .)
parameters, especially in a xed-bed CLSR, where slow kinetics
will lead to very low utilization of the beds.
The SESR can ensure a high yield of hydrogen and also
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integrates a CO2 or H2 management scheme and gas clean up in

2.3 Sorption-enhanced reaction process
2.3.1 Sorption-enhanced steam reforming. In the past few
decades, the sorption-enhanced steam reforming (SESR)
concept by in situ CO2 removal has been extensively studied to
change the normal equilibrium limits of the water–gas shi
(WGS) reaction and increase feedstock and steam conver-
sion.186–190 It is a low-cost hydrogen production method due to
the reduction in the number of processing steps required for
subsequently separating products and decreasing reforming
temperatures for energy usage.191 The SESR with in situ CO2
removal can be described as follows:
Reforming:
CxHyOz / CO + H2
WGS:
the steam reforming process. In the SESR, the enhanced
hydrogen production has a very strong dependence on the in
situ CO2 removal by solid sorbents, and very fast sorption and
regeneration rates are required to allow for compact steam
reforming, WGS, CO2 capture and regeneration reactions. The
effectiveness of hydrogen production from the SESR and the use
of CaO-based sorbent mixed with steam reforming catalyst has
been demonstrated in our previous works;188–195 the total
concentration of CO2 in the product gas can be decreased to less
than 50 ppm under the most favorable conditions, and CaO
based sorbents have been tested to show strong affinity for CO2
sorption and capture with the capacity of 17.8 mol CO2 per kg.
Many sorbents including hydrotalcite, lithium metal oxide
and calcium oxide can achieve CO2 sorption. The advantage of
a low-cost sorbent is the most apparent. Some sorbents
including Li2ZrO3 and Na2ZrO3 are likely to be prohibitively
expensive for in situ CO2 sorption in SESR. It has been argued
that the performance of Li-based sorbents must be proven for

Fig. 6 Gas concentration with time for the CLSR cycle using different OCs: (a) NiO/Al2O3; (b) NiO/MMT; (c) NiO/MCM-41; (d) NiO/SBA-15.

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up to 10 000 cycles to be economically competitive with
sorbents derived from naturally occurring limestone.195 Thus,
dolomite has been extensively used for the SESR with in situ CO2
removal, and the main challenge is that its stability and capacity
for CO2 sorption decreases as the carbonation and regeneration
cycle number increases, which is mainly attributed to the
decrease in the reactive surface area as a result of sintering.
Another problem is that the sintering of catalyst at high calci-
nation temperatures above 850
C causes a decay in its activity
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when a mixture of catalyst and sorbent is used.196
The development of appropriate patterns by mixing sorbent
and catalyst for hydrogen production from the SESR has
received particular attention. In the case of physical mixing
particles of catalyst and sorbent, either the sorbent or the
catalyst needs to be recharged separately if the lifetimes of both
materials are not matched. It is inconvenient to remove/replace
sorbent or catalyst separately because the weight and size
distribution of both materials could be fairly similar in many
cases.197 Combining catalyst and sorbent in a single pellet of
hybrid state material seems to promote the mass transfer rate,
eliminate mass diffusional limitations, and simplify the process
of steam reforming and CO2 separation for various hydrocarbon
feedstocks. The Al-stabilized CaO–Ni hybrid sorbent–catalysts
were integrated into a single particle for the SESR and the
surface properties of the Ni/Al2O3 catalyst could be modied by
adding CaO due to the increase in the steam and carbon reac-
tion and the neutralization of the acidity of the support.198
Wu et al. studied hydrogen production by the SESR of
ethanol with sorption of CO2 by Ni–CaO–Al2O3 catalysts derived
from hydrotalcite-like compounds, and the results showed that
the catalysts demonstrated multifunctional activity for excellent
CO2 removal and catalytic steam reforming.199 Some studies
demonstrated that Ni–Zr–CaO and Ni–Ce–CaO in the SESR of
biogas can produce H2 of 90% and 85% purities, respectively,
and the CH4 conversion decreased signicantly over ve
cycles.200,201 The bi-functional materials with catalytic activity in
the steam reforming of biomass and CO2 sorption from iron
acetate and calcium acetate by mechanical mixing have indi-
cated that in the temperature range of CO2 sorption and steam
reforming, the activity of iron species and CaO can be limited by
Fe–Ca interactions as a consequence of the Ca2Fe2O5 phase
formation during catalyst preparation.201 The Fe-based/CaO
activity could be mainly dependent on the presence of Fe2O3
and the stability of Fe–Ca interactions.202 The bifunctional
catalyst prepared by extruding sol–gel-derived Ni/CaO–
Ca5Al6O14 powder was used in the SESR, and the results indi-
cated the positive effect of Ca5Al6O14 incorporation in the
catalyst.203 The Ni/CaO–Ca5Al6O14 extrudate consisting of
15 wt% (mass fraction) Ni, 61.7 wt% CaO and 23.3 wt%
Ca5Al6O14 provided high activity and stability for the SESR.
