Energy Conversion and Management 226 (2020) 113497

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Energy Conversion and Management

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

Review

Assessment of supercritical water gasification process for combustible gas

production from thermodynamic, environmental and techno-economic
perspectives: A review
Jingwei Chen a, b, Jiamin Liang a, Zhengyong Xu c, Jiaqiang E a, b, *
a
College of Mechanical and Vehicle Engineering, Hunan University, Changsha 410082, China
b
Institute of New Energy and Energy-Saving & Emission-Reduction Technology, Hunan University, Changsha 410082, China
c
Hunan Provincial Science and Technology Affairs Center, Changsha 410013, China

A R T I C L E I N F O A B S T R A C T

Keywords: Supercritical water gasification (SCWG) technology is an effective gasification technology without the energy-
Supercritical water gasification intensive drying process, especially for feedstocks with high water content. In this paper, energy and exergy
Thermodynamic analysis efficiencies, thermodynamic equilibrium, life cycle assessment (LCA), and economic costs for combustible gas
Environmental assessment
production in various SCWG systems are investigated and summarized. Through sensitivity analysis, the effects
Techno-economic analysis
of operating parameters including temperature, pressure, concentration, oxidant addition, residence time, system
scale, and heating mode on the SCWG process are analyzed to optimize the SCWG process from the perspectives
of thermodynamics, environmental and economic performance. Additionally, the environmental impact and
economic costs of SCWG technology are compared with those of other hydrogen production technologies to
ascertain the feasibility of its large-scale application. In terms of the average global warming potential (GWP)
and acidification potential (AP) generated from various hydrogen production technologies, the environmental
competitiveness of SCWG is significantly higher than steam reforming and auto-thermal reforming, but inferior
to water electrolysis, water-splitting, and conventional gasification technologies. The techno-economic analysis
results show that the average hydrogen production cost (HPC) of SCWG technology is lower than that of con­
ventional biomass gasification, steam reforming, water electrolysis, and thermochemical hybrid sulfur cycle,
slightly higher than that of pyrolysis, thermochemical S-I water-splitting cycle and Cu-Cl water-splitting cycle.
This review is expected to guide future research on the optimization of the SCWG process from the aspects of
thermodynamic, environmental, and economic analysis.

energy demands [3]. Hydrogen also plays an integrating role among

1. Introduction
Due to the rapid population growth and social development, the
global primary energy consumption grew at a rate of 2.9% in 2018
almost double its 10-year average of 1.5% per year, and the total energy
consumption is forecast to reach 20,000 million tons of oil equivalent in
2050 [1]. At present, the energy consumption is dominated by oil and
coal. The oil and coal consumptions were 4662.1 and 3772.1 million
tons of oil equivalent in 2018, respectively, generating 780 billion cubic
meters of carbon emissions [2]. Given the depletion of fossil fuels and
the environmental and socio-economic problems caused by their
excessive use, hydrogen, a renewable energy source characterized by
stable combustion, zero emissions, high calorimetric combustion, easy
storage, and transportation, is considered as a viable solution to future
energy-related sectors and hydrogen is regarded as an intermediate
storage option for the grid electricity with more reliability and less
environmental impact [4].
For getting rid of the high dependence of fossil fuels in producing
hydrogen energy, hydrogen production technologies with environment-
friendly, energy-saving, and high-efficiency are progressing rapidly.
Benefiting from the excellent physical and chemical properties of su­
percritical water, SCWG for hydrogen production is considered as a
promising method for converting biomass with high water content into
hydrogen-rich gas [5,6]. Compared with conventional hydrogen pro­
duction methods, SCWG avoids the energy-intensive drying process.
Meanwhile, SCWG has good raw material adaptability, which brings
better results on material decomposition and high gas production with
low char and tar formation [7–10]. Moreover, the SCWG process

* Corresponding author at: College of Mechanical and Vehicle Engineering, Hunan University, Changsha 410082, China.
E-mail address: ejiaqiang@hnu.edu.cn (J. E).

