Energy Conversion and Management 165 (2018) 696–719

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Review

Evaluation of thermochemical routes for hydrogen production from T

biomass: A review
⁎
Aitor Arregi, Maider Amutio, Gartzen Lopez , Javier Bilbao, Martin Olazar
Department of Chemical Engineering, University of the Basque Country UPV/EHU, P.O. Box 644, E48080 Bilbao, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: H2 is regarded as one of the cleanest future energy carrier that can be generated from renewable sources and will
Biomass give rise to a reduction of CO2 emissions and environmental problems related to the use of petroleum based
Bio-oil feedstock. Thus, the thermochemical routes from biomass for sustainable H2 production compared to other
Gasification biomass treatment routes have a great potential for its industrial implementation. Gasification of biomass and
Pyrolysis
reforming of the bio-oil produced by biomass pyrolysis are the most researched pathways, although some studies
Reforming
dealing with supercritical water gasification and bio-oil gasification can also be found in the literature.
Hydrogen
Nevertheless, pyrolysis and in-line catalytic steam reforming strategy is gaining great attention due to its ad-
vantages compared to gasification and bio-oil reforming, especially those related to the optimization of each step
(pyrolysis and catalytic steps) and bio-oil feeding. This review deals with the different reactor configurations,
operating conditions and catalysts used in each process and compares the different alternatives in terms of H2
production, with emphasis placing on the advantages of the two-step strategy.

1. Introduction olefins and H2.

The urgent need to reduce the current energy dependence on fossil
fuels has promoted a large number of studies that focus on the devel-
opment of existing and new processes that use biomass based materials
as feedstock. Biomass derived fuels and chemicals can play a major role
in reducing CO2 emissions as well as become a strategic source in order
to guarantee energy competitiveness and sustainability [1]. However,
the establishment of a sustainable energy system should be based on
biomass exploitation policies that take into account land usage in order
to avoid competition with human and animal food and soil exhaustion
[2]. Accordingly, lignocellulosic biomass wastes and crops are regarded
as the most suitable alternative feedstocks [3].
Lignocellulosic biomass can be treated using several thermo-
chemical or biochemical processes in order to produce energy, bio-fuels
and bio-chemicals [4]. Thermochemical processes, such as gasification
and pyrolysis, are characterized by their scalability to industrial units,
where the syngas and bio-oil produced as intermediate products can be
subsequently converted into valuable fuels and chemicals [5]. These
processes have the advantage of being similar to the ones already im-
plemented in oil refineries, although need further development in order
to be cost effective compared to fossil fuels [6]. Fig. 1 displays the main
processes involved in a lignocellulosic thermochemical bio-refinery for
the production of valuable products such as automotive fuels, light
The global hydrogen production accounts for approximately 7.7 EJ/
year, which may rise to 10 EJ/year by 2050 [7]. The main applications
are related to ammonia production (51%), oil refining (31%), methanol
production (10%), and other uses (8%) [7] (Fig. 2). Furthermore, H2
market is expected to increase in the near future in a 5–10% per year,
basically due to its consumption in refineries for treating heavy oil
fractions and because of the projected demand in the transportation
sector or as energy vector [8].
The 96% of the H2 production technologies are based on non-re-
newable sources, with the most used processes being natural gas (48%)
and oil (30%) reforming, followed by coal gasification (18%) [9]. Only
4% of the H2 produced is obtained by means of water electrolysis [9]
(Fig. 3). Consequently, in order to meet the fossil fuel consumption and
CO2 release reduction targets, new sustainable processes derived from
renewable sources must be developed, such as the thermochemical ones
that use biomass as feedstock shown in Fig. 1.
Although each biomass conversion method has its own advantages
and disadvantages, it has been reported that the H2 production cost for
gasification and pyrolysis is similar, around $1.2–2.4/kg (slightly
higher for the former), which is actually between two and three times
higher than the cost for CH4 steam reforming [10]. Therefore, the
choice of the most adequate one needs a thorough assessment of the
economic aspects in the area where it has to be implemented, as well as

⁎
Corresponding author.
E-mail address: gartzen.lopez@ehu.eus (G. Lopez).

https://doi.org/10.1016/j.enconman.2018.03.089
Received 24 January 2018; Received in revised form 27 March 2018; Accepted 28 March 2018
Available online 06 April 2018
0196-8904/ © 2018 Elsevier Ltd. All rights reserved.
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

Nomenclature LHSV liquid hourly space velocity

RHC rice husk char
BCC brown coal char S/B, S/C, S/CH4 steam to biomass ratio, steam to carbon ratio,
BTX benzene, toluene, xylene steam to methane ratio
CFB circulating fluidized bed T, TP, TG, TR temperature, pyrolysis temperature, gasification tem-
CNT carbon nanotube perature, reforming temperature
DFB dual fluidized bed WGS Water Gas Shift
DME dimethyl ether WHSV, WBHSV weight hourly space velocity and bio-oil weight
GHSV, GC1HSV gas hourly space velocity and gas hourly space ve- hourly space velocity
locity in equivalent CH4 units

Fig. 1. Schematic representation of the main processes involved in a lignocellulosic thermochemical bio-refinery.

the availability of biomass resources, and the existence of large cata-
lytic conversion units that can treat the intermediate products. These
aspects allow making the choice between centralized processes, in
which the final product is produced at the same unit where the biomass
is primarily converted, or decentralized processes, in which the inter-
mediate product (such as the bio-oil derived from flash pyrolysis) can
be easily transported to catalytic conversion units.
The mostly studied and developed technologies for H2 production
are steam gasification [11–18] and the reforming of the bio-oil pro-
duced in biomass flash pyrolysis [19–25]; however, the biomass fast
pyrolysis and in-line reforming of the volatiles has recently gained at-
tention, with several studies published in the literature over the last
years [26–31]. In this scenario, this one aims at reviewing the pyrolysis
and in-line reforming strategy and comparing this technology with the
main thermochemical biomass conversion processes for H2 production.
2. Biomass steam gasification
Biomass gasification has been widely studied during last decades,
which is due to the fact the gaseous product can be directly used as fuel
or as an intermediate product for the large scale production of fuels and
chemicals [32–36]. The process characteristics entail establishing ga-
sification plants in the regions where biomass is available, because the
costs for the transportation of the raw material or the formed gaseous
products would be excessive [37]. Fig. 4 shows a schematic

Fig. 2. Global consumption of hydrogen [7]. Fig. 3. Current sources of hydrogen [9].

697
A. Arregi et al.
Fig. 4. Schematic representation of the biomass steam gasification process for hydrogen production.
representation of the steam gasification process.
Biomass gasification typically takes place at temperatures between
700 and 1200 °C, using air, oxygen, steam or their mixtures as gasifying
agent, which leads to a gaseous product mainly formed by H2, CO, CO2,
CH4 and other hydrocarbons. The use of steam enhances H2 formation
and produces a high heating value gas with no nitrogen. Although the
highly endothermic nature of steam gasification increases energy costs
compared to air gasification, it avoids the need for a costly oxygen
separation process [10].
The main steps involved in biomass steam gasification are drying,
pyrolysis, heterogeneous char gasification and homogeneous reactions
undergone by pyrolysis volatiles, i.e., reforming, cracking and Water
Gas Shift (WGS) reactions. These gasification steps have been sum-
marized in Fig. 5.
In the drying process, the evaporation of the moisture contained in
the biomass takes place, which is usually a fast step and occurs at low
temperatures, with its influence on the overall gasification process
being limited. In the pyrolysis process, biomass is thermally degraded to
yield gases, condensable products and char. The liquid product or pri-
mary tar formed in biomass pyrolysis is a complex mixture of oxyge-
nates made up of alcohols, furans, ketones, saccharides, acids, phenols
and so on [38–40]. However, these compounds are in general of marked
unstable nature, and under gasification conditions are rapidly cracked
or reformed, or evolve towards more stable aromatic structures, such as
secondary and tertiary tars [41,42]. The tar contained in the syngas is a
serious problem for its valorisation, given that it is polymerized or
condensed below 300 °C, and so may cause fouling, corrosion and
Fig. 5. Biomass steam gasification reactions and steps involved.
698
Energy Conversion and Management 165 (2018) 696–719
blocking of pipes, heat exchangers and particle filters [15,43]. There-
fore, the improvement of tar cracking performance is one of the greatest
challenges in the gasifier design [44], with the increase in residence
time being an objective usually pursued. However, total elimination of
the most stable tertiary tars requires temperatures of around 1250 °C
and residence times above 0.5 s [42].
The char formed in the pyrolysis step is gasified by steam gasifica-
tion and Boudouard reactions. However, the rate of both reactions is
low, even at typical gasification temperatures. Thus, char gasification
represents the limiting step in biomass gasification and an adequate
reactor design requires a suitable residence time in order to attain high
char conversion efficiency [45–47].
Therefore, biomass steam gasification products are as follows: a
gaseous fraction typically composed of 30–50 vol% of H2, 25–40 vol%
of CO, 8–20 vol% of CO2 and 6–15 vol% of CH4; a heavier fraction (tar),
which consists of a complex mixture of aromatic hydrocarbons; and a
solid fraction derived from the biomass that has not been totally gasi-
fied. The yields and properties of these products are influenced by a
number of factors, with the most important ones being reactor config-
uration (which determines the contact mode, and therefore mass and
heat transfer rates), biomass initial characteristics, operating conditions
(such as temperature and steam to biomass ratio), and the use of cat-
alysts [10,36,48]. Table 1 shows a summary of several biomass steam
gasification research papers, in which the effect of the aforementioned
variables is studied. For the sake of clarity, studies using only steam as
gasifying agent have been analyzed. The discussion of the results re-
ported is detailed below.
 Table 1
Studies involving different strategies, feeds, catalysts and operating conditions, and main results obtained (maximum H2 production) reported in the literature for biomass steam gasification.
Reactor configuration Kind of study Biomass Operating conditions Catalyst H2 production Gas yield Tar content Ref.
A. Arregi et al.

(wt%)a (Nm3/kgbiomass) (g/Nm3)

Updraft fixed bed Demonstration plant Pallets wood chips T = 750 °C; S/B = 1.4–2.7 None 6.4 1.3 60 [11]
(1.2 tn day−1)
Downdraft fixed bed Bench scale Pine wood T = 850 °C None 6.2 1.4 – [49]
Fixed bed Laboratory scale (5 g min−1) Pine sawdust T = 600–900 °C; S/B = 1.2 Primary: Dolomite 7.3 1.6 2.5 [50]
Fixed bed Laboratory scale (5 g min−1) Pine sawdust T = 600–900 °C; S/ Primary: Dolomite 11.2 2.53 n.d. [51]
B = 0–2.8
Fixed bed + fixed bed reformer Bench scale (1 kg h−1) Sawdust Gasifier: T = 800 °C; S/ Secondary: nano-Ni–La–Fe/γ- 12.1 2.4 0.08 [52]
B = 0.6 Al2O3
Secondary reactor:
T = 750–850 °C
Fluidized bed Bench scale (1–2.5 kg h−1) Waste wood T = 900 °C; S/B = 1 Silica sand 5.9 1.22 12.5 [53]
Entrained flow Pilot plant (0.67 kg h−1) Dealcoholised marc of grape T = 1050 °C; S/ None 1.3 0.6 – [13]
B = 1.02–3.19
Rotary kiln Pilot plant (3–4 kg h−1) Palm shells T = 850 °C; S/B = 0.6–1 None 3.7 0.8 1.2 [14]
Plasma Pilot plant (10 g) Distillers grains T = 600 °C; S = 1–3 ml/min None 53 vol%b – – [54]
Free fall Laboratory scale (4 g min−1) Legume straw and pine sawdust T = 750–850 °C; S/B = 0–1 Primary: Limestone; Olivine; 5.2 1.2 3.7 [55]
Dolomite
External circulating concurrent moving Laboratory scale Pine sawdust T = 650–800 °C; S/ Primary: Calcined olivine 9.5 2 0.7 [56]
bed (0.24 kg h−1) B = 0–1.2
Conical Spouted Bed Bench scale Pinewood sawdust T = 800–900 °C; S/B = 0–2 None 3.3 0.96 142 [57]
(0.75–1.5 g min−1)
Conical Spouted Bed Bench scale (1.5 g min−1) Pinewood sawdust T = 900 °C; S/B = 1 Primary: Olivine; γ-Alumina 4.4 1.15 22.4 [15]
Circulating Spout-Fluid Bed Bench scale (1.5 g min−1) Rice straw T = 860–900 °C; S/B = 2 Primary: Limestone; 5.5 1.25 2.55 [58]
Dolomite; Synthetic 0–20%