Radfarnia and Iliuta studied the CaO–Ni and CaO–Zr/Ni
bifunctional hybrid catalysts prepared by wet-mixing and soni-
cation for sorption-enhanced steam methane reforming, and
the results showed that the above 90% H2 yield obtained was
remarkably high as compared to traditional steam reforming.204
We also studied the synthesis and application of Ni-based
multifunctional catalysts with the addition of the CaO
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component to the Ni-based catalyst for hydrogen production
from the SESR in a xed-bed reactor.205 Non-isothermal and
isothermal experiments were performed to test the activities of
multifunctional catalysts for CO2 sorption ability. Recently,
a series of multifunctional catalysts, derived from lamellar
montmorillonite (MMT) via an ultrasound-assisted cation-
exchange method, was synthesized and the characterization
results showed that metal–support interactions, together with
Ni and Ca dispersion, is interrelated to the connement effect
of MMT.206
To date, only a limited number of studies on the continuous
operation of the SESR have been reported. The circulating
uidized-bed (CFB) reactors would be useful in the SESR due to
continuous cyclic regeneration of the catalyst and sorbent. The
SESR of methanol in CFB reactors with calcined dolomite and
Ni/NiAl2O4 was reported, and the system consisted of a reformer
and a regenerator, a riser, and two loop seals, and the results
showed that the methane conversion was drastically lower in
the CFB reactor than in the xed-bed reactor. There should be
an excess amount of catalyst in a CFB system relative to a xed-
bed situation.207
We reported the continuous H2 generation from glycerol by
the SESR using two moving-bed reactors, and a continuous ow
concept of catalyst and sorbent mixture for reaction/
regeneration by two slow moving-bed reactors was devel-
oped.193 High-purity hydrogen was produced in “one single
reactor” by integrating the steam reforming, WGS, and CO2
capture to improve the process efficiency and reduce capital
costs. A pure stream of CO2 produced in this system is quite
suitable for storage. The results showed that the moving-bed
reactor can well integrate the steam reforming, WGS and in
situ CO2 removal while eliminating the need for a WGS catalyst
under certain conditions, and the catalyst and sorbent can be
simultaneously regenerated in another moving-bed reactor at
the temperature of 900
C.
2.3.2 Sorption-enhanced chemical looping steam reform-
ing. The sorption-enhanced chemical looping steam reforming
(SE-CLSR) has several benets over current SESR technology as
it offers the novel integrated processes of SESR and CLSR for
producing high purity hydrogen in auto-thermal operation also
with carbon management incorporated in it, and the process is
characterized by the high potential of the combined two-step
looping concepts to reduce the heat demands of CaO-based
sorbent regeneration and attain low energy penalties. Rydén
and Ramos investigated the SE-CLSR of fuel (methane) and
their process involved three uidized bed reactors, namely,
a reforming reactor for oxidizing the methane, a calcination
reactor for the regeneration of sorbent, and the oxidation
reactor for the oxidation of OC by air.208 Antzara et al. studied
the feasibility of the energy efficient SE-CLSR process using
a mixture of a NiO-based OC supported on ZrO2, and a ZrO2-
promoted CaO-based sorbent and the experiments were per-
formed in a xed bed reactor.209 They conducted SE-CLSR
experiments with three NiO/CaO molar ratios of 0.2, 0.5 and
0.8, and the high NiO/CaO ratio reduced the performance of the
process in terms of energy requirements and H2 production.209
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In fact, an increase in the amount of sorbent to more than the
critical value did not improve the SE-CLSR performance.