https://doi.org/10.1016/j.enconman.2020.113497
Received 22 June 2020; Received in revised form 29 September 2020; Accepted 30 September 2020
Available online 9 October 2020
0196-8904/© 2020 Elsevier Ltd. All rights reserved.
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Nomenclature LCIA Life cycle impact assessment

GWP Global warming potential
Acronyms EP Eutrophication potential
SCWG Supercritical water gasification AP Acidification potential
ISCWGC-HPP Integrated supercritical water gasification of coal for ADP Abiotic depletion potential
power and hydrogen production ODP Ozone layer depletion potential
HTE Heat transfer efficiency POFP Photochemical oxidation potential
SKLMF State Key Laboratory of Multiphase Flow in Power EQ Ecosystem Quality
Engineering CC Climate Change
GE Gasification efficiency RS Resource Scarcity
RFR Recycle flow ratio CED Cumulative energy demand
TOC Total organic carbon TEA Techno-economic analysis
CCS Capture and storage TRR Total revenue requirement
ORC Organic Rankine cycle ROI Return on investment
EnR Energy recovery IRR Internal rate of return
EOS Equation of state TCI Total capital investment
PR Peng-Robinson TPC Total production cost
SRK Soave-Redlich-Kwong OMG Operation and maintenance costs
RMSE Root-mean-square error NPV Net present value
R2 Pearson’s correlation factor FC Fuel cost
MHV2 Modified Huron-Vidal OC Operating cost
BM Boston-Mathias modifications EPC Equipment costs
CC Carbon conversion SNG Synthetic natural gas
CE Carbon gasification efficiency HPC Hydrogen production cost
HE Hydrogen gasification efficiency FT Fischer-Tropsch
UNIFAC Universal functional activity coefficient CHP Combined heat and power
LCA Life cycle assessment

involves the production of high-pressure syngas, enabling the technol­
ogy to achieve the cogeneration of heat and power while producing
hydrogen [11–13].
The research on SCWG can be traced back to 1978 when Modell
gasified organics in supercritical water for the first time and hydrogen-
rich products were obtained [14]. From then on, the application of su­
percritical water on extracting organic materials to produce synthetic
fuels has sparked a research boom. There have been some developments
in process scale, reactor type, and integration studies. In terms of process
scale, it has expanded from laboratory to pilot scale [15,16]. For­
schungszentrum Karlsruhe [17] constructed the first pilot-scale SCWG of
wet residues system with the capacity of 100 L/h, which could operate
stably within 10 h. General Atomics built a supercritical water partial
oxidation system to handle 200 kg/h of biomass slurry [18]. A well-
equipped SCWG system was built in Enschede, with a maximum
throughput capacity of 30 L/h [19]. In Japan, a pilot-scale SCWG system
with a scale of 1 ton/day was built at Hiroshima University [20]. In
China, the State Key Laboratory of Multiphase Flow in Power Engi­
neering (SKLMF) developed the first pilot plant of SCWG-Solar with a
throughput of 1.03 t/h. The continuous and stable operation of the
demonstration plant verifies the feasibility of large-scale application of
the technology [21]. In terms of SCWG process optimization, a great
progress has been made in the development of the reactor configuration,
