i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6

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Hydrogen production through biomass gasification

in supercritical water: A review from exergy aspect

Yaning Zhang*, Liqing Li, Pingfei Xu, Bingxu Liu, Yong Shuai**, Bingxi Li***
School of Energy Science and Engineering, Harbin Institute of Technology (HIT), 92 West Dazhi Street, Harbin,
Heilongjiang 150001, China

article info abstract

Article history: Hydrogen production through supercritical water gasification (SWG) of biomass has been
Received 1 November 2018 widely studied. This study reviews the main factors from exergy aspect, and these include
Received in revised form feedstock characteristics, biomass concentration, gasification temperature, residence time,
12 January 2019 reaction catalyst, and reactor pressure. The results show that the exergy efficiencies of
Accepted 15 January 2019 hydrogen production are mainly in the range of 0.04e42.05%. Biomass feedstock may affect
Available online 14 February 2019 hydrogen production by changing the H2 yield and the heating value of biomass. Increases
in biomass concentrations decrease the exergy efficiencies, increases in gasification tem-
Keywords: peratures generally increase the exergy efficiencies, and increases in residence times may
Hydrogen production initially increase and finally decrease the exergy efficiencies. Reaction catalysts also have
Biomass gasification positive effects on the exergy efficiencies, and the reviewed results show that the effects
Supercritical water are followed KOH > K2CO3 > NaOH > Na2CO3. Reactor pressure may have positive, negative
Exergy analysis or negligible effects on the exergy efficiencies.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Generally, hydrogen can be produced through ways

Introduction
Hydrogen (H2) is an important energy source in our economy,
and it attracts significant interests of scientific researchers
and policy makers all over the world. These are due to the
advantages that hydrogen: (a) is non-toxic, (b) is clean, (c) has
high heating value (on mass basis), (d) has versatile applica-
tions (in food, petrochemical, microelectronics, polymer syn-
thesis, metallurgical process, etc.), (e) produces non-toxic
emissions (only water left), (f) the original materials may be
renewable, (g) many existing technologies can be used, (h) can
be easily transported (through pipelines), (i) can be safely
stored (for very long time), etc. [1e3].
including: (a) water electrolysis, (b) solar light photo-
electrolysis, (c) natural gas steam reforming, (d) coal or
biomass gasification, etc. [4,5]. Among these methods, biomass
gasification is of significant interests due to the reasons that (a)
the process is fast, (b) the process is efficient, (c) biomass is
environment friendly, (d) biomass is renewable, etc. [6,7].
Recently, hydrogen production through supercritical water
gasification (SWG) was developed and caught enormous
attention because: (a) supercritical water is at a special state
(temperature is higher than 374
C and pressure is higher than
22.1 MPa), (b) the solubility is high, (c) the reactivity is high, (d)
the diffusivity is high, (e) the dielectric constant is low, (f) the
viscosity is low, (g) the polarity is weak, (h) the hydrogen

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: ynzhang@hit.edu.cn (Y. Zhang), shuaiyong@hit.edu.cn (Y. Shuai), libx@hit.edu.cn (B. Li).
https://doi.org/10.1016/j.ijhydene.2019.01.151
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
15728 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6