We tested two methods for the SE-CLSR process including
two moving-bed reactors166 and an alternating xed-bed
reactor,3 and the results are shown in Fig. 7. In the moving-
bed reactor system, continuous hydrogen production was real-
ized by combining the oxidation, steam reforming, water–gas
shi, and CO2 capture using NiO-based OC and the CaO-based
sorbent for the in situ CO2 removal. The process was charac-
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terized by the simultaneous ow of the OC and sorbent mixture
using two slow moving-bed reactors. The effects of temperature
and the ratio of steam to carbon (S/C) on the production of
hydrogen were evaluated experimentally and the results in
Fig. 7(a) show that hydrogen above 93.6% can be produced auto-
thermally and the exothermic reactions of steam reforming can
be integrated into the endothermic reactions of air oxidation,
leading to superior kinetics and an energy efficient system. In
the alternating xed-bed reactor, OC reduction, hydrogen
production as SESR, N2 sweeping and air oxidation/
regeneration can be carried out step by step.166 Fig. 7(b) shows
the H2, CO2 and O2 concentrations from SE-CLSR before the
CO2 pre-breakthrough and air feeding stages for Ca/Ni ¼ 3.0
with multiple cycles, and high-purity hydrogen was also ach-
ieved during all the cycles, and the amounts of CO2 at the outlet
were very small. Carbon deposited on the OCs was combusted
in the air step. It can be concluded that the Ni-based OC and
CaO-based sorbent completely retain the intrinsic initial activity
or capacity in the SE-CLSR cycles, even under high temperature
Fig. 7 Gas products from the SE-CLSR cycle by Ni-based OC and CaO-based sorbent using different methods: (a) moving-bed reactor; (b)
alternating fixed-bed reactor.
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in the air step. The formation of acetaldehyde and water has
been reported previously during the CLSR process.3
In fact, in a typical cycle of the SE-CLR process, OC can play an
important role in providing heat for the sorbent calcination in
the air feed step and the results show that the enhanced oxygen
mobility can contribute to more heat release.210 As can be seen
from the SE-CLSR of glycerol in Fig. 8, during the CO2 pre-
breakthrough period, NiO reduction, steam reforming and in
situ CO2 removal occur simultaneously, leading to high purity H2
production during the fuel stage, and at the same time, there was
no additional external heating for about 20 min for the air stage.
As the Ni oxidation was gradually completed, the reactor
temperature decreased from 830 to 650
C, while the external
heating was switched on to regenerate the remaining CaCO3. In
this study, the fuel feed step was performed at 650
C, while the
air feed step was performed at 800
C because of the regeneration
of the sorbent. The gas hourly space velocity (GHSV) in the fuel
feed step was 250 h1, and in the air feed step it was 400 h1.210
The possible reaction pathway for hydrogen production from
ethanol with and without in situ CO2 removal was studied in our
previous work. In the case of CLSR without sorbent addition,
the formation of hydrogen, CH4, CO, CO2 and acetaldehyde was
clearly observed, indicating the occurrence of the bio-ethanol
dehydrogenation reaction:
absorbed H
C2 H5 OH ƒƒƒ! C2 H5 OH* ƒ! C2 H5 O*/H2 ;
CO2 ð þ CH4 ; CO; CH3 CHOÞ
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Fig. 8 Hydrogen production from the SE-CLSR of glycerol using Ni/ZrO2CaO and CeNi@ZrO2CaO. (a) Fuel feed step for Ni/ZrO2CaO; (b) air feed
step for Ni/ZrO2CaO; (c) fuel feed step for CeNi@ZrO2CaO; (d) air feed step for CeNi@ZrO2CaO ((1) dead time, (2) pre-breakthrough, (3)
breakthrough and (4) post-breakthrough).