and a variety of unique SCWG reactors have been developed, such as the
diamond anvil cell autoclaves batch reactor [22,23], quartz capillaries
batch reactor [24], micro-tuber reactor [25–28], tubular and hybrid
reactors [29], Y-shape reactor [30,31], and bubbling fluidized bed
SCWG reactor [32,33]. To promote the performance of SCWG technol­
ogies, some studies integrated other systems with the SCWG process.
Guo and Jin [8] proposed a novel thermodynamics cycle power gener­
ation system which was based on SCWG of coal and multi-staged steam
turbine reheated by hydrogen combustion. The industrial prospects of
coal and SCWG process and the novel thermodynamics cycle power
generation system were proved. Cao et al. [34] proposed an innovative
integrated system of pulping and SCWG of black liquor, fully utilizing
the hydrogen, power, steam generated from SCWG to meet the energy
requirement of the pulping process. Darmawan et al. [12] integrated the
SCWG of black liquor with syngas chemical looping and adopted the
exergy-recovery technologies, forming a highly-efficient and
environmentally-clean black liquor utilization system. Albarelli et al.
[35] integrated the SCWG process with a sugarcane biorefinery system.
A microalgae SCWG process based on enhanced process integration was
proposed by Aziz [36]. In a conceptual process that integrated SCWG
and reforming process, Hantoko et al. [37] enhanced the productivity of
syngas to 151.12 kg⋅100 kg− 1 (feed) compared to 120.61 kg⋅100 kg− 1
(feed) of the conventional SCWG.
Along with the development of technology, some evaluation studies
on the SCWG system have been done successfully to optimize the SCWG
system. The researches focused on the energy, exergy, and hydrogen
efficiencies analysis, the environmental impact, and economic compet­
itiveness of the SCWG technology. Through the thermodynamic anal­
ysis, the potential of diosgenin solid waste for hydrogen production via
SCWG in a fluidized-bed reactor was firstly verified by Cao et al. [38].
The product distribution, thermodynamic analysis of phase behavior
and phase equilibria both in the reactor and separators of the SCWG
process were studied to look for the favorable operating parameters that
are conducive to high hydrogen yield [39–42]. Gasafi et al. [43] con­
ducted a detailed exergy analysis on SCWG of sewage sludge to improve
the energy utilization efficiency of the system. Rahbari et al. [44] con­
ducted a sensitivity analysis of the factors affecting energy and exergy
efficiencies in SCWG of algal biomass system. A comprehensive effect of
parameters on energy and exergy flow was investigated by Zhang et al.
[45]. In order to analyze the environmental impact of the SCWG system,
LCA has been widely used as the evaluation method. Chen et al. [46]
conducted a sensitivity analysis on LCA of the SCWG-Solar system to
determine the optimization means in construction, operation, and
dismantling stages of the system. Wang et al. [47] calculated the energy,
raw material consumption, and environmental emissions during
different life cycles of the SCWG system, and the environmental per­
formance of the system was improved by optimizing operational