699
CaO/Al2O3
Bubbling fluidized bed Pilot plant (4 kg h−1) Pinewood chips T = 750–780 °C; S/ None 6.9 1.4 38 [59]
B = 0.53–1.1
Bubbling fluidized bed Bench scale (8 g min−1) Miscanthus X Giganteus T = 800, 900 °C; S/B = 1 Primary: Olivine; 3.9 wt% Ni/ 7.8 1.7 5.9 [60]
olivine
−1
Bubbling fluidized bed Bench scale (0.3 kg h ) Almond shells T = 700–820 °C; S/ Primary: Dolomite; Olivine 9.4 1.9 0.6 [61]
B = 0.5–1
−1
Bubbling fluidized bed Bench scale (5–8 g min ) Almond shells T = 800–830 °C; S/ Primary: 10 wt% Fe/olivine 6.6 1.4 1.4 [62]
B = 1.15–1.3
Bubbling fluidized bed Bench scale Almond shells T = 820 °C; S/B = 0.72 Primary: Olivine (0.9)/ 7.3 1.58 2.13 [63]
(6.8–11.62 g min−1) dolomite (0.1)
Bubbling fluidized bed + catalytic filter Bench scale (5–8 g min−1) Almonds shells Gasifier: T = 808–813 °C; S/ Primary: Olivine 14.5 2.9 0.15 [64]
B = 1.03–1.28 Secondary: Al2O3 filter; NiO
Filter: T = 740 °C (47 wt%)/MgO-Al2O3 filter
Bubbling fluidized bed + fixed bed Bench scale (9 g min−1) Pine sawdust Gasifier: T = 750–780 °C; S/ Secondary: Calcined – 2.3 0.5 [65]
reformer B = 1.1 dolomite, calcite and
Secondary reactor: magnesite; Ni/MgAl2O4
T = 740–880 °C
Bubbling fluidized bed + fixed bed Bench scale (0.3 kg h−1) Almond shells Gasifier: T = 770 °C; S/B = 1 Primary: Calcined dolomite 11.0 1.98 0.2 [66]
reformer Secondary reactor: Secondary: Calcined
T = 665–830 °C dolomite; Ni catalyst
Bubbling fluidized bed + tubular Bench scale (10 kg h−1) Pelletized mixture of hard and soft Gasifier: T = 615 °C; S/B = 2 Secondary: ∼25 wt% NiO/ 50 vol%b – 0.084 vol%c [67]
cracker + bubbling fluidized bed woods Thermal tubular cracker: K2O/Al2O3
reformer T = 775 °C
Secondary reactor:
T = 775–875 °C; S/C = 4.5
(continued on next page)
Energy Conversion and Management 165 (2018) 696–719
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

2.1. Reactor configurations

[68]

[69]

[70]

[71]

[72]
[73]
[74]
[75]
Ref.

Biomass gasification is an extensively studied process, with a rela-

Tar content

tively high technological development [76]. Therefore, a wide range of

(g/Nm3)

reactor configurations have been used, such as fixed bed (updraft and

1.25

10.3

0.02
downdraft), fluidized bed, entrained flow, spouted beds, rotary kiln or
n.d.

122
10

44
5
plasma reactors [34–36,77–79].
(Nm3/kgbiomass)

The assessment of the effect of reactor configuration on the results

shown is not straightforward, due to different scale, uneven biomass
Gas yield

composition, operating conditions and gas and tar analysis procedures

0.82
0.85
used. However, analyzing the non-catalytic gasification experiments
2.2
1
–

–
carried out in updraft fixed bed [11], entrained flow [12,13], rotary
kiln [14], plasma [54], free fall [55], fluidized bed [59,70] and spouted
H2 production

bed [57,80,81] reactors, and although all reactor configurations lead to

53.7 vol%b

48.7 vol%b

H2 productions between 1.3 and 8.5 wt% (with the average value being
51 vol%b

45 vol%b
(wt%)a

4.6 wt%), with tar concentrations in the 4–140 g/Nm3 range, it can be
0.76
3.9

1.8
3.6

concluded that fluidized bed reactors are suitable for the biomass steam
gasification process because high H2 productions (6.9 wt%), gas yields
Primary: Olivine and 3.7 wt%
Primary: Limestone; Olivine;

Secondary: NiO (% 16–40)/

(around 1–1.4 Nm3/kgbiomass), H2 concentrations (> 50 vol%) and low

Secondary: 6.6%NiO/3.4%

MgO/Al2O3 honeycomb.

tar ones (20–80 g/Nm3) are obtained [59,70].

MgO/4.0% K2O/Al2O3

Fe-olivine; Ni-olivine

Ni/olivine mixtures

Furthermore, the scale up of this technology has been satisfactorily

Primary: Olivine

Primary: Olivine

accomplished, solving the heat supply problems by means of the dual

fluidized bed (DFB) configuration, which is a combination of two
Silica sand
Silica sand

bubbling and/or circulating fluidized beds, with one of them acting as

Catalyst

None

gasifier and the other as char combustor [82]. The gasifier is blown
with steam, obtaining a syngas with high H2 content, whereas the char
Secondary reactor: T = 900 °C
Gasifier: T = 700 °C; S/B = 1

is burnt in the combustor in order to provide heat to the system

[18,75,83,84]. However, it has been reported that the heat provided by
Gasifier: T = 850–900 °C
Thermal tubular cracker:

T = 815 °C; S/B = 0.84

T = 820 °C; S/B = 1.5

Operating conditions

char combustion may not be enough, and therefore additional fuel must
T = 820 °C; S/B = 2
T = 650–870 °C; S/

T = 750–850 °C; S/

T = 750–900 °C; S/

Secondary reactor:

be used in order to meet heat specifications [85]. The pioneering DFB

T = 850–900 °C

biomass gasifier was developed by Dr. Kunni, in order to gasify muni-

B = 0.5–1.2

B = 0.3–0.9

B = 0.3–0.9
T = 850 °C

cipal solid wastes [85]. Currently, the vast majority of the biomass
steam gasification demonstration or commercial scale plants are based
on this technology [86]. Thus, among the DFB gasification technologies
reviewed by Göransson et al. [83], the ones that must be remarked due
Willow wood chips; Straw; Wood/

to their capacity are SilvaGas™ plant in USA (40 MWth), which consists
of two circulating fluidized beds, 32 MWth GoBiGas plant in Sweden,
Wood pellets and chips; Bark;

15 MWth Blue Tower plant in Germany, Güssing FICFB plant in Austria

(8 MWth) and Charlmers plant in Sweden (2 MWth), the four based on a
bubbling fluidized bed as gasifier and a circulating fluidized bed as
Pine wood pellets

combustor.
straw mixtures

Sewage sludge
Wood pellets

Wood pellets

Wood pellets

Wood chips
White oak
Biomass

2.2. Effect of biomass characteristics

The main biomass characteristics affecting gasification performance

are biomass type, moisture content and particle size [10]. Regarding
Pilot plant (15–22.5 kg h−1)

Full scale (282–300 kg h−1)

Pilot plant (3.6–5.4 kg h−1)

biomass type, special attention has to be paid to the ash content as, on
Pilot plant (15 kg h−1)

Pilot plant (30 kg h−1)

Pilot plant (25 kg h−1)

the one hand, high ash content biomasses lead to high char yields and,
Tar concentration in the gas (vol%). n.d. Not detected.

on the other, ash leaves the gasifier in the form of micron size parti-
Laboratory scale

culate matter, which has to be removed downstream by means of gas

Kind of study

Pilot plant

cleaning processes [87]. Wei et al. [55] compared legume straw and
pine sawdust gasification performance in a free fall reactor, with the
H2 production defined as gH2/100 gbiomass.

former having a higher ash content. Although legume straw lead to a

lower gas yield and higher char and tar ones than pinewood, the H2
H2 concentration in the gas (vol%).

content in the gas was higher, being 50 vol% for legume straw and
bed + fixed bed reformer
cracker + bubbling fluidized bed

44 vol% for pinewood at 850 °C, which correspond to a H2 production

Bubbling fluidized bed + tubular

of 5.2 and 4.5 wt%, respectively.

Gasifiers can handle biomasses having moisture contents below
35 wt%, although most of them are designed for a 10–15 wt%. The
main drawback of raw materials with high moisture contents lies in the
Reactor configuration
Table 1 (continued)

Dual fluidized bed

Dual fluidized bed

Dual fluidized bed

bed
bed
bed

loss of gasification efficiency due to the reduction of operation tem-

perature [86]. Pfeifer et al. [69] observed for a moisture content in the
fluidized
fluidized
fluidized
fluidized
reformer

original biomass between 6 and 40 wt% that H2 concentration in the

gas increased as the moisture content was higher, although the differ-
Dual
Dual
Dual
Dual

ences were not considerable (from 34 vol% for a moisture content of

b
a

6 wt%, to 38 vol% for 40 wt%).

700
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

The biomass particle size has a great influence on the gasification
performance. Thus, smaller particles provide larger surface areas per
unit mass, which increases heat and mass transfer, and therefore gasi-
fication rates, leading to high gas yields with high H2 concentrations
and low tar contents [10,86]. However, reducing biomass particle size
below 1 mm increases exponentially energy consumption [86]. There-
fore, it is essential to develop a versatile gasification technology that
may handle large biomass particles without compromising heat and
mass transfer phenomena. Thus, particle size hardly affects gasification
when the studies are carried out using reactor configurations with high
heat transfer rates, such as the one performed by Michel et al. [60] in a
bubbling fluidized bed by feeding wood pellets with a size between 6
and 8 mm and Erkiaga et al. [57] in a conical spouted bed with particles
in the 0.75–4 mm size range. The latter configuration has been proven
to be especially suitable for handling different types of residues without
operational problems, such as plastics [88,89] and biomass/plastic
mixtures [90].
2.3. Operating conditions
Gasifier temperature and steam to biomass (S/B) ratio are the
parameters that need to be carefully selected and controlled for im-
proving gasification performance [10,86]. Temperature has a great
impact on gas and H2 yields, due to the endothermicity of the reactions
involved (pyrolysis, steam reforming, Boudouard and char steam gasi-
fication reactions). Furthermore, an increase in temperature hinders the
WGS reaction equilibrium. Overall, at higher temperatures a gaseous
product with higher H2 and lower CO and CH4 concentrations is ob-
tained, as well as a reduced tar content and char yield.
[53]. In addition, tar formation and char yield are hindered due to the
enhancement of reforming and gasification reactions. However, the S/B
ratio has to be optimized for each process because an excess of steam,
on the one hand, does not entail an improvement in the quality of the
product gas and, on the other hand, it considerably increases the energy
consumption of the process [86]. Fig. 7 shows some of the studies in
which the effect of steam to biomass ratio on H2 production has been
studied.
Umeki et al. [11], operating in an updraft fixed bed gasifier with a
feed rate of 1.2 t/day, observed that H2 production passed through a
maximum value of 6.4 wt% at S/B = 2.15. However, tar content in-
creased from 50 g/Nm3 at S/B = 1.4 to 100 g/Nm3 at S/B = 2.7. In the
experiments carried out by Iovane et al. [14] in a rotary gasifier with S/
B ratios in the 0.6–1 range, it was concluded that gas yield was hardly
affected by this parameter (remaining at a value of around 0.8 Nm3/
kgbiomass), while the H2 produced increased from 2.9 to 3.7 wt% for S/
B = 1. Gil et al. [59] and Göransson et al. [70], operating in a fluidized
and dual fluidized bed, respectively, observed that the S/B ratio had a
positive effect in both H2 concentration and tar content, with the op-
timum value being the highest one studied (1.1 for the former and 0.9
for the latter). Thus, the H2 concentration and tar contents at the se-
lected operating conditions were 55 vol% and 38 g/Nm3 [59] and
51 vol% and 10 g/Nm3 [70].
In the studies where dolomite and olivine were used as in-bed cat-
alyst, S/B ratio also had a positive effect on gasification performance.
Thus, Luo et al. [51], operating in a free fall reactor at 900 °C, observed
that even with the lowest S/B ratio of 0.73, tar was totally cracked and
that the highest H2 production was obtained with a S/B ratio of 2.1
(11.2 wt%).