The previous results have indicated the role of in situ CO2
removal by solid sorbent during the CLSR process and the
ethanol dehydration may be important:3
absorbed H2 O sorbent-CO2
C2 H5 OH ƒƒƒ! C2 H5 OH* ƒ! C2 H4 * ƒƒƒƒƒ! H2
The ethanol oxidation on solid OCs may be very fast as
compared with the reforming and WGS reactions, which is
indicated by the data from the NiO reduction to Ni.3 C–C carbon
bonds in the oxidation of ethanol with in situ CO2 removal are
rst broken and the ethanol molecules form CO*, which is
further oxidized to CO2 by OCs. The produced OH and CO
radicals can also react to form a bidentate formate (HCOO)
intermediate to CO2 and H2:
CO + OH / HCOO / 0.5H2 + CO2
In the hydrogen production from ethanol without in situ CO2
removal, the C–C carbon bond cleavage is avoided, resulting in
the formation of the CH3CHO by-product:
CH3CH2OH + 2OH / CH3CHO + 2H2O
In situ CO2 removal during the CLSR process can denitely
improve all the elemental reactions related to the production of
CO2, including the decomposition of the produced H2COO and
H2CO species at high temperatures to enhance the CLSR process:
H2COO / H2 + CO2
H2CO + H2O / 2H2 + CO2
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2.4 Multistage thermochemical processes
Although thermochemical processes including pyrolysis, gasi-
cation and steam reforming accept variable feeds, the varying
nature of the biomass feedstock leads to inconsistency in
conversion, product behavior and selectivity. The scale-up from
the laboratory scale to industrial pilot plants becomes difficult
with this inconsistency. Extensive work is needed to reveal the
correlation between the different kinds of biomass and ther-
mochemical methods. The introduction of multi-scale and
multistage methods by integrating technologies to improve the
performance with a high selectivity of desirable products will be
of great assistance to treat complex biomass with high efficiency
and environmental friendliness.
We demonstrated a 30 kg h1 scale system integrating
different thermochemical processes for bio-waste treat-
ment.211,212 As can be seen in Fig. 9(a), the system consists of
three sections, namely, a moving pyrolysis chamber that
compresses and heats the bio-waste in an oxygen-starved envi-
ronment, a slag combustion furnace, and a gasication
chamber that terminates the gaseous combustibles and
pollutants with additional steam or air injections and gas
cleaning. The gases and liquids produced can be used as
hydrogen and syngas, and the carbonaceous residue can be
burnt as fuel or safely disposed of since the heavy metals are
xed in the carbonaceous matrix. The industrial-scale processes
have been operated in Korea. The system was operated in
successive processes of pyrolysis, combustion, and gasication,
which may be promising in the treatment of all of the biomass.
Recently, we reported a system for continuous hydrogen
production by uidized-bed gasication (FBG) combined SESR
in Fig. 9(b).190 The system was also operated in successive
processes as follows: (a) A raw gas comprising CO, H2, CH4, and
total hydrocarbons (THC) was produced as well as a small
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amount of HCl by solid gasication. (b) Hydrogen production 2.5 Prospects of hydrogen production from biomass
from raw gas was carried out through two moving-bed reactors
Non-uniform knowledge of biomass pyrolysis and gasication
by SESR. (c) CaCO3 was formed and the catalyst with coke
among organizing institutions, local communities, nancial
deposits was simultaneously regenerated in the moving-bed
institutions, entrepreneurs, other stakeholders and consumers
reactor. (d) The mixture of catalyst and sorbent was carried
is the challenge to the wide dissemination of the use of
between two moving-bed reactors by the riser. In this system, we
biomass. These barriers can be overcome based on the extensive
used waste plastics as feed to test the feasibility; despite waste
exploitation of hydrogen production from biomass in different
plastics not being biomass, the system can be used in biomass methods. In some countries, rural communities do not readily
conversion. The results demonstrated that 88.4 vol% of
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accept biomass conversion technology and thus, combustion of

hydrogen was obtained at 818
C of FBG temperature with 706–
biomass is still used. In addition, some information related to
583
C of SESR temperature. With a decrease in the temperature
biomass conversion and operating parameters is oen not
of the SESR reactor, there is a decrease in CO2 concentration,
available to users. Also, biomass users are not well trained to
which can ensure high-purity H2 production. The results showed
deal with the reactors and technology costs are still very high.
that the CaO sorbent is capable of reducing CO2 and HCl to very
These restrict the acceptance of the use of biomass energy.
low levels at the temperatures ranging from 538–788
C.

Fig. 9 (a) Integrating pyrolysis, combustion and the gasification system; (b) fluidized-bed gasification combined sorption-enhanced steam
reforming system.