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J. Chen et al. Energy Conversion and Management 226 (2020) 113497

parameters. Chen et al. [13] examined the environmental impact of the ∑

En,out
operation phase in the system of integrated supercritical water gasifi­ ηen = ∑ × 100% (1)
En,in
cation of coal for power and hydrogen production (ISCWGC-HPP). In
order to minimize combustible gas costs and maximize profits of the
where the energy input En,in (kJ⋅h− 1) is the energy contained in the raw
SCWG system, General Atomics firstly conducted an economic analysis
materials input to the system and the external energy consumed in the
on the SCWG system in 1997 [48]. Subsequently, various economic is­
gasification process. The energy output En,out (kJ⋅h− 1) includes the en­
sues about the SCWG system have been extensively investigated.
ergy produced by the SCWG system and the calorific value contained in
Albarelli et al. [35] conducted a multi-objective analysis with the aid of
the products of the combustible gas. The energy contained in each
the Pareto curve to minimize the total investment costs of SCWG system
substance can be calculated as follows [13]:
of sugarcane biorefinery residues. Gasafi et al. [49] carried out an eco­
nomic analysis of SCWG using sewage sludge as feedstock and assessed En,i = M × Q (2)
the competitiveness of the SCWG process in comparison to conventional
technologies of hydrogen production. where M is the mass flow rate of substance, and Q is the low calorific
The interest in SCWG promoted the exploration of some review pa­ value per kilogram of substance. The energy loss ratio is defined as:
pers that partially settled the issues of SCWG. Yakaboylu et al. [50]
(En,loss )i
overviewed the current status of SCWG technology from the perspec­ εen = ∑ × 100% (3)
(En,loss )i
tives of thermophysical properties and chemical reactions of water. Hu
et al. [51] had an in-depth understanding of chemistry and kinetics of Along with the energy analysis, the exergy analysis is also a
the SCWG system of biomass model compounds (cellulose, hemicellu­ remarkable tool for evaluating the system performance [60], which re­
lose, lignin, lipid, and protein). Matsumura et al. [52] reviewed the re­ fers to the maximum work potential of matter or a form of energy with
action mechanism, catalyst, and experimental results of low- respect to its environment. The exergy of material stream in the SCWG
temperature catalytic and high-temperature SCWG. The heterogeneous system covers four exergy forms [61]:
catalysts used for SCWG were reviewed in refs. [53,54]. Moreover, the
Ex = Exch + Exph + Exki + Expo (4)
effects of different operating parameters such as gasification tempera­
ture, reactor pressure, feedstock concentration, residence time, and
where Ech ph ki po − 1
x , Ex , Ex and Ex (kJ⋅kg ) represent chemical, physical, ki­
catalysts on the gasification were investigated by numerous studies
netic, and potential exergy of material streams respectively. Generally,
[55–57]. The effect degree of those operating parameters was deter­
the Eki po
x and Ex are neglected due to their especially small value. Eq. (3)
mined by Lu et al. [58] via adopting the orthogonal experimental design
results in [41,62,63]:
method.