2.3.1. Temperature
2.4. Catalysts
Most of the authors that studied the influence of temperature on
product yields and compositions agreed that a more severe operation
The syngas that leaves the gasification reactor requires several
led to an improved gasification performance, minimizing the tar con-
complex and costly purification steps in order to meet specifications for
tent, as shown in Fig. 6. Thus, in the non-catalytic study performed by
the downstream catalytic conversion processes, which are designed for
Wei et al. [55], the maximum H2 productions of 5.2 and 4.5 wt% were
removing the particulate matter (micron size char and ash), the N, S
obtained at the highest temperature of 850 °C for legume straw and
and Cl containing gaseous compounds (such as NH3, HCN, H2S and
pinewood, respectively. At this temperature, tar content was mini-
HCl) and specially the tar components present in the gas
mized, with a reduction from 62.8 to 3.7 g/Nm3 for legume straw and
[42,43,97–101]. Many strategies have been developed in order to ob-
from 45.6 to 6 g/Nm3 for pinewood, in the 750–850 °C temperature
tain a tar free (or low tar content) syngas, and they can be classified into
range. Erkiaga et al. [57] operating in a conical spouted bed reactor,
primary processes, which hinder tar formation in the gasifier, or sec-
concluded that gas yield and H2 concentration increased from
ondary processes, which imply a cleaning of the produced syngas.
0.73 Nm3/kgbiomass and 28 vol% at 800 °C to 0.96 and 38 at 900 °C,
respectively (which corresponds to an increase in the H2 production
from 1.8 to 3.3 wt%).
Similarly, the utilization of a catalyst in the gasification bed resulted
in an analogous effect of temperature on gasification operation. Luo
et al. [51] using dolomite as in bed catalyst in a fixed bed observed the
maximum H2 production of 11.2 wt% at the highest temperature stu-
died (900 °C), and no tar was detected under those conditions. Olivine
also leads to a similar trend with temperature, with the best results
being observed at the highest temperatures studied. Thus, Rapagná
et al. [61] and Michel et al. [16], gasifying almond shells and mis-
canthus in a fluidized bed, attained the maximum gas yields of 1.9 and
1.2 Nm3/kgbiomass and H2 productions of 9.4 and 4.9 wt%, at 820 and
880 °C, respectively. Tar contents were also found to be minimum at the
highest temperature with a value of 0.6 g/Nm3 for the study with al-
mond shells [61]. Therefore, gasification temperature will be limited by
the economics of the process because higher temperatures lead to
higher H2 productions and a gas with lower tar content.

2.3.2. Steam to biomass ratio

Steam to biomass ratio (S/B) also plays a crucial role in gas and H2 Fig. 6. Effect of gasification temperature on tar content in the gaseous product
yields. As S/B is increased, the WGS reaction and steam reforming ones stream. Wei et al., 2007 [55]; Goransson et al., 2011 [70]; Rapagnà et al., 2000
are favoured, thus leading to a higher gaseous yield, i.e., H2 and CO2 [61]; Carpenter et al., 2010 [91]; Koppatz et al., 2011 [18]; Erkiaga et al., 2014
formation is promoted and the one of CO and hydrocarbons is reduced [57]; Zhang and Pang, 2017 [73]; Wang et al., 2017 [92].

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A. Arregi et al.
Amongst the primary methods for tar elimination the design of the
gasifier is usually the first measure adopted. This is the case of fluidized
bed gasifiers whose flexible design allows for several modifications
aimed at improving tar cracking efficiency, which are as follows: in-
crease in residence time in the freeboard region [59], location of the
feeding zone [102,103] or secondary air injections in the case of air
gasification [104].
Catalytic gas cleaning methods for tar removal have the advantage
of an additional increase in gas and H2 yields, due to the enhancement
of tar cracking and steam reforming reactions. The most widely used
catalysts in steam gasification studies are natural minerals, such as
dolomite or olivine, and Ni based catalysts [105–108]. The former have
the advantage of their availability and low cost, whereas Ni based
catalysts have a high activity for tar cracking and reforming [109].
They can be used as primary catalysts, directly in the gasifier, or as
secondary catalysts in downstream catalytic processes. Fig. 8 shows the
tar contents obtained with different catalysts by several authors.
2.4.1. Primary catalysts
Dolomite has been widely used as primary catalyst due to its per-
formance and availability [41]. Thus, Wei et al. [55], tested in a free fall
reactor the performance of different naturally occurring catalysts, such
as limestone, olivine and dolomite, finding that dolomite was the one
that led to the lowest tar yield, accounting for a tar content in the gas of
11.2 g/Nm3 for legume straw and 9.4 g/Nm3 for pinewood at 800 °C.
However, dolomite undergoes a severe attrition, especially in fluidized
beds, which has boosted the utilization of other catalysts with higher
mechanical resistance.
Olivine has gained attention as primary catalyst in fluidized or high
solid circulation beds due to its high mechanical strength, together with
its good tar cracking activity, as mentioned previously. Koppatz et al.
[18] tested the performance of olivine as primary catalyst in a 20 kg/h
dual fluidized bed reactor, observing that H2 production and gas yield
were increased from 3.1 to 4.2 wt% and 0.99 to 1.13 Nm3/kgbiomass,
respectively, when olivine was used instead of silica sand and that the
tar content in the gas was reduced from 18.9 to 11 g/Nm3. Erkiaga et al.
[15] compared the influence of olivine and γ-alumina addition in a
conical spouted bed reactor, and observed that both catalysts were
active for tar cracking, i.e., tar was reduced from 142 with sand to 30.1
and 22.4 g/Nm3 with olivine and γ-alumina, respectively.
In order to improve the tar cracking activity of olivine, Rapagná
et al. studied the effect of Fe [62] and Ni [60] addition in a fluidized
bed. An addition of a 10 wt% of Fe increased H2 production from 3.5 to
6.6 wt% and gas yield from 1 to 1.4 Nm3/kgbiomass and reduced tar
content from 3.6 to 1.4 g/Nm3, compared to olivine. Furthermore, these
authors did not observed any coke deposition during the runs [62]. The
addition of 3.9 wt% Ni to the olivine catalyst improved gas production,
from 1 to 1.7 Nm3/kgbiomass and also H2 production, from 3.4 to 7.8 wt
% at 800 °C, with olivine and Ni/olivine, respectively. Tar production
was also reduced by three times, leading to a content of 5.9 g/Nm3 with
the Ni/olivine catalyst [60].
2.4.2. Secondary catalysts
Regarding secondary gas treatments, Delgado et al. [65] corrobo-
rated that Ni based catalysts are more active for tar elimination than
natural minerals. Thus, in the experiments performed in a fluidized bed
gasifier followed by a fixed bed downstream reactor, although both the
dolomite and the commercial Ni catalyst used reduced tar content from
9 g/Nm3 to less than 0.5 g/Nm3, the Ni based catalyst required a lower
operation temperature (740 vs. 800 °C), and lead to a higher gas yield
(2.3 vs. 1.8 Nm3/kgbiomass) and H2/CO ratio (2.55 vs. 2.2) than dolo-
mite. Rapagná et al. [66] also compared dolomite and Ni based catalyst
for tar removal in a similar reactor configuration, concluding that the
latter was more active because it lead to an increase in gas yield from 1
to 1.98 Nm3/kgbiomass and reduction in tar content from 100 to 0.2 g/
Nm3, obtaining a H2 production of 11 wt% at 830 °C. However, a slight
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Energy Conversion and Management 165 (2018) 696–719
deactivation caused by coke deposition was observed after 2 h of op-
eration.
Accordingly, efforts are being directed to the development of active
and coke resistant Ni based catalysts. As observed in Table 1, most of
the secondary catalysts are based on Ni as active phase, Al2O3 as sup-
port and a promoter such as Mg, Ca, K or La. Pfeifer and Hofbauer [75]
operated in a dual fluidized bed and secondary downstream fixed bed
reactor using 16–40 wt% NiO/Al2O3 monolithic catalysts, doped with
MgO or K2O. Tar content decreased from 8.5 to 0.02 g/Nm3 with the
highest Ni loading in the catalyst, and a gas with a H2 content of 45 vol
% was produced at 900 °C. Regarding catalyst deactivation, a tem-
perature increase from 850 to 900 °C reduced coke content by 25%.
The catalytic tar elimination performance of these catalysts can be
further enhanced by the utilization of a primary catalyst in the gasifier
bed. For example, Di Carlo et al. [17] gasified hazelnut shell in a flui-
dized bed of olivine particles and reformed the produced gas in a fixed
bed made of a Ni-mayenite (Ca12Al14O33) catalyst. The gas leaving the
gasifier had an approximate tar content of 26 g/Nm3, and the secondary
treatment reduced this content in an 84% at 800 °C, increasing H2
concentration in the gas from 48 vol% to 55 vol%. The authors observed
no catalyst deactivation under these conditions for 12 h operation.
Finally, although the majority of the secondary catalytic treatment
processes have been carried out in a fixed bed reactor, Bain et al. [67]
and Yung et al. [68] studied the secondary tar cracking and reforming
step in a fluidized bed, which was placed downstream a fluidized bed
gasifier, followed by a thermal cracking tubular reactor. Operation in a
fluidized bed reactor implies developing fluidizable Ni based catalysts,
with high attrition resistance. Yung et al. [68] used olivine as primary
catalyst in the gasifier and developed a fluidizable 6.6%NiO/3.4%
MgO/4.0%K2O/Al2O3 reforming catalyst for the reforming step. H2
concentration in the gas increased from 32.8 vol% for gasification to
53.7 vol% including the reforming step, whereas the tar, whose content
was 13.5 g/Nm3 without the reforming step, practically disappeared.
The authors performed 10 reaction-regeneration cycles, in which H2
concentration was reduced to 52.4 vol%, and although the catalyst was
still active for tar reforming, CH4 concentration increased from 0.17 to
2.7 vol%, which was attributed to H2S deactivation.
Fig. 7. Effect of steam to biomass ratio on hydrogen production in the gasifi-
cation process. Gil et al., 1999 [59]; Wei et al., 2006 [56]; Umeki et al., 2010
[11]; Rapagnà et al., 2000 [61]; Franco et al., 2003 [93]; Karmakar et al., 2011
[94]; Erkiaga et al., 2014 [57]; Luo et al., 2009 [51]; Gao et al., 2009 [95]; Song
et al., 2012 [96]; Fremaux et al., 2015 [53].
A. Arregi et al.
Fig. 8. Effect of different catalysts on tar content in the syngas. Rapagnà et al.,
2000 [61]; Erkiaga et al., 2013 [15]; Miccio et al., 2009 [110]; Rapagnà et al.,
2011 [62]; Koppatz et al., 2011 [18]; Berdugo Vilches et al., 2016 [72].
3. Supercritical water gasification
Supercritical water gasification has been proposed as alternative to
steam gasification for high moisture content biomass (typically > 30 wt
%), such as food derivatives [111], algae [112] or sewage sludge, as no
drying pretreatment is required [113]. The process takes place at
temperatures higher than 374 °C and pressures above 22.1 MPa
[114,115], with H2 production being enhanced at temperatures above
600 °C (lower ones have been reported to increase CH4 concentration).
However, the process presents serious drawbacks for large scale
feasibility. Pumping of the feedstock is a technological challenge, as
biomass needs to be converted into a pumpable slurry or solution,
which limits the dry biomass content in the slurry to 20 wt%, depending
on the biomass type. In addition, plugging by char, tar or alkaline
catalysts may occur in long time runs and the severe operating condi-
tions may lead to material corrosion problems [116]. The high energy
consumption of the process is one of the most important factors, as
water has to be maintained at supercritical conditions.
These drawbacks have hindered the scalability of the process, and
therefore laboratory scale reactors have been used for biomass super-
critical gasification studies, with most of the runs being carried out in
batch reactors [117–125] and, to a lesser extent, in continuous flow
tubular [126,127] or fluidized bed reactors [128]. The largest super-
critical water gasification facility implemented is the VERENA pilot
plant at Karlsruhe Institute of Technology (100 kg/h), which has been
designed for 700 °C, 35 MPa and a maximum solids content of 20 wt%,
and includes a down-flow reactor and a biomass and water preheating
step with the reactor outlet stream [113,129].
In order to reduce the operating temperature and increase H2 se-
lectivity, several catalysts have been developed, which can be classified
into alkali based (such as Na2CO3, K2CO3 or NaOH), transition metal
based (Ni and Ru) and activated carbon catalysts. Although all of them
have proven to be suitable for enhancing gasification and improving H2
yield, alkali catalysts lead to corrosion and plugging problems, whereas
transition metal and activated carbon based catalysts undergo a severe
deactivation [115,130].
Several studies have been carried out analyzing the supercritical
gasification of food and agricultural residues, in which the H2 pro-
ductions reported vary in a wide range, between 0.1 and 11 wt% (de-
fined as gH2/100 gbiomass) which depend on the biomass type and
loading, operating conditions and catalysts used. Thus, in the non-cat-
alytic supercritical gasification studies carried out in batch reactors in
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Energy Conversion and Management 165 (2018) 696–719
which the influence of biomass type was analyzed, Safari et al. [117]
observed that biomasses with a high cellulose content and low lignin
one lead to higher H2 productions, with the maximum value of 1.5 wt%
being obtained for wheat straw at 440 °C and 25 MPa, with a biomass
loading of 1 wt% in a batch micro reactor system. However, Yanik et al.
[118] concluded that other organic materials apart from cellulose and
lignin are responsible for the differences in gasification yields. The H2
production values reported by these authors in a batch autoclave at
500 °C ranged between 0.4 and 0.9 wt%.
Regarding the influence of catalyst on gasification performance, the
studies performed reveal that although alkali, transition metal and ac-
tivated carbon based catalysts improve H2 production, there is no
consensus regarding which type of catalyst is the most adequate one.
Ding et al. [122] compared the performance of Ni/CeO2/Al2O3, KOH
and calcined dolomite, and concluded that KOH had the best activity in
pinewood supercritical gasification, with H2 production being increased
from 0.2 to 1.1 wt% at 550 °C. Contrarily, Jin et al. [123] compared the
catalytic behaviour of Ca(OH)2, Na2CO3, K2CO3, NaOH, KOH, LiOH,
and ZnCl2, three kinds of Raney-Ni, dolomite, and olivine, in peanut
shell gasification at 400 °C and 24 MPa, observing that the Raney-Ni
catalyst with the highest Fe content was the most active one, obtaining
a H2 production of 2.1 wt%. Furthermore, Ru based catalysts have also
proven to have a high activity, as confirmed by Elif and Nezihe [124],
who improved H2 production from 3.2 to 11 wt% in the gasification of
pulp fruit at 600 °C, using a Ru/C catalyst, and by Osada et al. [125],
who also found that H2 production was enhanced, from 0.1 to 1 wt%,
when a Ru/TiO2 catalyst was used in sugarcane bagasse gasification at
400 °C.
4. Bio-oil reforming
Bio-oil is the liquid fraction obtained from biomass pyrolysis, which
is the thermal decomposition of biomass in absence of oxygen, and one
of the most energetically efficient and low cost process to obtain liquid
fuels from a renewable source [131–133]. Thus, under fast pyrolysis
conditions (high heating rates and short residence times), bio-oil yields
between 60 and 75 wt% are achieved [38,134–137], which can be va-
lorised by the catalytic steam reforming process to produce H2 as main
product.
Although bio-oil properties change depending on pyrolysis condi-
tions, reactor configuration and the feedstock used, its direct applica-
tion involves several drawbacks related to its high viscosity, low
heating value, high oxygen and water content and high corrosiveness,
which make it chemically unstable and cause ageing problems in its
storage [136]. In spite of the disadvantages of the bio-oil compared to a
conventional fuel, it is a good alternative for H2 production from a
renewable source [106,138–140]. Thus, the aforementioned problems
lead to consider different alternatives for its upgrading, such as mix it
with other fuels or physical, thermal and catalytic treatments (catalytic
cracking, esterification, hydrodeoxygenation, steam reforming, etc.)
[136,138,140]. The catalytic steam reforming of bio-oil (Fig. 9) is one
of these routes that has been considerably researched, using different
reactor configurations, catalysts and operating conditions. The high
water content of the bio-oil is not a problem for this valorisation route.
The aforementioned difficulties related to bio-oil properties and its
feeding problems boosted the use of bio-oil model compounds as feed,
which helps understanding the mechanisms of reforming reactions
[141], with acetic acid [142–158], acetone [159–166] and ethanol
[167–170] being among others the most studied ones. Nevertheless,
although some works have been published concerning reforming of
phenols [150,151,165,166,171–173], and especially m-cresol
[174–179], furans [176,177,180], saccharides [162,174] and aromatic
compounds, such as toluene [181–183] or m-xylene [162], cyclic
oxygenated compounds (phenols, saccharides and furans) are less in-
vestigated, but they are supposed to be responsible for the catalyst
deactivation by coke deposition [180].
A. Arregi et al.
Consequently, this strategy focuses on the valorisation of the bio-oil
aqueous fraction and, especially, raw bio-oil, which has recently gained
increasing attention. Therefore, Tables 2 and 3 summarize some of
these studies, in which reforming of bio-oil aqueous fraction (Table 2)
and raw bio-oil (Table 3) have been performed. Although different re-
actors and operating conditions have been used, a discussion of the
main results has been detailed below. In this section, the values of H2
production are generally given as g of H2 per 100 g of organic com-
pounds in the feed, and otherwise it will be specified in each case.
Moreover, H2 yield is based on the maximum allowable by stoichio-
metry.
4.1. Reactor configurations
Many studies on the reforming of bio-oil aqueous fraction are found
in the literature, which have been carried out mainly in fixed
[23,24,184,186,188–191,196,210] and fluidized bed [21,185,187] re-
actors. Similarly to the reforming of the bio-oil aqueous fraction, the
reforming of raw bio-oil has also been performed mainly in fixed bed
[25,161,198,200,203–207,210] and fluidized bed [197,202,208] re-
actors. Higher conversion and H2 yield were obtained by Remón et al.
[209] in a fixed bed reactor compared to fluidized bed reactor.
Nevertheless, Lan et al. [201] reported lower carbon deposition in the
fluidized bed reactor than in the fixed bed reactor, obtaining carbon
contents of around 2.3 wt% and 0.3 wt%, respectively, at 650 °C in
60 min on stream.
Moreover, some authors used a two-stage system for bio-oil re-
forming. The steam reforming of bio-oil aqueous fraction
[192,194,213], raw bio-oil [22,211,212] and bio-oil/bio-ethanol mix-
tures [214,215] was investigated by Remiro et al. and Valle et al. using
a two-stage thermal-catalytic process, in which the pyrolytic lignin was
deposited by repolymerization of certain bio-oil components in the first
stage and the treated bio-oil together with the gases formed in the first
step were in-line reformed in a fluidized bed reactor. Yao et al. [195]
used a two-stage fixed bed reactor, where firstly the bio-oil aqueous
fraction was volatilized at 400 °C and subsequently the reforming step
was carried out on modified Ni-Al catalysts.
Nevertheless, although different reactors have been used for bio-oil
reforming, the main issue to be solved is related to raw bio-oil feeding,
which causes several problems in the reforming reactions. Basagiannis
et al. [186] reported coke deposition on the reactor wall due to the
polymerization of unstable compounds in the bio-oil. Although the
feeding system was cooled, Kechagiopoulos et al. [20] reported plug-
ging of the injection nozzle, due to the thermal instability of the aqu-
eous fraction of the bio-oil used for the process, which required a new
injection-cooling system to feed adequately the bio-oil fraction. More-
over, some authors reported aging problems of the bio-oil, which have
been solved by adding different alcohols such as methanol [197] or
ethanol [215] in order to stabilize the bio-oil and reduce its viscosity.
Fig. 9. Schematic representation of the bio-oil reforming process for hydrogen production.
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Energy Conversion and Management 165 (2018) 696–719
4.2. Operating variables
In spite of the fact that a detailed comparison of results is difficult,
the most relevant ones on the effect operating conditions have on
product yields and, especially, on H2 production, have been summar-
ized in this section.
4.2.1. Temperature
Temperature is one of the key variables that should be taken into
account in the reforming processes. On the one hand, higher tempera-
tures enhance reforming kinetics of oxygenated compounds of the bio-
oil and, therefore, higher H2 yield and production are obtained. On the
other hand, using high temperatures the coke deposition can be reduced
given that its in situ gasification is promoted [192,199,201,216].
Fig. 10 displays the effect of temperature on H2 yield in several bio-oil
reforming processes studied in the literature.
The effect of this variable on conversion and product distribution
and, especially, on H2 production has been extensively studied in the
literature in the reforming of bio-oil aqueous fraction. Thus, Czernik
et al. [185] reported that coke gasification was enhanced at 850 °C,
obtaining a maximum conversion and H2 yield of 95% and 89%, re-
spectively, with 1000 h−1 and S/C of 7, which corresponds to a H2
production of 16.8 wt%. Yan et al. [188] reported a very low H2 yield at
450 °C (9.4%), whereas a maximum H2 yield of 69.7% was attained at
the highest temperature studied (800 °C), with water to bio-oil ratio
being 4.9 and with Ni and Ce contents 12 and 7.5%, respectively. The
effect of temperature in the 600–800 °C range was also studied by
Bimbela et al. [190], obtaining higher conversion and H2 yield and
production as temperature was increased, with the maximum values
being 82.62%, 77% and 13.8 wt%, respectively. Nevertheless, the
highest H2 concentration was obtained at 650 °C (65.48 vol%), which
decreased to 56.87 vol% at 800 °C. Yao et al. [195] studied the influ-
ence of temperature in the 600–900 °C range, with conversion and H2
yield being increased from 8.11 to 90.40% and from 5.64 to 57.21%,
respectively (maximum H2 production of 10.4 wt%).
Therefore, most studies reveal that high temperatures are needed to
achieve full conversion of bio-oil aqueous fraction. Nevertheless,
Remiro et al. [192] reported full conversion above 550 °C, although
catalyst deactivation was lower as temperature was increased in the
500–650 °C range.
Concerning raw bio-oil reforming, similar effect of temperature on
conversion and product distribution has been reported in the literature,
with both increasing at higher reforming temperatures [203,204,207].
Thus, Wang et al. [198] reported higher carbon conversion and H2 yield
as temperature was increased in the 250–750 °C range, obtaining a
maximum conversion, H2 yield and H2 production of 96%, 80% and
20.1 wt%, respectively, at 750 °C and S/C ratio of 9 when C12A7-O−/
18% Mg catalyst was used. As temperature was increased in the
400–550 °C range by Hou et al. [200], higher conversion and H2 yield
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