bonds are weak, (i) it dissolves organic matters, (j) it dissolves material, reactor pressure, gasification temperature, reaction
gaseous products, (k) it favors hydrolysis reactions, (l) the re- time, and feedstock concentration. Guo et al. [40] reviewed the
actions involved can be performed in low temperature at- catalysts used for SWG of biomass for hydrogen production.
mosphere and no catalyst is required, (m) the low temperature Azadi and Farnood [41] reviewed the heterogeneous catalysts
atmosphere inhibits the formation of NOx and SOx, (n) the used for sub- and supercritical water gasification of biomass
produced CO2 can be separated through controlling the tem- and wastes for hydrogen production. However, no reviews
peratures and pressures in downstream units and processes, have been conducted on the exergy analysis of hydrogen
etc. [8e11]. Therefore, SWG has been widely studied to pro- production through SWG of biomass. This study was therefore
duce hydrogen, the used materials include coal [12], lignite to review hydrogen production through SWG of biomass from
[13], glycerol [3], indole [14], guaiacol [15], furfural [16], exergy aspect. After the exergy method is presented, the ef-
dimethylhydrazine [17], black liquor [18], polycyclic aromatic fects of feedstock characteristics, biomass concentration,
hydrocarbon [19], etc. gasification temperature, residence time, reaction catalyst,
Exergy is the maximum work obtainable when a material and reactor pressure on the exergy efficiencies of hydrogen
or matter is brought to a state of thermodynamic equilibrium production are detailed.
with the common components of natural surroundings by
means of reversible processes [20]. Together with energy,
exergy is also an important tool for evaluating energy mate- Exergy analysis
rials and systems [21,22]. Compared with the traditional en-
ergy analysis which uses the conservation of energy principle Exergy of hydrogen
(embodied in the first law of thermodynamics), exergy anal-
ysis uses the conservation of energy principle (embodied in The exergy of hydrogen includes four exergy forms [7]:
the first law of thermodynamics) together with non-
conservation of entropy principle (embodied in the second Ex ¼ Exki þ Expo þ Exph þ Exch (1)
law of thermodynamics) for the analysis, design, and where:
improvement of energy sources and systems [21,23]. Gener-
ally, exergy analysis is more meaningful and useful than en- Ex: exergy of H2 (kJ/kg)
ergy analysis and it provides more insights in efficiency Exki: kinetic exergy of H2 (kJ/kg)
assessment [24,25]. These are due to the facts that exergy is a Expo: potential exergy of H2 (kJ/kg)
measure of the approach to the ideal condition and it quan- Exph: physical exergy of H2 (kJ/kg)
tifies the locations, types, and magnitudes of wastes and los- Exch: chemical exergy of H2 (kJ/kg)
ses [26,27].
Exergy analysis has been widely used to assess or evaluate If we neglect the kinetic exergy and potential exergy which
hydrogen production/conversion, i.e., hydrogen production/ are very small parts of the total exergy (2.0E-8 ~ 7.0E-5 and
conversion in fuel cell [28], biomass-based system [29], solid 2.0E-7 ~ 9.0E-5, respectively [42]) [22,43], equation (1) results
oxide electrolyser [30], solid oxide electrolysis cell [31], com- in [29]:
bined photovoltaic/thermal (PV/T) fuel cell [32], combined
solid oxide fuel cell and electrolyser cell [33], integrated Ex ¼ Exph þ Exch (2)
photovoltaic system [34], integrated geothermal energy-based
The physical exergy of H2 is calculated through [44]:
system [35], integrated underground coal gasification with
SOFC (solid oxide fuel cell) fuel cell system [36], etc. Exph ¼ n½ðh  h0 Þ  T0 ðs  s0 Þ (3)
Hydrogen production through SWG of biomass has also
where:
been widely studied. These mainly include the hydrogen
production as affected by biomass characteristics, biomass
n: molar yield of H2 (mol/kg)
concentration, gasification temperature, residence time, re-
h: specific enthalpy of H2 at arbitrary temperatures (kJ/
action catalyst, reactor pressure, etc. Even some reviews have
kmol)
been published. Kalinci et al. [37] reviewed the various pro-
h0: specific enthalpy of H2 in the environment (8468 kJ/kmol
cesses used for conversion of biomass into hydrogen, and
[45])
these included pyrolysis, conventional gasification, super-
T0: environmental temperature (298.15 K)
critical water gasification (SCWG), fermentation, photosyn-
s: specific entropy of H2 at arbitrary temperatures (kJ/
thesis, biological water gas shift reactions (BWGS). Reddy et al.
kmol K)
[38] compared the degradation routes of biomass model
s0: specific entropy of H2 in the environment (130.574 kJ/
compounds (i.e., cellulose, glycerol, and lignin) at near and
kmol K [45])
supercritical conditions. The effects of operating parameters
on hydrogen production from SWG of biomass were also
The chemical exergy of H2 is [44]:
reviewed, and these mainly included gasification tempera-
ture, reactor pressure, feedstock concentration, reaction time, Exch ¼ nexch (4)
H2
reaction catalyst, and reactor configuration. Correa and Kruse
[39] reviewed the main factors influencing hydrogen produc- where:
tion from SWG of biomass, and these mainly included
biomass compositions, heterogeneous catalyst, reactor exch
H2 : standard chemical exergy of H2 (236100 kJ/kmol [46])
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Exergy of biomass
Many equations can be used to estimate the chemical exergy
of a biomass [20,47,48]. For an easy and also reliable estima-
tion [49,50], the following equation can be used to calculate
the chemical exergy of biomass [51]:
exbiomass ¼ bLHV
pressure are the main factors affecting the hydrogen pro-
duction processes and results, they are therefore detailed in
this study. The other minor factors can be referred to in the
other publications, i.e., biomass to water (BTW) ratio [56,57],
oxidant equivalent ratio (ER) [6], etc.
Effect of feedstock characteristics
(5)