As mentioned above, there are no relevant reviews of thermody­ Ex = Exch + Exph (5)
namic, environmental, and economic evaluation on the SCWG process.
Therefore, the main objectives of this review are to (1) present a holistic ph
Ex,i = (h − ho ) − To (s − so ) (6)
overview of SCWG systems from the aspects of energy and exergy effi­
∑ ph
ciencies, chemical equilibrium, and gas–liquid equilibrium; (2) sum­ Exph = yi Ex,i (7)
marize the environmental impact analysis of different SCWG processes i

based on available LCA studies; (3) identify the techno-economic ∑ ∑

feasibility of SCWG plant through the production cost of combustible Exch = ch
yi Ex,i + RTo yi ln yi (8)
gas. The environmental impacts and economic assessment of several i i

well-developed hydrogen production technologies are also compared In Eqs. (5)–(8), Eph x,i and Ex,i are the physical and chemical exergy of i
ch

with SCWG technology in this study.

matter, respectively. yi represents the molar fraction of i matter. h and s
This review can be used to guide future research on optimizing the
are the enthalpy and entropy at arbitrary temperatures, respectively.
SCWG process, decreasing environmental pollution, and reducing
Furthermore, ho and so are the specific enthalpy and entropy under
operating costs (OC) to promote the commercialization of the SCWG
standard conditions (pressure = 1 atm, temperature To = 298.15 K). In
technology.
Eq. (7), R is the universal gas constant.
For an open system like the SCWG system, the exergy balance is
2. Thermodynamic analysis of SCWG process
usually considered as an important factor for determination of system
deficiencies because of its ability to identify the exergy destruction rate,
The thermodynamic analysis provides theoretical support for the
and the energy balance is expressed as [63]:
system design, optimization, and operation of the SCWG system. In this ∑ ∑ ∑ ∑ ∑
section, the analysis of energy conversion efficiency, chemical equilib­ Ex,in + Ex,Qin = Ex,out + Ws + Ex,loss (9)
rium in chemical reactors, and phase equilibrium in separation pro­ ∑ ∑
cesses are adopted as thermodynamic analysis methods to analyze the where Ex,in and Ex,Qin are the mass exergy and heat exergy
∑ ∑
SCWG process. entering the SCWG system, respectively. Ex,out and Ws give the mass
∑
exergy and the work leaving the system. Ex,loss is the exergy losses. So
2.1. Energy and exergy analysis the exergy efficiency and exergy loss ratio of the SCWG system are
usually expressed as follows [64]:
Based on the first and second laws of thermodynamics, the energy (∑ ∑ )
Ex,out + Ws
and exergy efficiencies are selected in this section to assess the perfor­ ηex = ( ∑ ∑ ) × 100% (10)
Ex,in + Ex,Qin
mance of the SCWG energy production process and identify the location,
types, and magnitudes of energy and exergy losses [59]. (Ex,loss )i
εex = ∑ × 100% (11)
(Ex,loss )i
2.1.1. Method for energy and exergy analysis
Energy efficiency is defined as the ratio of useful energy output over However, in some studies, only the exergy of feedstock and gas
the energy input of the system: products were considered for the calculation of exergy balance and
exergy efficiency but the heat exergy entering the SCWG system, the
work leaving the system, and the exergy losses were ignored.