Table 2
Studies involving different strategies, feeds, catalysts and operating conditions, and main results obtained (maximum H2 yield or production) reported in the
literature for reforming of bio-oil aqueous fraction.
Reactor Kind of study Biomass Catalyst Operating conditions Conversion H2 H2 production Ref.
configuration yield (wt%)b
(%)a

Dual fixed bed Laboratory scale Poplar Ni/Al2O3 (reference) T = 825–875 °C 98 88 12.4* [184]
(150 mg min−1) wood Commercial: G-91, C11- GC1HSV = 126,000–80,000 h−1
NK, ICI46-1, ICI46-4 S/C = 4.92–11
Co-promoted Ni and Cr-
promoted Ni supported on
MgO-La2O3-α-Al2O3
Bubbling Bench scale Pine C11-NK T = 800–850 °C 95 89 16.8* [185]
fluidized (120–300 g h−1) sawdust GC1HSV = 700–1000 h−1 3.0d
bed S/C = 7–9
Nozzle-fed fixed Bench scale Beech Ru/MgO/Al2O3 T = 700–800 °C 100 100c – [186]
bed (290–1050 ml min−1) wood GHSV = 4880–16,570 h−1
S/C = 7.2
Fluidized bed – Sawdust Ni/dolomite T = 600–800 °C – 73 – [187]
Ni/modified dolomite WHSV = 1.5 h−1
S/C = 2–10
Laboratory-scale Laboratory scale Rice hull Commercial: Z417 T = 450–800 °C – 69.7 – [188]
fixed bed Ni/CeO2-ZrO2 Water/bio-oil = 3.2–5.8
Ni loading = 5–12 wt%
Ce loading = 5–10 wt%
Fixed bed Laboratory scale Corn G90-LDP T = 500–700 °C 80 65 12.5 [189]
(4 ml h−1) stover WHSV = 0.87 h−1
S/C = 4–18
Bench scale Small bench scale Pine wood Ni/Al coprecipitated T = 600–800 °C 82.62 77 13.8 [190]
fixed bed catalysts Space
Ni loading = 23–33% time = 0–5.01 gcatalyst min gorganic−1
S/C = 5.58
Fixed bed – Pine wood Ni-Mo supported on T = 600–800 °C 98 67.5 – [191]
sawdust modified sepiolite WHSV = 0.9–5.4 h−1
S/C = 2–25
Fixed bed/ Laboratory scale Pine Ni/La2O3-αAl2O3 T1 = 500 °C 100 96 15.6* [192]
fluidized (0.1 ml min−1) sawdust T2 = 600–800 °C 10.1d
bed Space time = 0.10–0.45 gcatalyst h gbio-
−1
oil
S/C = 12
Fixed bed or Laboratory scale Pine Ni/Al-Mg-O modified with T = 650 °C 80 – 13.8 [193]
fluidized (0.12–0.76 ml min−1) sawdust Co or Cu Space time = 4 gcatalyst min gorcanic−1
bed S/C = 7.6
Fixed bed/ Laboratory scale Pine Ni/αAl2O3 T1 = 200 °C 100 96 15.6* [194]
fluidized (0.1 ml min−1) sawdust Ni/La2O3-αAl2O3 T2 = 600–800 °C 10.1d
bed Space time = 0.10–0.45 gcatalyst h gbio-
−1
oil
S/C = 12
Fixed bed/fixed Laboratory scale Corn stalk Ni-Al modified with Ca, T1 = 400 °C (volatilization) 90.4 57.2 10.4* [195]
bed (0.3 g min−1) Ce, Mg, Mn and Zn T2 = 600–900 °C
Space time = 1.67 gcatalyst min gbio-oil−1
S/C = 3.54–9
Fixed bed Laboratory scale Pine/ Ni/Mg-Al modified with T = 650 °C 78.7 – 14.7 [196]
(0.12 ml min−1) poplar Ce GC1HSV = 13,000 h−1
wood

a
H2 yield referred to maximum allowable by stoichiometry.
b
H2 production defined as gH2/100 gorganic.
c
H2 selectivity.
d
H2 production defined as gH2/100 gbio-oil.
* Calculated by H2 yield and bio-oil composition.