where: Table 1 shows the H2 yields and exergy efficiencies of SWG of

different biomass feedstocks. Gong et al. [58] studied
exbiomass: exergy of biomass (kJ/kg) hydrogen production from SWG of different dewatered
b: correlation factor sewage sludges (B, C, D, and E) at reactor pressure of 22.1 MPa,
LHV: lower heating value of biomass (kJ/kg) gasification temperature of 400
C, and residence time of
10 min. The results showed that sludge D had the highest
b can be calculated through [20,52]: exergy efficiency (2.55%), this was mainly because sludge D
had the highest H2 yield (0.9 mol/kg). According to equation
1:044 þ 0:0160H=C  0:3493O=Cð1 þ 0:0531H=CÞ þ 0:0493N=C (5), the higher heating value of a fuel would make a higher
b¼
1  0:4124O=C chemical exergy for the fuel. According to equation (9), the
(6) higher chemical exergy of a fuel would make a lower exergy
where: efficiency for the hydrogen production process. Sludge C
showed the lowest exergy efficiency (0.70%) was mainly
C: weight fraction of carbon (%) because it had the highest exergy value (13.52 mol/kg) which
H: weight fraction of hydrogen (%) was mainly resulted from its highest HHV (12.60 MJ/kg).
O: weight fraction of oxygen (%) Nanda et al. [56] studied hydrogen production from SWG of
N: weight fraction of nitrogen (%) different fruit and food wastes (aloe vera rind, banana, orange
peel, lemon peel, pineapple peel, coconut shell, and sugarcane
The higher heating value (HHV) of a biomass fuel can be bagasse) at the pressures of 23e25 MPa, gasification temper-
measured directly, or it can be estimated through the modified ature of 600
C, and residence time of 45 min. The results
Dulong's formula [53]: showed that banana had the lowest exergy efficiency (2.31%)
whereas coconut shell had the highest exergy efficiency
HHV ¼ ð0:3393  CÞ þ ½1:443  ðH  O=8Þ þ ð0:01494  NÞ (7) (3.30%). These were mainly because banana had the lowest H2
yield (1.52 mol/kg) whereas coconut shell had the highest H2
The LHV of a biomass fuel can then be calculated through
yield (2.17 mol/kg).
the following relationship [20,54]:
Yanik et al. [59] studied hydrogen production from SWG of
HHV ¼ LHV þ 21:97H (8) different biomass feedstocks (corncob, corn stalk, oreganum
stalk, cotton stalk, sunflower stalk, tobacco stalk, vegetable
where:
waste, and chromium-tanned) at gasification temperature of
500
C and residence time of 60 min. The results showed that
HHV: higher heating value of biomass (MJ/kg)
tobacco stalk resulted in the highest exergy efficiency (6.78%)
LHV: lower heating value of biomass (MJ/kg)
whereas chromium-tanned gave the lowest exergy efficiency
(2.09%). These were mainly because tobacco stalk had the
highest H2 yield (4.81 mol/kg) whereas chromium-tanned had
Exergy efficiency
the lowest H2 yield (1.46 mol/kg). It should be noted that
sunflower stalk produced lower H2 yield (3.69 mol/kg) than
The exergy efficiency of hydrogen production can be defined
vegetable waste (3.96 mol/kg), oreganum stalk (4.13 mol/kg),
by [55]:
and cotton stalk (4.19 mol/kg), whereas it had higher exergy
ExH2 efficiency (5.93%) than vegetable waste (4.93%), oreganum
h¼  100% (9)
Exbiomass stalk (5.57%), and cotton stalk (5.92%). These were mainly due
where: to the facts that sunflower stalk had lower LHV (12.83 MJ/kg)
than vegetable waste (16.90 MJ/kg), oreganum stalk (15.42 MJ/
h: exergy efficiency (%) kg), and cotton stalk (13.85 MJ/kg), making sunflower stalk
ExH2: exergy of H2 (kJ/kg biomass) have lower exergy (14.75 MJ/kg) than vegetable waste
Exbiomass: exergy of biomass (kJ/kg biomass) (19.07 MJ/kg), oreganum stalk (17.58 MJ/kg), and cotton stalk
(16.01 MJ/kg).
Generally, the exergy efficiency of hydrogen production
from SWG of a biomass feedstock is mainly determined by (a)
Results and discussion the H2 yield (the higher H2 yield the higher exergy efficiency),
and (b) the heating value of biomass (a lower heating value
Feedstock characteristics, biomass concentration, gasification makes a higher exergy efficiency, and this can be seen from
temperature, residence time, reaction catalyst, and reactor the definition in equation (9)). Because some other fuels may
15730 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6