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A large investment can usually be associated with the
conversion of biomass to hydrogen, and this is also problematic
due to such factors as a lack of funds and policies. For example,
the principal capital costs for a conventional plant for hydrogen
production from biomass include site construction, biomass
collection and preparation units, pyrolysis, gasication, steam
reforming, WGS, PSA and other reactors, modied engine
genset and subsidies for the dissemination and commerciali-
zation of the technology. In addition, hydrogen use and elec-
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tricity distribution network are also needed. Such high budget
projects and high-risk technology are also major challenges in
developing countries. New technologies and methods for effi-
cient hydrogen production from biomass with low-cost are
being developed. The hydrogen production system efficiency
increases with an increase in unit capacity, due to the low
energy density and high distribution of biomass, and the SE-
CLSR with minimal procedures and high cycle efficiency may
be suitable for biomass.
2.5.1 Improving the performance of catalytic materials.
The supported nickel catalysts are widely used for most of the
catalytic reforming reactions, which are key processes for
generating hydrogen from biomass with very low cost. Li and
Gong reviewed the strategies for improving the performance
and stability of Ni-based catalysts for reforming reactions.213
They discussed three challenges facing the design of Ni cata-
lysts, including the preparation of highly dispersed supported
nickel catalysts with strong interactions of metal and support,
the promotion of the mobility of the surface oxygen for the yield
of desired products while promoting the removal of surface
carbon deposition, and the process intensication via the in situ
CO2 removal for a hydrogen-rich gas with low CO concentra-
tion.213 These approaches could also guide the heterogeneous
base-metal catalyst design, and a decrease in catalyst and
sorbent particle size is very important for improving the activity.
However, nanoclusters are apt to agglomerate and sinter under
catalytic reforming conditions of high temperatures, and
additionally, hydrogen production with a low concentration of
CO is a challenge using the nickel-based catalysts, which are not
so active in the WGS reaction.
Supports with high specic surface area were reconstituted
and noble metals were simultaneously incorporated to increase
the activity. The active and sustainable catalysts for hydrogen
production from the WGS reaction were obtained by noble
metals of less than 0.5 wt%. The study showed that trace
amounts of Pt can enhance both the intrinsic activity and the
sustainability of the Ni-/Cu-based catalysts by accelerating the
reduction–oxidation between Cu0 and Cu+ as well as by sup-
pressing the oxidative sintering of active Cu metal species by
hydrogen-spillover from Pt metal to Cu metal particles.214 In
fact, having enough data on the crucial steps in the steam
reforming reaction is important and should be obtained to
accurately predict the structures of the most efficient catalysts
that would speed the process with the least amount of
unwanted by-products.
Sorption-enhanced reaction processes with in situ CO2
removal using sorbents are among the most promising and
effective routes to enhanced hydrogen production. The most
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crucial step of this process is in situ CO2 removal. The control-
lable steering of product selectivity is thereby an obvious key
criterion for technical usage. Given the structural and chemical
complexity and diversity of the materials (catalysts and
sorbents) used, questions about the common elementary reac-
tion steps of the steam reforming reaction and in situ CO2
removal are imperative. For structurally complex materials,
a multifunctional catalyst is usually assumed, where the
participating catalytic entities (or the in situ created interface)
synergistically act in the catalytic reaction. The reactivity of
heterogeneous catalysts and sorbents is dictated by their atomic
congurations, electronic structure, and the interaction with
sorbents. The attrition performance and poisoning stability of
catalysts and sorbents in chemical looping processes are quite
crucial for their lifetimes and appear to be a signicant obstacle
to their applications. Group VI transition metals loaded on the
supports by high-temperature synthesis methods exhibit high
attrition resistance and mechanical strength. High-
performance computing to understand the reactivity of the
existing reactions and to develop design principles for new
catalysts and sorbents is important.