and production were achieved, obtaining maximum values of 94.9%,
92.5% and 17.5 wt%, respectively, at 550 °C with the highest S/C ratio
studied on a 15% Ni-CNT catalyst. Valle et al. [211] obtained a H2 yield
of around 88% above 650 °C, 0.10 gcatalyst h gbio-oil−1 and S/C ratio of 6.
4.2.2. Space time
Space time is an important variable whose effect has been studied
by several authors in the reforming of bio-oil aqueous fraction. Most
studies reported that higher space times enhance reforming and WGS
reactions, and therefore higher H2 yields are obtained. Thus, Medrano
et al. [21] studied two different space time values (4.11 and
8.97 gcat min gorganics−1) in the steam reforming of bio-oil aqueous
fraction at 650 °C on a Mg modified Ni-Al catalyst, obtaining a sig-
nificant increase in conversion and H2 concentration from 81.01% to
83.26% and from 63.13 vol% to 67.37 vol%, respectively, and
achieving a maximum H2 production of 13.3 wt%. Liu et al. [191]
studied the effect of space velocity at 750 °C and S/C ratio of 16, ob-
taining the highest values of conversion (98%) and H2 yield (62.5%)
below 1.8 h−1.
Similar results were obtained in the literature when raw bio-oil
reforming was carried out, obtaining higher H2 yields as space velocity
is decreased [22,25,204,207,208]. Wu et al. [199] reported that lower
GHSV values lead to higher CH4 conversion and H2 yield, obtaining full
conversion and a H2 yield of 81.1% at 800 °C and with a GHSV value

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A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

Table 3
Studies involving different strategies, feeds, catalysts and operating conditions, and main results obtained (maximum H2 yield or production) reported in the
literature for reforming of raw bio-oil.
Reactor configuration Kind of study Biomass Catalyst Operating conditions Conversion H2 H2 Ref.
yield production
(%)a (wt%)b

Fixed bed Laboratory scale Beech wood Pt, Pd, Rh supported on T = 650–950 °C – 75 14.5d,* [161]
(14 μL min−1) Al2O3 and CeZrO2 GHSV = 3090 h−1
S/C = 5/10.8
Fluidized bed Bench scale (84 g h−1) Hardwood + 10% C11-NK T = 850 °C 95 80 12.9d [197]
methanol Laboratory Ni catalysts GC1HSV = 920 h−1
S/C = 5.8
Fixed bed Laboratory scale Biomass C12A7-O-/M catalysts T = 250–750 °C 96 80 20.1* [198]
M = Mg, K, Ce GHSV = 10,000 h−1 12.4d,*
S/C = 1.5–9
Fixed bed/fixed bed Laboratory scale Sawdust 1 – Dolomite T1 = 700–900 °C 100 81.1 13.2d,* [199]
2 – Ni/MgO T2 = 600–800 °C
(WBHSV)1 = 0.5–5 h−1
(GHSV)2 = 1800–14,400 h−1
(S/C)1 = 1–16
(S/CH4)2 = 1–4
Fixed bed – Sawdust Ni-CNT T = 350–550 °C 94.9 92.5 17.5* [200]
Ni loading = 5, 15, 35% GHSV = 12,000 h−1
S/C = 2.0–6.1
Fixed bed or fluidized bed Bench scale Rice husk Ni/MgO-La2O3-Al2O3 Tfixed = 650–950 °C – 75.88 17.6* [201]
LHSVfixed = 0.8–2.5 h−1
S/Cfixed = 3–14
Tfluidized = 500–800 °C
LHSVfluidized = 0.2–1.5 h−1
S/Cfluidized = 8–20
Fluidized bed Bench scale Rice husk NiO/MgO T = 500–800 °C – 56.3 13.1* [202]
(100 g h−1) WHSV = 0.2–0.8 h−1
S/C = 8–20
Fixed bed Laboratory scale Biomass Ni/Al2O3 T = 750–950 °C 81 85 14.3d,* [203]
(2.13 ml min−1) Ru-Ni/Al2O3 WBHSV = 13 h−1
Ni-MgO/Al2O3 S/C = 5
Ni loading = 0–18%
Ru loading = 0.5%
Fixed bed Laboratory scale Biomass Ni/Al2O3 T = 650–950 °C 79 73 12.3d,* [204]
(2.13 ml min−1) Ni loading = 0–18% WBHSV = 9–26 h−1
S/C = 1–8
Fixed bed Laboratory scale Sawdust NiCo/Ce-Zr-O T = 850 °C – 72.15 13.2* [205]
(12 ml min−1) Ni loading = 2–10% WHSV = 2.62 h−1
Co loading = 2–10%
Fixed bed Laboratory scale Biomass Ni/ZrO2 T = 850 °C – 92 20.1* [206]
(2.13 ml min−1) Ni/Al2O3 WBHSV = 13 h−1 15.5d,*
Ni loading = 0–18% S/C = 5
Fixed bed/fluidized bed Laboratory scale Pine sawdust 1 – Dolomite T1 = 500 °C 100 95 15.4* [22]
(0.1 ml min−1) 2 – Ni/La2O3-αAl2O3 T2 = 600–800 °C 11.7d
GC1HSV = 8000–156,000 h−1
S/C = 1–15
Fixed bed Laboratory scale Maize stalk Ni-Ce/Al2O3 T = 700–900 °C – 71.4 11.1d,* [207]
Ni loading = 5.1–20.4% WBHSV = 8–24 h−1
S/C = 1–9
Fluidized bed Bench scale Pine sawdust Ni/dolomite T = 500–800 °C 80.0 45c – [208]
(100 g h−1) Ni/modified dolomite WHSV = 0.2–1 h−1
S/C = 8–20
Fixed bed or fluidized bed Laboratory scale Pine sawdust Ni/Co-Al-Mg T = 650 °C 95 – 17.0* [209]
(0.3 g min−1) GC1HSV = 13,000 h−1
S/C = 7.6
Fixed bed Laboratory scale Corn cob Ce-Ni/Co-Al2O3 T = 650–850 °C – 85 11.7* [25]
LHSV = 0.08–0.23 h−1 6.6d,*
S/C = 9–15
Fixed bed Laboratory scale (1 g/ Coconut shell Fe/olivine T = 800 °C 97.2 79.3 – [210]
h) WBHSV = 0.5 h−1
S/C = 2
Fixed bed/fluidized bed Laboratory scale Pine sawdust Ni/La2O3-αAl2O3 T1 = 500 °C 100 93 – [211,212]
(0.08–0.1 ml min−1) T2 = 550–700 °C
Space
time = 0.04–0.38 gcat h gbio-oil
S/C = 1.5–6

a
H2 yield referred to maximum allowable by stoichiometry.
b
H2 production defined as gH2/100 gorganic.
c
H2 concentration in the gas (vol%).
d
H2 production defined as gH2/100 gbio-oil.
* Calculated by H2 yield and bio-oil composition.