Table 1 e Hydrogen production from supercritical water gasification of different biomass feedstocks.
Fuel H2 (mol/kg) Exergy efficiency (%) Conditions Reference
Sludge C 0.4 0.70 22.1 MPa, 400
C, 10 min [58]
Sludge E 0.4 0.79 22.1 MPa, 400
C, 10 min [58]
Sludge D 0.9 2.55 22.1 MPa, 400
C, 10 min [58]
Banana 1.52 2.31 23e25 Mpa, 600
C, 45 min [56]
Lemon peel 1.55 2.36 23e25 Mpa, 600
C, 45 min [56]
Orange peel 1.62 2.47 23e25 Mpa, 600
C, 45 min [56]
Pineapple peel 1.62 2.47 23e25 Mpa, 600
C, 45 min [56]
Sugarcane bagasse 1.66 2.53 23e25 Mpa, 600
C, 45 min [56]
Aloe vera rind 1.67 2.54 23e25 Mpa, 600
C, 45 min [56]
Coconut shell 2.17 3.30 23e25 Mpa, 600
C, 45 min [56]
Chromium-tanned 1.46 2.09 500
C, 60 min [59]
Corncob 2.13 2.83 500
C, 60 min [59]
Vegetable waste 3.96 4.93 500
C, 60 min [59]
Oreganum stalk 4.13 5.57 500
C, 60 min [59]
Cotton stalk 4.19 5.92 500
C, 60 min [59]
Sunflower stalk 3.69 5.93 500
C, 60 min [59]
Corn stalk 4.15 6.16 500
C, 60 min [59]
Tobacco stalk 4.81 6.78 500
C, 60 min [59]

produce much higher H2 yields, much higher exergy effi-
ciencies may be obtained, i.e., a coal had a H2 yield of
88.71 mol/kg and the exergy efficiency was 69.97% [60], a
semicoke had a H2 yield of 85.89 mol/kg and the exergy effi-
ciency was 83.06% [61].
water (374
C), supercritical water (SCW) would act as a
medium with complete solubility of organic compounds [69].
In this case, less ionic products would be formed according
to the free-radical mechanism, thereby resulting in higher H2
yields [56].