2.5.2 Improving energy input. The thermochemical
reforming process for hydrogen production includes some
highly endothermic chemical reactions and thus requires
a massive energy input. Different technologies including
chemical looping reforming with OCs have already been
developed to provide the energy input for a hydrogen produc-
tion system. As mentioned above, the SE-CLSR process has the
potential to be self-sufficient with heat; part of the oxidation of
fuels can be performed with O2 provided by the OC, and the
subsequent reoxidation of the OC produces heat. If a sufficient
amount of this heat is transferred from the air reactor to the
calcination reactor by the solids circulation, all the reactors
could be operated without heating or cooling, which would be
very elegant indeed. Abbas et al. performed the thermodynamic
analysis of the SE-CLSR process to study the main features, and
the results indicated that the SE-CLSR relied on the exother-
micity of both OC oxidation and the in situ CO2 capture by
carbonation onto a solid sorbent to provide the heat demand of
hydrogen (H2) production by steam reforming while generating
a nearly pure H2 product.215
Hydrogen production from steam reforming requires a heat
source to provide the necessary heat, and this could burn at
least 20% of the biomass feedstocks for energy supply. In order
to save the biomass resource, the use of concentrated solar
power for the conversion of biomass and other carbonaceous
materials has been investigated.216 The solar process produces
hydrogen and no part of the feedstock is combusted for process
heat. This also eliminates the need for upstream air separation
due to air combustion and reduces costly downstream gas
cleaning and separation requirements. The advantages of the
solar-driven steam reforming compared to the conventional one
include the following: (1) higher hydrogen output per unit of
feedstock, thanks to the solar power input, and (2) the avoid-
ance of product contamination and air separation units. The
solar-driven reactor and receiver technologies consist of directly
and indirectly irradiated processes. Directly irradiated
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processes can offer efficient heat transfer. The solar packed bed
reactor has been developed by some studies, and the device
employs indirect heat transfer to the packed bed of fuel through
a quartz window. This system provides simple operation that
enables high reliability and robust performance with a wide
range of feedstock. The directly irradiated uidized-bed reactor
employs a beam-down conguration to irradiate the top of the
bed, and is also limited by the rate of heat transfer through the
top of the bed and transported downward through the bed.
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Hydrogen production systems employing solar processes were
developed, and biomass-derived feedstock and steam were
introduced into the reactors; the heat transfer to the reactants
was driven by radiant and convective heat transfer through the
walls of the tubes, which were irradiated with the concentrating
solar reactor. A small-scale lab system was set up by the authors.
2.5.3 Exploring in situ H2 sorption. Very few studies have
been carried out on steam reforming or WGS to hydrogen
production with in situ hydrogen sorption or extraction. Fig. 10
shows hydrogen production from circulating uidized bed
gasication (CFBG) and water–gas shi (WGS) with in situ
hydrogen sorption by solid materials; the system can produce
almost pure H2 by materials desorption. The thermodynamic
analysis with in situ hydrogen sorption by minimization of the
Gibbs free energy was performed by Wang et al.217 The effects of
the pressure of 1–5 atm, the temperature of 600–1000 K, water to
glycerol ratio of WGR, 3–12 and fraction of H2 removal of 0–1 on
the reforming reactions and carbon formation were investi-
gated. The results suggested that in situ hydrogen separation
can substantially enhance hydrogen production from glycerol
steam reforming. It was indicated that atmospheric pressure
and a WGR of 9 are suitable for hydrogen production and the
optimum temperature for glycerol steam reforming with in situ
hydrogen removal is about 825–875 K. High temperature and
WGR are favorable to inhibit carbon production.
Metal hydride (MH) materials have been used in a number of
promising gas-phase processes such as hydrogen separation,
storage and recovery, thermally-driven compressors and heat
pumps, etc. These materials used in H2 sorption exhibit
Fig. 10 Hydrogen production from circulating fluidized bed gasification (CFBG) and water–gas shift (WGS) with in situ hydrogen sorption.