706
A. Arregi et al.
lower than 3600 h−1. Remiro et al. [22] reported higher conversion and
H2 yield when space velocity was decreased, obtaining full conversion
and H2 yield of 95% at a S/C ratio of 9 and for GC1HSV lower than
65,000 h−1. Moreover, as space velocity was decreased lower coke
content on the catalyst was observed, which decreases from 1.14 to
0.1 wt% in the 156,000–8000 h−1 range.
Nevertheless, when low space velocity values are used, higher
performance of the WGS reaction is observed, given that CO con-
centration decreases and CO2 concentration increases, at the same time
as secondary products such as CH4 and light hydrocarbons produced
from mainly cracking reactions disappear [21,186,190].
4.2.3. Steam/C ratio
The most important effect of S/C ratio is the enhancement of the
WGS reaction, which favours the formation of H2 and CO2 as main
products. Thus, most studies reported that CO, CH4 and light hydro-
carbon yields are decreased as S/C ratio is increased
[22,187,188,198,208]. Fig. 11 shows the effect of steam to C ratio on
H2 yield in several bio-oil reforming studies.
When S/C ratio was increased from 2 to 5 by Li et al. [187] in the
reforming of bio-oil aqueous fraction, H2 yield was significantly af-
fected, although above this value the influence of S/C ratio was less
pronounced. Ortiz-Toral et al. [189] reported that for S/C > 8 the
effect of this variable on H2 production was negligible. Liu et al. [191]
reported that for S/C ratios above 12, the yields become constant, ob-
taining a H2 yield of 61% with the highest S/C ratio, at 750 °C and
1.8 h−1.
Similarly, studies related to raw bio-oil reforming also report higher
H2 yields and carbon conversions when higher S/C ratios were used
[202]. Thus, Wang et al. [198] observed the enhancement of the WGS
reaction as S/C ratio was increased in the 1.5–9 range, especially be-
tween 1.5 and 4, with the increase being smaller in the 4–9 range. Lan
et al. [201] reported the enhancement of reforming and WGS reactions
at high S/C values in both fixed bed and fluidized bed reactors, al-
though the steam needed in the fluidized bed reactor was higher be-
cause it acted also as a fluidizing agent. Remiro et al. [22] reported
higher H2 yields as S/C ratio was increased in the 1–15 range, although
above S/C of 5 the increase was less significant, obtaining a maximum
H2 yield of 95% at the highest S/C ratio studied.
Moreover, at high S/C ratios water adsorption on the catalyst sur-
face is enhanced, favouring the gasification of coke, and therefore im-
proving the overall reforming process [184,198,207]. Thus, when S/C
ratio was increased by Li et al. [187], lower coke yield was obtained,
with the decrease being more pronounced from 2 to 5.
4.3. Catalysts
Different catalysts have been studied in the literature in the re-
forming of bio-oil aqueous fraction and raw bio-oil, although Ni based
are the most used ones [106,139,216,217]. Czernik et al. [197] com-
pared a commercial (C11-NK) and laboratory prepared catalysts in the
reforming of raw bio-oil and reported higher stability of the commercial
catalyst due to the higher Ni content and surface area of that catalyst.
Furthermore, it has high initial conversion (95%) and H2 production
(12.9 wt% by mass unit of bio-oil). Nevertheless, some authors also
used noble metals, which are very active for reforming reactions, al-
though its high cost is a drawback for its industrial implementation.
Thus, Rioche et al. [161] studied Rh and Pt catalysts supported on
Al2O3 and CeZrO2 in the reforming of raw bio-oil, obtaining a max-
imum H2 yield of 75% using 1% Pt/CeZrO2 catalyst, with these values
being noticeably higher compared to Al2O3 supported catalysts.
Furthermore, different promoters have also been studied in the re-
forming of bio-oil aqueous fraction in order to improve catalyst activity
and stability, with Ce, La, Mg and Ca being the most studied ones. The
effect of La2O3 addition to Ni/Al2O3 catalyst was studied by Valle et al.
[194] and a good performance was reported, which was explained by
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Energy Conversion and Management 165 (2018) 696–719
its capacity for water adsorption, and therefore for enhancing the WGS
reaction. Moreover, higher stability of the catalyst was also observed
when La2O3 was added, maintaining almost full conversion for up to
20 h on stream, whereas it decreased subsequent to 7 h when the Ni/
Al2O3 catalyst was used. Different Ni-Al catalysts modified with Ca, Ce,
Mg, Mn and Zn were used by Yao et al. [195] in the reforming of bio-oil
aqueous fraction at 800 °C and a S/C ratio of 3.54. The highest H2 yield
of 56.46% was obtained when Ni-Mg-Al catalyst was used, followed by
Ni-Ce-Al (55.30%) and Ni-Zn-Al (52.01%) catalysts.
Similarly, the addition of promoters has also been investigated in
bio-oil reforming. Salehi et al. [203] compared Ru-Ni/Al2O3 and Ni/
Al2O3 catalyst with different Ni contents, obtaining a maximum H2
yield of 85% at 950 °C when Ru-Ni/Al2O3 catalyst was used with a Ni
content higher than 10.7%.
The effect of metal content on the catalyst has also been analyzed in
the literature for the reforming of bio-oil aqueous fraction. Yan et al.
[188] studied different Ni (between 5 and 12 wt%) and Ce (between 5
and 10 wt%) loadings in Ni/CeO2-ZrO2 catalysts and they did not ob-
serve high differences between the different loadings, although a little
increase in H2 yield was achieved at the highest Ni loading studied.
Bimbela et al. [190] investigated the effect of Ni content in the 23–33%
range on product distribution and the highest conversion (63.35%) and
H2 concentration (65.48 vol%) were obtained with the 28% Ni catalyst
at 650 °C and 1.67 gcatalyst min gorganic−1.
Concerning raw bio-oil reforming, the influence of Ni content on a
Ni/Al2O3 catalyst was studied by Seyedeyn-Azad et al. [204], obtaining
the highest conversion (79%) and H2 yield (73%) when a Ni content of
14.1% was used. The same authors reported the effect of the support by
comparing Ni/ZrO2 and Ni/Al2O3 catalysts, achieving higher H2 yields
when the Ni/ZrO2 catalyst with 14% Ni was used [206]. Nevertheless,
the amount of coke deposited on the catalyst was much higher when the
Ni/ZrO2 catalyst was used than when the Ni/Al2O3 catalyst was used.
The effect of Ni and Co content on a NiCo/Ce-Zr-O catalyst was studied
by Zhang et al. [205] in the 2–10% range for both metals, obtaining the
best results in terms of H2 yield (72.15%), H2 production (13.2 wt%)
and coke deposition with 3Ni9Co/Ce-Zr-O catalyst.
Moreover, increasing attention is being paid to the use of CO2 ad-
sorbents in reforming processes, given that the thermodynamic equili-
brium of bio-oil reforming reaction is shifted, and therefore higher H2
yields are obtained [22,165,213,218,219]. Thus, Remiro et al. [213]
used dolomite as CO2 adsorbent in the catalytic steam reforming of bio-
Fig. 10. Effect of reforming temperature on the hydrogen yield (percentage of
the maximum allowable by stoichiometry) in aqueous and raw bio-oil re-
forming processes. Li et al., 2009 [187]; Liu et al., 2013 [191]; Remiro et al.,
2013 [192]; Yao et al., 2014 [195]; Wang et al., 2007 [198]; Xu et al., 2010
[202]; Valle et al., 2018 [211].
A. Arregi et al.
Fig. 11. Effect of steam to C ratio on H2 yield (percentage of the maximum
allowable by stoichiometry) in aqueous and raw bio-oil reforming studies. Li
et al., 2009 [187]; Liu et al., 2013 [191]; Wang et al., 2007 [198]; Lan et al.,
2010 [201]; Seyedeyn-Azad et al., 2011 [204]; Fu et al., 2014 [207]; Valle
et al., 2018 [212].
oil aqueous fraction, obtaining full conversion of the bio-oil and H2
yields around 99%. Nevertheless, further studies dealing with reaction/
regeneration cycles are required in order to study the loss of activity of
the adsorbents.
4.4. Catalyst deactivation
Some authors reported high deactivation of the catalyst due to coke
deposition on its surface. Catalyst deactivation leads to secondary re-
actions, such as thermal decomposition of bio-oil and Boudouard re-
actions. Although it has not been extensively studied in the literature,
some authors reported that H2 and CO2 yields decrease and CO, CH4
and hydrocarbons yields increase with time on stream due to the at-
tenuation of oxygenated compound reforming and the enhancement of
secondary reactions in the reforming of bio-oil aqueous fraction
[21,185,191,192]. Moreover, coke deposition may also be attributed to
the dehydration and polymerization of the aromatic compounds in the
bio-oil [220]. This trend on product yields was observed by Garcia et al.
[184], obtaining by-products, such as CH4, methanol, benzene, toluene
and naphthalene as the catalyst was deactivating. Czernik et al. [185]
reported a conversion of around 100% of the bio-oil aqueous fraction
and an initial H2 yield of 85%, although it decreased to 77% after 12 h
on stream due to coke deposition. Bimbela et al. [190] reported a de-
creasing trend of conversion with time on stream due to the low activity
of the catalyst for WGS reaction, at the same time as H2 production
decreases and those of CO, CH4 and C2 increase. Nevertheless, at the
highest space time studied, H2 yield was maintained constant for up to
120 min on stream. Moreover, Valle et al. [194] reported higher sta-
bility (conversion constant for up to 5 h on stream) and lower coke
deposition with Ni-La2O3/αAl2O3 catalyst than with Ni/Al2O3 catalyst,
obtaining a coke content of 1.40 and 2.50 wt% at 600 °C and 0 and
0.10 wt% at 800 °C, respectively.
The same trend was observed when raw bio-oil was valorised by
catalytic steam reforming [22,198]. Thus, Rioche et al. [161] per-
formed a long experiment with 1% Pt/CeZrO2 catalyst, obtaining a slow
deactivation of the catalyst after 9 h on stream, with H2 yield being
between 50 and 60%. Hou et al. [200] studied the stability of a 15% Ni-
CNT catalyst at 500 °C, GHSV of 12,000 h−1 and S/C ratio of 6.1, re-
gistering a slow decrease on carbon conversion and H2 yield for the first
8 h on stream, whereas above that time H2 yield decreased considerably
(50% lower) until 15 h on stream. Zhang et al. [205] studied the
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Energy Conversion and Management 165 (2018) 696–719
stability of 3Ni9Co/Ce-Zr-O catalyst, obtaining a decrease of 12% in H2
yield in 360 min on stream and a value of around 64% when the cat-
alyst was deactivated. Fu et al. [207] reported slow deactivation of the
Ni-Ce/Al2O3 catalyst up to 6 h on stream at 850 °C, S/C ratio of 6 and
WBHSV of 12 h−1, whereas the deactivation was faster subsequent to
6 h until a low H2 yield was obtained in 10 h on stream.
5. Bio-oil steam gasification
Bio-oil gasification has been proposed as an alternative to biomass
gasification for syngas production, with the aim of reducing the ex-
pensive biomass transport costs [221]. Therefore, as in the case of bio-
oil reforming, several decentralized pyrolysis plants coupled with a
centralized bio-oil gasification facility would be required in order to
take advantage of the economies of scale [222]. In addition, the pyr-
olysis char may also be upgraded together with the bio-oil, by feeding it
as bio-slurry, thus taking advantage of the potential of biomass pyr-
olysis char to produce H2 [223,224]. In this way, the biomass that has
an energy density of about 2 GJ/m3 is upgraded to a bio-slurry with a
density of 25 GJ/m3, thereby considerably reducing the transport costs
[36]. It has been reported that bio-oil gasification becomes more at-
tractive economically than biomass gasification for large scale plants,
low energy density biomass and very long transport distances. How-
ever, improvements in biomass pyrolysis efficiency and gasification
plants’ capital costs would make bio-oil gasification cost-competitive
also in smaller distances [225].
The differences between bio-oil gasification and reforming are
vague and sometimes are not well distinguished in the literature. In this
paper, gasification has been considered as the process that takes place
at higher temperatures than bio-oil reforming (around 800–1400 °C),
and is carried out non-catalytically or in the presence of primary mi-
neral catalysts, as in biomass gasification. Therefore, bio-oil gasification
produces a syngas with a similar composition than the one obtained in
biomass gasification, whereas bio-oil reforming yields a gas with higher
H2 content. The lower H2 yield and energy efficiency and higher costs of
bio-oil gasification are responsible for the lower technological devel-
opment of this thermochemical route [226].
The H2 productions (defined in this section as gH2/100 gbio-oil) ob-
tained by several authors in the literature vary in a wide range, as a
result of differences in the bio-oils used, reactor configurations and
operating conditions. In the non-catalytic studies analyzed, the average
H2 production can be established at around 4 wt%, although values
between 1.4 and 12.6 wt% have been reported. Thus, Panigrahi et al.
[227], operating in a fixed bed micro-reactor at 800 °C, obtained the
maximum H2 production of 4.4 wt% with a steam/carbon ratio of 2. A
similar value of 4 wt% was attained by Kan et al. [228], also in a fixed
bed at 800 °C and a S/C of 10.6. Furthermore, Latifi et al. [229], op-
erating in a Jiggle bed reactor at 800 °C, without adding additional
steam to the bio-oil, observed a H2 production of 3.5 wt%. Van Rossum
et al. [230] obtained a lower H2 production of 1.4 wt% in a fluidized
bed at 790 °C and S/C of 1.9. Finally, Chhiti et al. [231] reached the
highest H2 production of 12.6 wt% at 1400 °C and S/C = 8.3 in a la-
boratory scale high temperature entrained flow reactor.
6. Pyrolysis and in-line steam reforming
Among the different thermochemical routes aforementioned for H2
production from biomass, the two-stage pyrolysis-reforming strategy
has been gaining increasing attention recently, given that it has several
advantages in relation to the gasification process due to the separation
of pyrolysis and reforming steps in different zones. Thus, this process
allows for independent temperature optimization in the pyrolysis and
reforming steps [232]. Moreover, compared to catalytic gasification
process, the direct contact between the feedstock and its impurities
with the reforming catalyst is avoided [233]. In addition, the reforming
step is carried out at lower temperature in comparison to catalytic
A. Arregi et al.
gasification, and therefore catalyst deactivation by sintering can be
avoided [234,235], especially when Ni is used as active phase, which is
the most widely used catalyst in reforming of oxygenated compounds
and hydrocarbons. Furthermore, the gasification process does not focus
on H2 production, but syngas is the main product. The quality and
concentration of the syngas depends on the gasifying agent used, and
therefore subsequent catalytic processes are needed to enhance H2
production. Moreover, highly active steam reforming catalysts allow for
attaining complete conversion of biomass derived volatiles, with the gas
product being free of tars, which is a remarkable advantage over con-
ventional gasification [31].
Regarding bio-oil reforming, volatiles from biomass are valorised in-
line, and therefore condensation and volatilization of the intermediate
compounds from biomass pyrolysis are not required, which avoids the
difficult handling of these products in addition to possible mass loss and
re-polymerization during the raw bio-oil volatilization step. Moreover,
the main advantage of the pyrolysis-reforming process lies in its ease
scaling up with continuous feed. Fig. 12 shows a schematic re-
presentation of the two-step pyrolysis-reforming process.
Although the routes described in previous sections such as direct
gasification or bio-oil reforming have been extensively studied in the
literature, the operating problems reported by some authors in these
processes [201,236] have made the two-step process an interesting al-
ternative for H2 production from biomass.
Therefore, the following section focuses on an in-depth review on
this process, in which the most relevant factors affecting product dis-
tribution will be discussed. Among others, the type of the reactor for
both pyrolysis and reforming steps and their configuration plays an
essential role for the process. Therefore, a comparison of the most re-
levant results in the literature using different feeds, catalyst and oper-
ating conditions for the two-stage pyrolysis-reforming process is sum-
marized in Table 4. The results have been arranged according to the
reactor configuration used in each study.
6.1. Reactor configurations
The main reactors used in the literature for biomass pyrolysis are
bubbling fluid beds, circulating fluid beds and transporter beds, ro-
tating cone, ablative reactor, vacuum reactor, screw kiln reactor and
spouted bed reactor [134]. The kind of pyrolysis reactor and its features
are relevant factors for this process, given that they condition the dis-
tribution of pyrolysis products and their yields. Thus, bubbling fluidized
bed reactors are the most developed technology, using sand as flui-
dizing solid because it allows an excellent gas-solid contact, and
therefore improves heat transfer [134]. Moreover, it should be taken
into account that the product stream of the pyrolysis step is the feed of
the subsequent reforming step, which is usually carried out in fixed or
Fig. 12. Schematic representation of the pyrolysis-reforming of biomass.
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Energy Conversion and Management 165 (2018) 696–719
fluidized bed reactors. Although the use of fixed bed reactors is more
extended, fluidized bed reactors avoid operational problems related to
bed blockage by coke deposition in the reforming step [201,236]. Thus,
Fig. 13 shows the different reactor configurations studied in the lit-
erature for this two-step process.
The group headed by Prof. Williams carries out the process in dis-
continuous mode, using a two stage fixed bed reactor (Fig. 13a), in
which the biomass is pyrolyzed in the first stage and the volatiles from
the pyrolysis circulate through the catalytic reforming step, with wood
sawdust and pellets being the feedstock used for most of the studies
[26,27,239,240], although other materials, such as cellulose [241], rice
husk, sugar cane bagasse and wheat straw [242] or biomass/plastic
mixtures [251,252] have also been investigated. This two-stage fixed
bed reactor strategy has also been used by other authors for the pyr-
olysis-reforming of different materials, such as pine wood chip, pig
manure compost, sewage sludge [28,243], cedar wood [253], bagasse
[254] and corncob [246–248]. The process developed by the research
group headed by Prof. Yoshikawa consists also in a two-step pyrolysis-
reforming reactor, in which pyrolysis and reforming zones are also se-
parate [244,245,255].
Although most studies in the literature are carried out in laboratory-
scale batch reactors, Xiao et al. [249] worked in a two stage fluidized-
fixed bed configuration with continuous biomass in the feed, with the
pyrolysis step being carried out in a fluidized bed reactor of silica sand
and the reforming step in a fixed bed reactor on a commercial Ni/Al2O3
and Ni/BCC (brown coal char) bed (Fig. 13b). Wang et al. [256] used a
similar configuration, in which continuous pyrolysis of cellulose was
carried out at the lower section of the reactor (fluidized bed) and the
upper section is the reactor for the catalytic reforming step (fixed bed).
Koike et al. [29] and Li et al. [257,258] studied the pyrolysis-reforming
process in a continuous feed laboratory scale dual-bed reactor, which
includes a primary bed for biomass pyrolysis and a secondary catalyst
bed for the reforming of pyrolysis products. A different reactor con-
figuration was used by Efika et al. [250], which was provided by a
screw-kiln reactor for the continuous biomass pyrolysis and a fixed bed
reactor for the reforming of pyrolysis vapours (Fig. 13c).
Ma et al. [30] improved this two step process introducing another
stage between the pyrolysis and reforming reactors for gas-solid si-
multaneous gasification (Fig. 13d). A different reactor configuration has
been used by Arregi et al. [31,259] for the pyrolysis-catalytic steam
reforming of biomass, in which a spouted bed reactor was used for the
pyrolysis step and the volatile stream leaving this reactor was in-
troduced in a fluidized bed reforming reactor (Fig. 13e). The use of this
configuration has been successfully applied to the valorisation of plas-
tics [234,236,260,261] and biomass/plastic mixtures [262]. Moreover,
this technology has many possibilities for industrial implementation
due to the suitability of the spouted bed for the pyrolysis step
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