Effect of biomass concentration

Table 2 e Hydrogen production from supercritical water
For hydrogen production in a supercritical water biomass gasification of biomass at different biomass
gasification process, biomass concentration is also a very concentrations.
important factor. Fuel Biomass H2 yield Exergy
Table 2 shows the H2 yields and exergy efficiencies of SWG concentration (wt%) (mol/kg) efficiency (%)
of biomass at different concentrations. Nanda et al. [62]
Pinecone (23 Mpa, 550
C, 30 min) [62]
studied hydrogen production from SWG of pinecone at 10 1.18 1.25
different concentrations (10, 15, 20, and 25 wt%). The results 15 0.98 1.05
showed that when the concentration was increased from 20 0.83 0.88
10 wt% to 25 wt% (1.5 times in increase), the exergy efficiency 25 0.83 0.89
generally decreased from 1.25% to 0.88% (29.6% in decrease). Sugarcane bagasse (24 MPa, 400
C, 20 min) [63]
1 6.54 5.54
These decreases were mainly due to the facts that higher
2 4.03 3.41
biomass concentrations led to lower water fractions which 4 2.42 2.05
lowered (a) the water-gas shift reaction (H2O þ CO 4 Sewage sludge (25 MPa, 540
C) [64]
H2 þ CO2) and (b) the steam reforming reactions (CnHm þ n H2O 4 9.23 13.53
4 n CO þ (n þ m/2) H2), thereby decreasing the H2 yields 7 4.91 7.20
(0.83e1.18 mol/kg) [62,68]. Increases in biomass concentra- 10 3.03 4.45
12 1.89 2.77
tions resulted in decreases in the exergy efficiencies were also
Almond shell (27 MPa, 460
C, 10 min) [65]
observed from the results reported by Rashidi and Tavasoli
1 7.86 9.11
[63] for sugarcane bagasse, by Chen et al. [64] for sewage 2 4.35 5.04
sludge, by Safari et al. [65] for almond shell, by Lu et al. [66] for 3 3.03 3.51
corn cob, and by Cao et al. [67] for chicken manure. Corn cob (25 MPa, 650
C) [66]
5 12.0 15.38
Effect of gasification temperature 7 9.1 11.71
10 7.9 10.10
12.5 6.2 7.96
For hydrogen production of a supercritical water biomass
14.5 4.7 6.00
gasification process, gasification temperature is also a very 18 3.8 4.88
important factor. Because the hydrogen production reactions Chicken manure (24 MPa, 580
C) [67]
(i.e., water-gas shift reaction: H2O þ CO 4 H2 þ CO2) are 3 20.07 37.97
endothermic reactions, a higher gasification temperature 6 18.07 34.19
favors the production of hydrogen [56]. Also, if the gasifica- 9 17.49 33.08
12 15.84 29.96
tion temperature is higher than the critical temperature of
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Table 3 shows the H2 yields and exergy efficiencies of SWG resulted from the continuous increases in the H2 yields
of different biomass feedstocks at different gasification tem- (0e0.80 mol/kg). Nanda et al. also studied hydrogen produc-
peratures. Nanda et al. [62] studied hydrogen production from tion from SWG of different biomass feedstocks (timothy grass
SWG of pinecone at different gasification temperatures (300, [69], orange peel [56], pinewood [70], wheat straw [70], and
350, 370, 450, and 550
C). The results showed that as the horse manure [71]) at different gasification temperatures (300,
gasification temperature was increased in the range of 400, 450, 500, 550, 600, and 650
C), the results also showed
300e550
C (83.33% in increase), the exergy efficiency increases in the exergy efficiencies when the gasification
increased from 0% to 0.85%. These increases were mainly temperatures were increased. Increases in the gasification
temperatures resulted in increases in the exergy efficiencies
were also observed from the results reported by Safari et al.
Table 3 e Hydrogen production from supercritical water [65] for almond shell, by Lu et al. [66] for corn cob, by Chen
gasification of biomass at different gasification et al. [64] for sewage sludge, and by Cao et al. [67] for chicken
temperatures. manure.