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J. Chen et al. Energy Conversion and Management 226 (2020) 113497

2.1.2. Evaluation of energy and exergy efficiencies on system components
Energy and exergy analysis have been extensively studied to achieve
efficient steady-state operation. The pinch method was often used to
calculate the minimum heat required to evaluate the possible heat ex­
change between cold and hot fluids to facilitate energy integration
[65,66]. Due to the irreversibility associated with chemical reactions,
the exergy destruction is accompanied by the gasification process. To
minimize the energy leaked into the unused environment and improve
the thermodynamic efficiency, it is necessary to study the energy and
exergy loss rate of system components.
Table 1 shows the energy and exergy analysis of components in
different SCWG plants. Based on a steady-state model, Gasafi et al. [43]
indicated that the combustion chamber with the highest proportion of
exergy destruction reached 34.01% in the SCWG complete plant of
sewage sludge, followed by the air preheater (15.58%). The total energy
and exergy efficiencies of the whole system were 52% and 56%
respectively. In a biomass SCWG system using external recycle of liquid
residual, Wang et al. [47] discussed the effect of various operating pa­
rameters on energy and exergy efficiencies. The maximum exergy loss of
the reactor accounted for 35.88% of the total exergy loss under the
conditions of 560 ◦ C and 25 MPa. In the sawdust SCWG system [41], the
energy loss rate of the heat exchanger is the highest, reaching 47.61%.
The exergy loss of the system is mainly caused by the reactor and heat
exchanger, accounting for 36.88% and 32.01% respectively. Iribarren
et al. [67] found that 47% of the overall fuel exergy vanishes as exergy
destruction within the individual components of the plant.
For the visual observation of exergy analysis results, Rahbari et al.
[44] drew a detailed Sankey diagram (as shown in Fig. 1) to illustrate the
exergy flow of system components and its effect on the overall behavior
of the solar-based SCWG system of algae. The arrow in the figure rep­
resents the direction of exergy flow. It was found that the reactor is the
main source of system exergy destruction because of the irreversibility
in chemical reactions as well as the heat transfer process. The other
primary exergy destruction originated from the heat exchangers and
separators due to the irreversibility of heat transfer. As shown in Fig. 2,
the x-coordinate, y-coordinate, and shaded areas between the curves
represent the energy change, energy level A, and exergy destruction,
respectively. Chen et al. [68] illustrated that the heating of water caused
the largest exergy destruction in the coal SCWG system, which accounts
for approximately 40.21% of the total exergy destruction. In the inte­
grated SCWG system of coal with syngas separation [69], the total
exergy destruction was comprised of four parts including gasifier, heat
exchanger, Rankine cycle, and pressure relief. Additionally, an increase
in coal-water-slurry concentration leads to an increase of exergy
destruction ratio, which reached a maximum of 50% at the coal-water-
slurry concentration of 10%.
As mentioned above, the components of the reactor, preheater, and
heat exchanger are proved to have a significant contribution to the
exergy destruction. The exergy destruction in the reactor mainly comes
from absorption, radiative heat loss, and chemical irreversibility. Using
external heat sources such as high-temperature waste heat instead of
electrical energy can improve the exergy efficiency of preheaters and
reactors [47]. For the separator and heat exchanger, the exergy
destruction is mainly due to the heat transfer between high-temperature
and low-temperature fluids [44], which can be reduced by decreasing
the mean temperature difference between material flows and increasing
the heat transfer temperature [43]. In terms of minimizing energy loss in
the SCWG of coal system, Yu et al. [70] reported that high carbon
content in coal was beneficial in increasing gaseous products, improving
gasification efficiency and reducing energy loss. In addition, several heat
exchangers can be appropriately installed in the SCWG process to
minimize energy loss and build the optimum heat integration network
system [71]. It has been reported that the unit with maximum available
energy loss is the cooler, and the loss can be reduced when the organic
Rankine cycle (ORC) is adopted [13,41].
2.1.3. Sensitivity analysis
From the perspective of molecular dynamics [72,73], the SCWG
process involves ionic and free-radical reactions. The type of dominant
reactions changes with the gasification condition, further affecting the
energy and exergy efficiencies. Zhang et al. [45] deeply overviewed the
effect of operation parameters on exergy efficiency of the SCWG system.
Lei et al. [74] performed equivalent cumulative exergy analysis based on
the orthogonal experimental results of glucose SCWG and obtained the
optimum parameters, including concentration, residence time, and the
inner diameter of a reaction tub.
Table 2 reviews the relationship between sensitivity factors and en­
ergy and exergy efficiencies from the available literatures. It can be seen
that energy and exergy efficiencies are highly dependent on the reaction
temperature [75]. An increase in gasification temperature is conducive
to an increase in energy and exergy efficiencies in most literatures
[13,44,47,66,76]. The most dramatic increase in energy efficiency
occurred in the SCWG system with external recycling of liquid residual
[47]. The energy efficiency increased from 45.23% to 63.67% when the
temperature increased from 500 ◦ C to 560 ◦ C. The exergy efficiency of
the glucose SCWG system increased by 17% when the temperature
increased from 450 ◦ C to 600 ◦ C [66]. However, when the char pro­
duction rate keeps unchanged, the exergy efficiency of the whole process
decreases with the increase of reactor temperature [44].
A low slurry concentration leads to a low exergy efficiency, which
also brings a burden on the system scale and investment cost. Cao et al.
[80] introduced a black liquor evaporator to improve the exergy