Table 4
Studies involving different strategies, feeds, catalysts and operating conditions, and main results obtained (maximum H2 production) reported in the literature for
pyrolysis and in-line reforming of biomass.
Reactor configuration Kind of study Biomass Catalyst Operating conditions H2 concentration H2 production Ref.
(vol%) (wt%)a

Fixed bed/fixed bed Modelling study (1 g) Wood sawdust 10 wt% Ni/Al2O3 TP = 300, 400, 500, 600 °C 38.1 2.2 [26]
(40 °C min−1)
TR = 800 °C
Steam flow rate = 4.74 g h−1 (second
step)
Fixed bed/fixed bed Laboratory scale Wood sawdust Nano Fe-Zn/Al2O3 TP = 500 °C (40 °C min−1) 40.0 1.9 [237]
(0.5 g) Zn/Al ratio: 1:1, 1:2, TR = 800 °C
1:3, 1:4 Steam flow rate = 0.05 g min−1
(second step)
Fixed bed/fixed bed Laboratory scale Wood sawdust Ni/CaAlOx TP = 500 °C (40 °C min−1) 45.0 3.1 [27]
(0.5 g) Ca/Al molar ratio: TR = 800 °C
1:3, 1:2, 1:1, 2:1, 3:1 Steam flow rate = 0.05 g min−1
(second step)
Fixed bed/fixed bed Laboratory scale Wood sawdust Nanosized NiZnAlOx TP = 535 °C (40 °C min−1) 48.1 4.0 [238]
(0.8 g) TR = 800 °C
Steam flow rate = 4.74 ml h−1
Fixed bed/fixed bed Laboratory scale (1 g) Wood sawdust Ca promoted Ni-Mg- TP = 550 °C (40 °C min−1) 53.3 4.3 [239]
AlOx TR = 800 °C
Steam flow rate = 4.74 g h−1
Fixed bed/fixed bed Laboratory scale Wood pellets Acid treated tyre char TP = 500 °C (40 °C min−1) 56 6.1 [240]
TR = 700–900 °C
S/B ratio = 1.82, 3.32, 4.32, 6 g g−1
Fixed bed/fixed bed Laboratory scale Cellulose 15 wt% Ni/Al2O3 TP = – – 5.9 [241]
(1.5 g) TR = 800 °C
Steam flow rate = 0, 0.01, 0.02, 0.1,
0.2 g min−1 (second step)
Fixed bed/fixed bed Laboratory scale (4 g) Rice husk/ Dolomite TP = 950 °C (20 °C min−1) 59.1 5.1 [242]
sugar cane 10 wt% Ni/dolomite TR = 950 °C
bagasse/wheat Steam flow rate = 0.1 g min−1
straw (second step)
Steam/biomass ratio = 1.37
Fixed bed/fixed bed Laboratory scale (1 g) Pine wood Ni-brown coal char TP = 700 °C (10 °C min−1) – 10.0 [28]
chip/pig TR = 450–700 °C
manure
compost
Fixed bed/fixed bed Laboratory scale Sewage sludge Commercial Ni/ TP = 900 °C (10 °C min−1) 70 11.6b [243]
Al2O3 TR = 400–750 °C
Space velocity = 4000–8000 h−1
Steam partial pressure = 30–53 kPa
(second stage)
Fixed bed/fixed bed Bench scale (5 g) Rice husk Raw, char, Fe char, TP = 800 °C 31.5 5.5 [244]
Ni-Fe/char, Ni-Fe TR = 600–900 °C
char and Ni char
Fixed bed/fixed bed Bench scale (20 g) Rice husk RHC Ni TP = 750 °C 24.3 – [245]
TR = 500–900 °C
Fixed bed/fixed bed Laboratory scale (1 g) Corncob Ni – lignite char TP = 900 °C (10 °C min−1) 72.7 12.2b [246]
TR = 500–700 °C
Space velocity = 2400–7200 h−1
Fixed bed/fixed bed Laboratory scale (1 g) Corncob Ni – exchanged resin TP = 900 °C (10 °C min−1) 72.5 12.3b [247]
char TR = 500–700 °C
Space velocity = 2400–7200 h−1
Fixed bed/fixed bed Laboratory scale (1 g) Corncob Limonite TP = 900 °C 70.4 14.8b [248]
TR = 400–750 °C
Space velocity = 2400–7200 h−1
Fluidized bed/fixed Bench scale Pine wood Ni/Al2O3 and Ni- TP = 530–700 °C 60.0 9.3 [249]
bed (1–2 g min−1) chip/pig brown coal char TR = 550–710 °C
manure Space velocity = 9100–11,300 h−1
compost S/C ratio = 0–3 mol/mol (first step)
Screw-kiln/fixed bed Bench scale Wood pellets NiO/Al2O3 TP = 500 °C 44.4 – [250]
(0.24 kg h−1) NiO/CeO2/Al2O3 TR = 760 °C
NiO/SiO2 Biomass feed rate = 0.24 kg h−1
Steam (second step)
Fluidized bed/ Bench scale Timber wood NiO/MgO TP = 600 °C 51.0 7.6 [30]
entrained flow sawdust TG = 700, 750, 800, 850 °C
gasification/fixed TR = 700, 750, 800, 850 °C
bed Steam/biomass ratio = 3 (first step)
Biomass/catalyst ratio = 1
Spouted bed/fluidized Bench scale Pine wood Commercial Ni/ 66.0 11.0 [31]
bed (0.6–1.5 g min−1) sawdust Al2O3 (G90-LDP)
(continued on next page)

710
A. Arregi et al.
Table 4 (continued)
Reactor configuration Kind of study Biomass Catalyst
a
H2 production defined as gH2/100 gbiomass.
b
H2 production defined as gH2/100 gbiomass, daf (dry and ash free).
[263–269]. In fact, this reactor has been satisfactorily scaled up for
continuous pyrolysis of 25 kg h−1 of biomass [270,271]. The ad-
vantages of the conical spouted bed reactor in relation to other pyr-
olysis technologies has been discussed elsewhere [272].
Thus, some of the technologies currently used for the pyrolysis-re-
forming process have some issues to resolve due to the discontinuous
mode of the process. Nevertheless, as described above, great progress
has been made recently, especially for the implementation of con-
tinuous biomass feed integrated into different kinds of reactors and
configurations, with all these improvements contributing to the suc-
cessful scaling up of the process.
6.2. Operating variables
The operating conditions play a vital role in pyrolysis and in-line
reforming of biomass. In this section, the effect of the most significant
operating variables on H2 production (defined as g of H2 per 100 g of
biomass) will be discussed, i.e., reforming temperature, reforming space
time and steam/carbon (S/C) ratio.
6.2.1. Reforming temperature
The product yields obtained in the reforming step depend especially
on the reforming temperature, given that steam reforming of the oxy-
genated compounds and hydrocarbons (CH4 and light hydrocarbons)
produced from biomass pyrolysis are endothermic reactions, and they
are therefore favoured at high temperatures. Nevertheless, the WGS
reaction is an exothermic reaction which is enhanced at low tempera-
tures, and therefore the optimum reforming temperature to enhance H2
production should be found. Consequently, most studies reveal that
high reforming temperatures enhance steam reforming reactions and
lead to high conversion or gas yield and low tar yields [249,258], at the
same time as H2 production is also enhanced (Fig. 14).
Xiao et al. [28] obtained lower tar yields above 600 °C, with the
minimum tar content observing at 700 °C, although the highest H2
production of 10.0 wt% was achieved at 650 °C. Higher activity of the
catalyst was also reported by Koike et al. [29] when temperature was
increased from 550 to 650 °C, with a considerable reduction in the
amount of coke deposited, which is the main deactivation cause of the
catalyst in the pyrolysis-reforming of biomass [219,242,250] and bio-
oil reforming processes [192,195,201,273,274]. Shen et al. [245] also
reported a slight increase in tar conversion efficiency from 92.3 to
100 wt% using RHC Ni catalyst when temperature was increased in the
500–900 °C range.
Concerning H2 production, Waheed and Williams [242] used a high
reforming temperature (950 °C) for the pyrolysis-reforming of rice husk,
sugar cane bagasse and wheat straw, obtaining a maximum H2 pro-
duction of 5.1 wt% when rice husk and wheat straw were fed, whereas
4.9 wt% was obtained with sugar cane bagasse on 10 wt% Ni/dolomite
catalyst, with these values being higher than those obtained with only
dolomite. When pine wood was valorised by Arregi et al. [31] by pyr-
olysis-reforming strategy, an increase in H2 yield was reported when
reforming temperature was increased from 550 to 600 °C, whereas in
711
Energy Conversion and Management 165 (2018) 696–719
Operating conditions H2 concentration H2 production Ref.
(vol%) (wt%)a
TP = 500 °C
TR = 550, 600, 650, 700 °C
Space time = 2.5, 5, 10, 15, 20,
30 gcat min gvolatiles−1
Steam flow rate = 3 ml min−1 (first
step)
S/C ratio = 3.9, 5.8, 7.7, 9.7
the 600–700 °C range H2 production kept at around 11.0 wt%.
In the same way, by increasing the reforming temperature, the
concentrations of H2 and CO in the gaseous stream increase, which is
explained by the endothermic nature of the reforming reactions (for
both oxygenated compounds and CH4). Cao et al. [243] obtained a H2
concentration of 66.6 vol% at 500 °C on a commercial Ni/Al2O3 cata-
lyst, with the maximum value being 70.0 vol% when a temperature of
550 °C was used, although the maximum H2 production (11.6 wt%) was
obtained at a temperature of 650 °C. The importance of the exothermic
WGS reaction should be noted, given that it plays an essential role in
this process and is favoured at relatively low temperatures, producing
H2 and CO2 as main products. Thus, Arregi et al. [31] reported similar
H2 concentration (of around 66 vol%) in the 550–700 °C range, al-
though a slight decrease in CO2 and, especially, an increase in CO
concentration was observed.
6.2.2. Space time
The reforming space time is another important factor in order to
ensure a tar-free gas product to be used for different applications. When
space time is increased, steam reforming and WGS reactions are en-
hanced, favouring the formation of H2 and CO2 and hindering that of
CO. This conclusion was reported by Xiao et al. [249], who observed a
slight increase in H2 production from 6.2 to 7.3 wt% and in CO2 from
70.0 to 87.1 wt% when space velocity was reduced from 11,000 to
9,200 h−1, whereas CO and CH4 decrease from 23.0 to 19.9 wt% and
from 9.1 to 2.9 wt%, respectively. Cao et al. [243] also observed that
higher total gas yield and H2 production were obtained and lower coke
was deposited on the catalyst when space time was increased. Higher
tar reforming efficiency was reported by Shen et al. [245], which in-
creased from 50.1 to 99.8% when catalyst mass was increased from 3 to
10 g, using a RHC Ni catalyst and a reforming temperature of 700 °C.
Moreover, this catalyst is highly stable, as evidenced by the almost
constant tar reforming efficiency (99.6%) after 5 reforming cycles. The
influence of space time between 2.5 and 30 gcatalyst min gvolatiles−1 using
a commercial Ni/Al2O3 catalyst was studied by Arregi et al. [31], who
reported a high H2 production of 11.7 wt% by displacing the WGS re-
action and at the same time reforming CH4 and light hydrocarbons.
6.2.3. Steam to C ratio
Amongst the different reforming agents, steam is one of the most
used in the literature and the S/C ratio is a relevant factor in reforming
processes. Efika et al. [250] studied the reforming process without and
with steam, and the enhancement of gas yield with steam addition was
reported, increasing from 40.5 to 45.3 wt% without catalyst and to
54.0 wt% when NiO/SiO2 catalyst was used. Moreover, H2 concentra-
tion increased from 14.0 (sand without steam) to 18.2 vol% (sand with
steam) and to 44.4 vol% when NiO/Al2O3 catalyst was used. Cao et al.
[243] also studied the effect of steam partial pressure (SPP) between 30
and 53 kPa, obtaining a higher H2 yield and lower carbon deposition at
high steam partial pressure values.
Moreover, higher H2 and CO2 and lower CO and CH4 yields are
obtained by increasing S/C ratio due especially to the displacement of
A. Arregi et al.
Fig. 13. Reactor configurations for pyrolysis and in-line catalytic steam reforming of biomass: (a) two-stage fixed bed reactor; (b) fluidized – fixed bed reactor; (c)
screw kiln – fixed bed reactor; (d) fluidized bed, entrained flow and fixed bed reactor, and; (e) spouted bed – fluidized bed reactor.
Fig. 14. Effect of temperature on hydrogen production in pyrolysis-reforming
studies. Xiao et al., 2013 [28]; Ma et al., 2014 [30]; Arregi et al., 2016 [31].
the WGS reaction equilibrium. A significant effect was reported by
Arregi et al. [31] when they increased S/C ratio between 3.9 and 9.7,
i.e., H2 yield increased from 89.2 to 94.2% and CO2 yield from 84.0 to
712
Energy Conversion and Management 165 (2018) 696–719
90.1%, whereas CO decreased from 14.4 to 8.9% in the same S/C ratio
range. Zou et al. [241] studied the influence of steam addition between
0 and 0.2 g min−1, obtaining a maximum H2 production of 5.9 wt%
between 0.05 and 0.1 g min−1 of steam addition, without any im-
provement above this value.
Thus, when steam to C ratio is increased, higher H2 production in
the gaseous fraction and lower tar content (non-converted product) are
obtained, given that steam enhances both reforming and WGS reac-
tions, although higher S/C ratio requires higher external heat supply
[249]. Therefore, the optimization of this factor is necessary in order to
obtain an economically viable process.
6.3. Catalysts
Although different catalysts can be used for reforming of oxyge-
nated compounds, the most used ones are those based on Ni and Co due
mainly to its low cost in relation to noble metals, such as, Pt, Pd, Ru or
Rh. Efika et al. [250] investigated three different catalysts: NiO/Al2O3,
NiO/CeO2/Al2O3 and NiO/SiO2 (prepared by an incipient wetness
method and by a sol-gel method). The sol-gel NiO/SiO2 catalyst pro-
duced the highest gas yield, whereas NiO/CeO2/Al2O3 was the catalyst
with the lowest gas production. Nevertheless, NiO/Al2O3 was the cat-
alyst giving the highest H2 concentration of 44.4 vol%. Koike et al. [29]
compared three different catalysts and the lower coke formation was
observed for Ni + MnOx/Al2O3 followed by Ni + CeO2/Al2O3 and Ni/
Al2O3 catalysts. Li et al. [258] investigated Ni-Cu/Mg/Al bimetallic
A. Arregi et al. Energy Conversion and Management 165 (2018) 696–719