Fuel Temperature H2 yield Exergy Generally, increases in the gasification temperatures
(oC) (mol/kg) efficiency (%) would result in significant increases in the exergy efficiencies.
Peat (peat/water ratio 0.01, 60 min) [57] However, Xu and Donald [57] studied hydrogen production
350 0.19 0.19 from SWG of peat at different gasification temperatures (350,
380 0.21 0.22 380, 410, and 440
C). The results showed that as the gasifi-
410 0.05 0.05 cation temperature increased in the range (350e440
C), the
440 0.16 0.17
exergy efficiency fluctuated between 0.05% and 0.22%. These
Pinecone (concentration 25 wt%, 23 Mpa, 30 min) [62]
were mainly resulted from the fluctuations in the H2 yields as
300 0 0
350 0.06 0.06 shown in Table 3 (0.05e0.21 mol/kg).
370 0.09 0.09
450 0.61 0.64 Effect of residence time
550 0.80 0.85
Orange peel (biomass/water ratio 1:5, 23e25 Mpa, 45min) [56] Table 4 shows the H2 yields and exergy efficiencies of SWG of
400 0.08 0.10
different biomass feedstocks at different residence times.
500 0.58 0.78
Nanda et al. [62] studied hydrogen production from SWG of
600 0.91 1.22
Pinewood (biomass/water ratio 1:10, 23e25 MPa, 45 min) [70] pinecone at different residence times (15, 30, 45, and 60 min).
300 0.22 0.26 The results showed that as the residence time was increased
400 0.69 0.79 in the range of 15e60 min (3 times in increase), the exergy
500 1.14 1.31 efficiency increased from 0.57% to 1.46% (1.56 times in
Horse manure (biomass/water ratio 1:10, 23e25 MPa, 45 min) [71] increase).
400 0.26 0.37
It is reported that longer residence time at high gasification
500 0.91 1.30
600 1.87 2.92
temperatures would favor hydrogen production for SWG of
Wheat straw (biomass/water ratio 1:10, 23e25 MPa, 45 min) [70] biomass through dehydration, deamination, bond cleavage,
300 0.42 0.50 decomposition, decarboxylation and depolymerisation
400 1.88 2.25 [73,74]. Nanda et al. studied hydrogen production from SWG of
500 3.71 4.45 different biomass feedstocks (timothy grass [69], orange peel
Timothy grass (biomass/water ratio 1:8, 23e25Mpa, 45min) [69]
[56], pinewood [70], wheat straw [70], and horse manure [71])
450 1.15 1.31
at different residence times (15, 30, and 45 min), the results
550 2.54 2.89
650 5.17 5.93 showed that the exergy efficiencies increased when the resi-
Almond shell (biomass/water ratio 0.01, 27 MPa, 10 min) [65] dence time was increased.
380 3.95 4.57 Generally, increases in residence times would result in
400 4.55 5.26 significant increases in the exergy efficiencies. However,
420 5.43 6.28 Barati et al. [72] studied hydrogen production from SWG of
440 6.45 7.47
bagasse when residence times (5, 15, 30, 45, and 60 min) were
460 7.85 9.04
different. The results showed that as the residence time was
Corn cob (25 MPa, concentration of 5 wt%) [66]
550 2.55 3.24 increased (5e60 min, 11 times in increase), the exergy effi-
600 5.31 6.77 ciency increased initially from 6.59% to 7.17% (1.56 times in
650 9.08 11.64 increase) and decreased from 7.17% to 1.94% with 15 min as
Sewage sludge (25 MPa, concentration of 4 wt%) [64] the critical residence time. The initial increases may be
450 6.71 9.79 caused by the water-gas shift (WGS) reaction (H2O þ CO 4
500 7.79 11.40
H2 þ CO2) whereas the final decreases may be due to the
520 8.92 13.06
540 9.26 13.58
methanation reaction (CO þ 3H2 4 CH4 þ H2O). Safari et al.
Chicken manure (24 MPa, concentration of 9 wt%) [67] [65] studied hydrogen production from SWG of almond as
500 6.89 12.99 affected by residence times (5, 10, 15, 20, 25, and 30 min). As
540 12.48 23.56 the residence time increased (5e30 min), the exergy efficiency
580 17.52 33.16 initially increased from 7.96% to 8.98% and then decreased
620 22.17 42.05
from 8.98% to 6.77% with 10 min as the critical residence time.
15732 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6