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a favorable combination of their properties, including revers-
ibility and selectivity of interaction with H2 under mild condi-
tions, and high volumetric density of hydrogen in the solid. The
H sorption oen requires high temperature and, correspond-
ingly, high hydride stabilities including LaNi4Cu, activated Mg,
Pd alloy, and Ti-based alloys and composites can be used.218
A challenging problem that hampers the MH application for
hydrogen sorption and separation from the gas mixtures con-
taining chemically-aggressive gases such as O2, H2O, CO, CO2,
etc., is the deterioration of MH performances. The gas impuri-
ties can easily react with MH surfaces in the formation of
surface compounds of oxides and hydroxides, carbonyls,
sulphides, which seriously limits hydrogen sorption. Most
likely, the impurities during the steam reforming deactivate the
MH surface centers responsible for H2 dissociation, resulting in
the retardation of the SESR. In fact, the removal of the impu-
rities during the steam reforming prior to H2 sorption in the
MH is not possible. The only approach for the SESR improves
the poisoning tolerance of MH by their structure and surface
modications.219 Hydrogen recovery and separation efficiency
mainly depend on the equilibrium pressure of sorption and the
study demonstrated that 94% of hydrogen recovery was ach-
ieved from the feed stream at 5.6 bar with hydrogen content of
59%.220 The latest developments of various types of MH,
comprising intermetallic compound complex hydrides, chem-
ical hydrides, and Mg-based alloys for solid-state hydrogen
storage applications have been discussed by Rusman and
Dahari.221
2.5.4 In situ hydrogen generation from liquid biomass-
derived feedstock. Due to the difficulties in hydrogen trans-
portation and storage, the small-scale applications for in situ
hydrogen generation and/or vehicular mobile station for the
reforming of liquid biomass-derived feedstock (as hydrogen
carrier) may have a promising future. Among all the liquids,
formic acid, methanol, ethanol, glycerol are some attractive
hydrogen sources and possess relatively high H/C ratios. Formic
acid and methanol, known as the main products of biomass
treatment, have been studied as the most promising and safest
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materials for hydrogen production. To apply these chemical
compounds in the technology of hydrogen energy, it is neces-
sary to develop sustainable methods with low cost to release H2
from them. The endothermic steam reforming reactions can
operate in the gas or aqueous phases and present more chal-
lenges and opportunities for future use in the release of H2; the
catalysts used are crucial. Onishi et al. reviewed the recent
progress in reversible hydrogen storage and production from
formic acid and methanol, and developed suitable catalysts that
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can maintain high activity and selectivity at low reforming
temperature.222
The in situ hydrogen production from a stable liquid
biomass-derived feedstock offers one way to ensure the safe
storage and transportation of hydrogen, and the catalysts based
on platinum, palladium, ruthenium, iridium, iron, copper,
nickel, etc. show promising performance. Ma et al. reported that
the platinum (Pt) atomically dispersed on a-molybdenum
carbide (a-MoC) enables low-temperature hydrogen production
through aqueous-phase reforming of methanol, with an average
turnover frequency reaching 18 046 moles of hydrogen per mole
of platinum per hour at low temperatures (190
C).223 As
mentioned above, high dispersion, small and narrow particle
size distribution and favored crystal planes are essential
elements for high-performance catalysts. The binding strength
with the support and anti-poisoning ability affect the lifetime
under real operation conditions. From the application
perspective, stability and durability are even more important
than activity. Cost is another key factor for catalysts. The
synthesis procedures for catalysts should be greatly simplied
using inexpensive and environmentally friendly agents for mass
production. The development of liquid biomass reforming for
in situ hydrogen production should also focus on process
intensication. SE-CLSR allows for the conversion of biomass to
high purity hydrogen in a single step without the use of prod-
ucts separation units. The large-scale implementation of this
technology will not be easy, but the potential gain should
outweigh the challenge.
3. Conclusions
Despite the various advantages of hydrogen production from
biomass, it is not being utilized at commercial levels due to the
existence of various challenges associated with the highly
distributed biomass-derived feedstock and the generic short-
comings of conversion technologies. The thermochemical
processes including pyrolysis, gasication and steam reforming
have great potential for biomass industrial implementation.
The conventional thermochemical processes are limited in
terms of H2 productivity and feedstock conversion due to the
thermodynamic boundaries of the reversible WGS reaction. The
Ni-based and noble metal catalysts exhibited catalytic and
thermal stability in high-temperature hydrogen production
processes. The sorption-enhanced steam reforming and chem-
ical looping steam reforming processes present the potential
intensied techniques in which the co-generated CO2 is selec-
tively removed in situ from the product gas mixture and high
purity hydrogen is produced by different reactor methods.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Sustainable Energy & Fuels
Herein, we analyzed effective catalyst modication strategies
and the application of oxygen carriers for chemical looping
processes can lead to auto-thermal hydrogen production and
CO2 capture. Some issues and challenges including improving
process performance and energy input as well as exploring in
situ H2 sorption and catalytic hydrogen generation in liquid
biomass-derived feedstock have been discussed. Based on this
review, we recommend chemical looping technologies for the
sustainable development of thermochemical hydrogen
production from biomass. Some of the barriers have been
identied as elementary and may be resolved with small efforts.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the Natural Science Foundation of
China [grant numbers 51876130, 91434129, 51476022,
51276032] and Joint project of the NSFC and the Royal Society
(RS) of UK (51311130126), and was supported by Capacity
Building Plan for some Non-military Universities and Colleges
of Shanghai Scientic Committee (No. 18060502600).
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