catalysts with different Cu/Ni ratios, obtaining higher activity and

reduce its deactivation, improve its stability

Optimization of conditions in pyrolysis and
lower deactivation by coke when Cu/Ni ratio was 0.25, with the results

Small units in centralized plants in the

Two-step biomass pyrolysis-reforming

Optimize the catalyst composition to

Lower temperature than gasification
being better compared to monometallic Ni/Mg/Al and Cu/Mg/Al cat-

regions where biomass is available

alysts. Chen et al. [237] studied Fe-Zn/Al2O3 nanocatalysts with dif-

Avoids bio-oil feeding problems

ferent Zn/Al ratios (1:1, 1:2, 1:3 and 1:4), and a maximum H2 con-

Tar-free product is obtained

and catalyst regeneration

centration and production of 40 vol% and 1.9 wt%, respectively, were

catalytic reforming steps

Continuous regime: 10 g

Scale up of the process

obtained when 1:1 ratio was used. They have also investigated Ni/
CaAlOx catalysts with different Ca/Al molar ratios (1:3, 1:2, 1:1, 2:1

Batch regime: 5 g
and 3:1) [27] and H2 concentration and production of 45 vol% and
3.1 wt%, respectively, were obtained when a Ca/Al molar ratio of 1:2
was used. Dong et al. [238] synthesized NiZnAlOx catalysts with dif-
ferent Ni molar fractions (5, 10, 15, 25 and 35%), obtaining the max-
imum H2 production (4.0 wt%) when 35% Ni was used.

Lower energy efficiency and higher

Concerning catalyst supports, although Al2O3 is commonly used,

coupled with a centralized bio-oil

Higher energy density of the bio-

different kinds of supports can be found in the literature. Li et al. [257]

Decentralized pyrolysis plant

reported a higher activity for Co catalyst when they are supported on

Technological development
slurry compared to bio-oil
BaAl12O19 than on other supports, such as Al2O3, ZrO2, SiO2, MgO and

Reduce energetic costs

TiO2 due to its high dispersion. Moreover, Waheed et al. [275] used a

Raw bio-oil feeding

Bio-oil gasification

gasification plant
10 wt% Ni-dolomite catalyst, obtaining a maximum H2 production of
6.1 wt% when rice husk was fed. Ye et al. [276] studied size-confined Ni
catalysts on acidic MCM-41 supports and obtained a maximum H2
production of 4.3 wt%. Jin et al. [239] studied the effect calcium ad-

costs
3a g
dition has on Ni-Mg-AlOx catalyst and observed that H2 production
increased from 2.1 to 3.6 wt%. Santamaria et al. [277] compared five

reduce its deactivation, improve its stability

Decentralized pyrolysis plant coupled with
different supports (Al2O3, SiO2, MgO, TiO2 and ZrO2) and Al2O3, MgO

Feeding lost in bio-oil condensation and

and ZrO2 were those leading to the most encouraging results.

Optimize the catalyst composition to

a centralized bio-oil reforming plant

Lower temperature than gasification

Higher energy density of the bio-oil
Furthermore, the use of char is gaining increasing attention recently
and several studies using it as support have been published. Thus, Xiao
et al. [249] compared a commercial Ni/Al2O3 catalyst and Ni/BCC

and catalyst regeneration

Comparison study of different strategies for hydrogen production from biomass and bio-oil by thermochemical processes.

Scale up of the process

(brown coal char), and higher H2, CO and CH4 yields, lower tar content

compared to biomass

Raw bio-oil feeding

volatilization steps
and higher resistance to coke deposition were observed when Ni/BCC
Raw bio-oil: 10a g
Bio-oil reforming

catalyst was used. Yao et al. [278] used biochar as a catalyst in the

(600–800 °C)
pyrolysis-reforming of wheat straw, obtaining a maximum H2 con-
centration and production of 64.02 vol% and 9.21 wt%, respectively.
The group headed by Prof. Yoshikawa also studied Ni-Fe catalysts [244]
and Ni catalysts [245,255] supported on rice husk char (RHC). They
reported higher tar removal efficiency with RHC Ni and RHC Ni-B

Technological development
Treatment of biomass with

High energy consumption

Unfeasible at large scale

catalysts, 96.9 and 98.6%, respectively, compared to Ni-Fe char cata-

Difficulties in feedstock

Reduce energetic costs

high moisture content
Without catalyst: 2 g

lyst, for which a maximum efficiency of 92.3% was achieved. It should

Supercritical water

With catalyst: 4 g

be pointed out that the recovery of the char from the pyrolysis step is of
great interest for the viability of the process.
gasification

pumping

7. Main remarks and conclusions

Table 5 compares different routes for H2 production from biomass

Unsuitable tar content even with secondary

and bio-oil by thermochemical processes. Considering the different re-

Centralized plants in the regions where

Optimize the catalyst composition to

actor configurations, plant size, operating conditions and catalysts used

catalysts for its further utilization in

Reduce energetic and material costs

reduce its deactivation, improve its
stability and catalyst regeneration
High temperatures (700–1200 °C)

in the processes studied in the literature, it is difficult to compare the H2

Calculated considering a bio-oil yield of 75 wt% [134].

production obtained by the different routes. In addition, it should be

Biomass steam gasification

pointed out that the values of H2 production mentioned in the previous

Decrease the tar content

sections have been calculated based using different feeds (based on

Without catalyst: 4 g

biomass is available

synthesis processes

100 g of biomass, bio-oil or organics). Consequently, an average H2

With catalyst: 7 g

production (wt%) based on 100 g of biomass has been calculated for all
the processes using the results obtained in the literature. In the pro-
cesses in which bio-oil is in the feed, H2 production has been calculated
considering a bio-oil yield of 75 wt% in the pyrolysis step [134]; that is,
the bio-oil lost in the condensation and vaporization processes not been
Advantages and disadvantages
Average H2 production (wt%,

considered in the calculation, which would decrease the production of

H2 in these processes. Moreover, biomass heterogeneity is a fact to be
g H2/100 g biomass)

taken into account. Thus, biomass type, particle size, moisture content
and ash composition are different in each study and so the values
showed in Table 5 are average values calculated from the literature. As
observed in Table 5, supercritical water gasification and bio-oil gasifi-
Challenges
Strategy

cation are the routes in which the lowest H2 production have been
Table 5

obtained, 4 g and 3 g of H2 per 100 g of biomass, respectively. It should

a

be pointed out that these routes have been scarcely studied in the

713
A. Arregi et al.
literature, and therefore their technology is less developed than those of
the other routes. Although supercritical water gasification can treat
biomass with high moisture content, this process has several drawbacks
involving biomass feeding and high energy costs, which makes it un-
feasible at large scale. In the case of bio-oil gasification, the higher
energy density of the bio-slurry compared to bio-oil is an interesting
advantage, although bio-oil feeding problems, low energy efficiency
and high energy costs explain the low technological development of this
process.
Biomass steam gasification is one of the main thermochemical
routes studied in the literature, achieving an average H2 production of
4 g (without catalyst) and 7 g (with catalyst) per 100 g of biomass. The
need of a secondary catalyst in the gasification process is noteworthy,
as evidenced by the low H2 production obtained with a primary cata-
lyst, which complicates the gasification process and increases energy
costs due to the high temperatures needed in both steps. The major
challenge of biomass gasification is tar reduction, given that tar causes
serious problems for syngas further use in synthesis, even when sec-
ondary catalysts are used. Therefore, optimization of the catalyst is
imperative in order to improve its stability and regeneration.
Concerning raw bio-oil steam reforming, which has also been ex-
tensively studied in the literature, an average H2 production of 10 g per
100 g of biomass has been achieved. The higher energy density of the
bio-oil compared to biomass and the lower temperatures needed for its
reforming compared to biomass gasification make it an interesting
strategy for bio-oil valorisation, although the scaling up of the process is
its major challenge nowadays. Moreover, as mentioned above, bio-oil
feeding still involves drawbacks because part of the bio-oil is lost in the
condensation and volatilization steps. Comparing both strategies, bio-
mass gasification is carried out in large centralized plants located in the
regions where biomass is available, whereas in the bio-oil reforming
strategy, biomass pyrolysis is carried out in decentralized small pyr-
olysis plants and the bio-oil is transported to centralized bio-oil re-
forming plants, thereby reducing the transportation costs due to the
higher energy density of the bio-oil compared to biomass. Nevertheless,
the technology for biomass gasification is more developed than that for
bio-oil reforming, which is still in a preliminary phase.
Furthermore, the results obtained in the two-step pyrolysis-re-
forming of biomass are encouraging as an alternative way of biomass
gasification and bio-oil reforming for H2 production, achieving an
average H2 production of 10 g per 100 g of biomass. This route allows
optimizing both pyrolysis and reforming steps and avoids the problems
related to raw bio-oil feeding. The main advantage of this process is that
a free-tar product is obtained, which is the biggest challenge of biomass
gasification. Moreover, it is a good strategy in the areas in which bio-
mass is available, although there are still issues to be resolved. The
deactivation of the catalyst and, especially, its stability are essential in
order to scale up this process, although few studies in the literature deal
with the deactivation of the catalyst and its influence on product dis-
tribution. Moreover, although different kinds of metal phases, supports
and promoters have been used, there are no studies in which their re-
generation by coke combustion or steam gasification has been carried
out, with these aspects being highly relevant for future studies.
Therefore, the two-step process is a different route for H2 produc-
tion, which may be a good alternative for gasification and bio-oil re-
forming processes. Moreover, easy scaling up is the main advantage of
the pyrolysis and in-line reforming process, which in turn avoids
transportation of the bio-oil needed in the bio-oil reforming process.
Nevertheless, the use of one or another strategy depends on the area in
which it will be installed, their technological development and the
measures taken in order to resolve the problems mentioned above.
Acknowledgments
This work was carried out with financial support from the Ministry
of Economy and Competitiveness of the Spanish Government
714
Energy Conversion and Management 165 (2018) 696–719
(CTQ2016-75535-R (AEI/FEDER, UE) and CTQ2015-69436-R
(MINECO/FEDER, UE)), the Basque Government (IT748-13) and the
University of the Basque Country (UFI 11/39). Aitor Arregi thanks the
University of the Basque Country for his postgraduate grant (UPV/EHU
2017).
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