0.04e0.11%. Hydrogen production during SWG of biomass is a

Table 4 e Hydrogen production from supercritical water
complicated process involving many reactions: (a) methana-
gasification of biomass at different residence times.
tion (CO þ 3H2 4 CH4 þ H2O), (b) hydrogenation (CO þ 2H2 4
Fuel Residence H2 yield Exergy
CH4 þ 0.5 O2), (c) water-gas shift reaction (H2O þ CO 4
time (min) (mol/kg) efficiency (%)
H2 þ CO2), etc. [56,69], making the H2 yields fluctuate in the
Peat (peat/water ratio 0.01, 410
C) [57] range of 0.04e0.10 mol/kg.
15 0.04 0.04
30 0.10 0.11
Effect of reaction catalyst
45 0.05 0.05
Orange peel (biomass/water ratio 1:5, 23e25 Mpa, 600
C) [56]
15 0.70 0.94 Reaction catalysts are important in hydrogen production
30 0.82 1.11 through SWG of biomass [75]. The widely used reaction cata-
45 0.90 1.23 lysts in SWG of biomass are mainly homogeneous catalysts
Pinecone (concentration 10 wt%, 23 Mpa, 550
C) [62] (NaOH, KOH, Na2CO3, K2CO3, etc.) and Ni-containing catalysts
15 0.54 0.57
[74,76].
30 1.13 1.20
45 1.26 1.34
Nanda et al. [56] studied hydrogen production from SWG of
60 1.37 1.46 different fruit and food wastes (orange peel, banana, lemon
Bagasse (biomass/water ratio 1:8, 400
C) [72] peel, coconut shell, pineapple peel, aloe vera rind, and sug-
5 6.98 6.59 arcane bagasse). Fig. 1 shows the exergy efficiencies of
15 7.59 7.17 hydrogen production from SWG at the pressure range of
30 4.75 4.49
23e25 MPa, gasification temperature of 600
C, and residence
45 2.36 2.23
time of 45 min. When 2 wt% reaction catalyst (K2CO3) was
60 2.05 1.94
Horse manure (biomass/water ratio 1:10, 23e25 MPa, 600
C) [71] used, all the exergy efficiencies were significantly increased
15 1.78 2.02 (from 2.31-3.30% to 4.98e7.34%). These were because the re-
30 2.08 2.35 action catalyst is an alkali salt which: (a) accelerates the
45 2.56 2.90 water-gas shift reaction (H2O þ CO 4 H2 þ CO2), (b) suppresses
Pinewood (biomass/water ratio 1:10, 23e25 MPa, 500
C) [70] char and tar formation, and (c) raises the pH (thereby inhib-
15 0.80 0.85
iting the dehydration of monomers) [74,77], consequently
30 1.66 1.77
significantly increased the H2 yields (from 1.52 to 2.17 mol/kg
45 2.83 3.03
Sugarcane bagasse (biomass/water ratio 0.023, 24 MPa, 400
C) [63] to 3.27e4.82 mol/kg). Gong et al. [58] studied hydrogen pro-
5 3.44 2.92 duction from SWG of four dewatered sewage sludges (B, C, D,
10 3.54 3.00 and E) at reactor pressure of 22.1 MPa, gasification tempera-
15 3.73 3.16 ture of 400
C, and residence time of 10 min. There were sig-
20 3.83 3.24 nificant increases in the exergy efficiencies (from 0.70-2.55% to
25 3.83 3.25
3.67e11.67%) when reaction catalysts (2.5% NaOH þ 2.5% Ni)
30 3.80 3.22
Timothy grass (biomass/water ratio 1:8, 23e25Mpa, 650
C) [69]
were used.
15 2.70 3.09 Hydrogen production from SWG of biomass is also signifi-
30 3.00 3.44 cantly affected by the concentrations of reaction catalysts.
45 5.16 5.91 Table 5 shows the H2 yields and exergy efficiencies of SWG of
Wheat straw (biomass/water ratio 1:10, 23e25 MPa, 500
C) [70]
15 1.85 2.13
30 3.43 3.95
45 5.78 6.66
Almond shell (biomass/water ratio 0.01, 27 MPa, 440
C) [65]
5 6.87 7.96
10 7.76 8.98
15 7.38 8.55
20 6.83 7.91
25 6.10 7.07
30 5.85 6.77

Rashidi and Tavasoli [63] studied hydrogen production from

SWG of sugarcane bagasse when the residence times were
different (5, 10, 15, 20, 25, and 30 min). The results showed that
as the residence time increased (5e30 min), the exergy effi-
ciency initially increased from 2.92% to 3.25% and then
decreased from 3.25% to 3.22% with 25 min as the critical
residence time.
Xu and Donald [57] studied hydrogen production from SWG
of peat at different residence times (15, 30, and 45 min). The
results showed that as the residence time increased Fig. 1 e Exergy efficiencies of hydrogen production from
(15e45 min), the exergy efficiency fluctuated in the range of biomass gasification with and without catalyst (K2CO3).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6 15733

(3.47%), followed by NaOH (2.89%) and Na2CO3 (2.07%). Chen

Table 5 e Hydrogen production from supercritical water
et al. [64] studied hydrogen production from SWG of sewage
gasification of biomass with reaction catalyst.
sludge with 0.5 wt% of different reaction catalysts (NaOH,
Fuel Reaction H2 yield Exergy
KOH, Na2CO3, and K2CO3). The results showed that KOH
catalyst (wt%) (mol/kg) efficiency (%)
resulted in the highest exergy efficiency (22.80%), followed by
Coconut shell (K2CO3: 23e25 Mpa, 600
C, 45 min) [56] K2CO3 (20.58%), NaOH (18.47%) and Na2CO3 (16.75%). Based on
0 2.15 2.42
the above results, a general order of KOH > K2CO3 > NaOH >
1 2.91 3.27
1.5 3.63 4.09
Na2CO3 can be summarized.
2 4.75 5.35
Horse manure (K2CO3: 23e25 MPa, 600
C, 45 min) [71] Effect of reactor pressure
0 2.56 2.90
1 4.04 4.57 The significant characteristic of SWG is the high pressure in
1.5 4.56 5.16 the reactor. Reactor pressure is therefore an important
2 5.19 5.88
parameter in the hydrogen production process.
Horse manure (Na2CO3: 23e25 MPa, 600
C, 45 min) [71]
0 2.52 2.85
Lu et al. [66] studied hydrogen production from SWG of
1 3.22 3.65 10 wt% glucose at different reactor pressures (23, 25, and 27
1.5 4.61 5.22 Mpa). The results showed that when the reactor pressure
2 5.33 6.03 was increased from 23 Mpa to 27 Mpa (17.39% in increase),
Sewage sludge (Ni: 22.1 MPa, 400
C, 10 min) [58] the exergy efficiency increased from 7.77% to 9.16% (17.89%
0 1.06 3.00
in increase). These may be because the increased density
1.25 1.20 3.40
and ion product of supercritical water (resulted from the
1.67 1.61 4.56
2.5 1.94 5.49 increased reactor pressure) promoted the hydrolysis reac-
3.33 2.31 6.54 tion, oxidant reaction, and water gas shift reaction, thereby
3.75 2.61 7.39 leading to the continuous increases in the H2 yields
5 3.58 10.14 (6.09e7.18 mol/kg).
Timothy grass (NaOH: 23e25 Mpa, 650
C, 45min) [69] However, Jin et al. [6] studied hydrogen production from
1 5.71 6.54
SWG of 10 wt% glucose at the same reactor pressures (23, 25,
2 5.99 6.86
and 27 Mpa). The results showed that when the reactor pres-
3 6.64 7.61
Timothy grass (KOH: 23e25 Mpa, 650
C, 45min) [69] sure was increased from 23 Mpa to 27 Mpa (17.39% in in-
1 6.44 7.38 crease), the exergy efficiency decreased from 12.08% to 10.81%
2 7.05 8.08 (10.51% in decrease). These decreases may be caused by (a)
3 8.19 9.38 higher reactor pressures inhibited gas formation reactions,
Timothy grass (K2CO3: 23e25 Mpa, 650
C, 45 min) [69] and (b) increased molecule numbers also inhibited gas for-
1 5.52 6.33
mation reactions according to Le Chatelier's principle, conse-
2 5.65 6.47
3 7.81 8.95
quently leading to the continuous decreases in the H2 yields
Sewage sludge (KOH: 25 MPa, 540
C) [64] (8.62e9.63 mol/kg).
0.1 9.84 14.43 Due to the three completing mechanisms of reactor pres-
0.3 10.85 15.91 sure on SWG ((a) the increased density and ion product of
0.5 15.36 22.53 supercritical water promote the hydrolysis reaction, oxidant
0.7 15.11 22.15
reaction, and water gas shift reaction, (b) higher reactor
0.9 14.97 21.95
pressures inhibits gas formation reactions, and (c) the
increased molecule numbers inhibit gas formation reactions),
biomass with different concentrations of reaction catalyst. SWG of biomass for hydrogen production is a complicated
Generally, increases in the concentrations of reaction catalyst process, and more researches are needed.
make increases in the exergy efficiencies of hydrogen pro-
duction. For example, Gong et al. [58] studied hydrogen pro-
duction from SWG of a dewatered sewage sludge at different Conclusions
concentrations (0, 1.25, 1.67, 2.5, 3.33, 3.75, and 5 wt%) of Ni.
The results showed that when the concentration was The main factors affecting hydrogen production in supercrit-
increased from 0 to 5 wt%, the exergy efficiency increased ical water biomass gasification were reviewed from exergy
from 3.00% to 10.14% (2.38 times in increase). These increases aspect. The following conclusions are obtained.
were mainly resulted from the continuous increases in the H2 The exergy efficiencies of hydrogen production are mainly
yields (1.06e3.58 mol/kg) which were fundamentally attrib- in the range of 0.04e42.05%, and they are mainly affected by
uted to the reaction mechanisms mentioned above. feedstock characteristics, biomass concentration, gasification
Hydrogen production from SWG of biomass is not only temperature, residence time, reaction catalyst, and reactor
affected by reaction catalyst concentrations but also by reac- pressure.
tion catalyst types. Nanda et al. [62] studied hydrogen pro- Biomass feedstock may affect hydrogen production by
duction from SWG of pinecone with 30 wt% of different changing the H2 yield and the heating value of biomass. In-
reaction catalysts (Na2CO3, NaOH, and KOH). The results creases in biomass concentrations decrease the exergy effi-
showed that KOH resulted in the highest exergy efficiency ciencies, increases in gasification temperatures generally
15734 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 5 7 2 7 e1 5 7 3 6
increase the exergy efficiencies, and increases in residence
times may initially increase and finally decrease the exergy
efficiencies. Reaction catalysts also have positive effects on
the hydrogen production, and the reviewed results show that
the effects are KOH > K2CO3 > NaOH > Na2CO3. Reactor pres-
sure may have positive, negative or negligible effects on the
exergy efficiencies.
Acknowledgments
This study was supported by National Natural Science Foun-
dation of China (No. 51606048).
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