Table 1
Energy and exergy analysis of components in different SCWG plants.
Ref Condition Indicator Components Total energy Total exergy
efficiency (%) efficiency (%)
Reactor Preheater Heat Separator Combustion Cooler
exchanger chamber

Sewage 600 ◦ C,28 Exergy 95.78 65.67 – – 70.53 – 56 52

sludge [43] MPa efficiency (%)
15–20 wt% Exergy loss 11.72 15.58 – – 34.01 –
rate (%)
Biomass [47] 560 ◦ C, 25 Exergy 84.44 64.48 89.87 – – – 63.67 48.29
MPa efficiency (%)
2.78 wt% Exergy loss 35.88 26.06 24.52 – – –
rate (%)
Sawdust [41] 600 C, 25
◦
Energy loss 17.90 9.86 47.61 0.44 – 19.3 44.21 42.26
MPa rate (%)
30 wt% Exergy loss 36.88 12.60 32.01 3.68 – 1.97
rate (%)
Algae [44] 605 ◦ C, 25 Exergy loss 61.7 – 12.2 16.1 – – 71.2 45.2
MPa rate (%)
15.2 wt%

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J. Chen et al.
Fig. 1. Sankey diagrams for exergy flow in a solar SCWG reactor integrated with a downstream autothermal reforming technology (adopted from [44]). (Notes: X
represents the exergy, MW; Xdest represents the exergy destruction, MW; Mix represents the mixer; Sep represents the separators; HX represents the heat exchanger;
PV represents the photovoltaic electrolyser; SMR represents the steam methane reforming).
Fig. 2. The energy-utilization diagram of SCWG technology when the coal-
water-slurry concentration is 20 wt% (adopted from [68]).
efficiency. The self-generated steam and power was used to increase the
slurry concentration, but this method came at the expense of the system
energy efficiency. A similar result was also obtained in the SCWG
glucose system. Hao et al. [77] increased the glucose concentration from
0.1 M to 0.8 M, and found that the exergy efficiency increased from
50.77% to 52.51%, but the energy efficiency decreased from 97.62% to
82.55%. In the solar-based SCWG of biomass system [76], the ideal
exergy efficiency of the system reached a peak of about 51.7% at
700–900 K, with a mean solar concentration ratio in the range of
150–300. At higher coal-water-slurry concentrations, more carbon was
used for gasification other than combustion in the SCWG process, which
leads to higher exergy efficiency and cold gas efficiency (CGE)
[13,68,69].
The heat transfer efficiency (HTE) was also considered as one of the
parameters that have great effects on the energy and exergy efficiencies.
Matsumura [79] indicated that the energy efficiency increased from
64.8% to 78.6% with the improvement of heat exchanger efficiency in
SCWG of water hyacinth system. Because of the unchanged energy input
and output of the system, the energy efficiency keeps 44.21% when the
5
Energy Conversion and Management 226 (2020) 113497
temperature of external heat resource changes in the study from Lu et al.
[41]. They found that increasing the HTE of heat exchanger, reactor and
preheater is beneficial to improve the energy and exergy efficiencies.
The substitution of external heating for the internal heating method as
well as the increase of HTE of the reactor were also favorable to the
energy and exergy efficiencies in the glucose SCWG system [77].
In addition to improving the energy and exergy efficiencies of the
SCWG system by optimizing various parameters, some studies have also
realized the improvement of the energy utilization efficiency of the
SCWG system through process designs. With the integration of external
recycle of liquid residual technology, the optimal energy and exergy
efficiencies reached 63.67% and 48.29% respectively. Energy and
exergy efficiencies go up as the increase of the RFR [47]. Ondze et al.
[66] indicated that in the glucose SCWG process, the adiabatic condition
brings better results of the energy and exergy efficiencies compared with
the isothermal condition at the same temperature and total organic
carbon (TOC). In the ISCWGC-HPP system [13], the technology of car­
bon dioxide capture and storage (CCS) and the technology of organic
Rankine cycle were proved to be effective measures to improve energy
and exergy efficiencies. To minimize the exergy destruction from the
microalgal utilization process, Aziz [36] proposed integrated energy
utilization processes which consist of the SCWG system and combined
cycle for power generation, and the total energy efficiency of the system
exceeded 40%. Darmawan et al. [12] adopt the concepts of exergy re­
covery and process integration to combine the SCWG process with the
syngas chemical looping system. The total net energy efficiency reached
as high as 80% and the CO2 capture efficiency reached 75%. Calcula­
tions by Yong et al. [78] upon the SCWG of oil palm indicated that the
energy recovery (EnR) technology can significantly improve energy ef­
ficiency at 727 ◦ C and 30 MPa. The energy efficiency reached 72.91%
with EnR and 46.54% without EnR. Meanwhile, due to the difference in
chemical energy and exergy ratio, the syngas composition in gasification
products also affects the overall exergy efficiency [61].
According to the sensitivity analysis of energy and exergy efficiencies
of the various SCWG systems, it is found that the improvement of energy
and exergy efficiencies is realized mainly in two ways. One is to change
the operating parameters of the gasification process, such as increasing
the reaction temperature, increasing the concentration of feedstock, and
controlling the heat transfer efficiency of various components. The other
is to couple the SCWG system with new technologies, such as external
recycle systems, CCS technology, and EnR method.
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Table 2 Table 2 (continued )

Sensitivity analysis on energy and exergy efficiencies of different SCWG systems. Technology Sensitivity factors Energy Exergy efficiency
Technology Sensitivity factors Energy Exergy efficiency efficiency
efficiency
ISCWGC-HPP T: 600–700 ◦ C (25 ↑: 28.5–31.5% ↑: 27.1–30.1%
SCWG of T of external heat Unchanged: ↓: 43.75–41.57% of coal [13] Mpa, 2 wt%,
biomass [41] resource: 44.21% without CCS)
1073–1473 K C: 2–15 wt% (25 ↑: 30.1–42.6% ↑: 31.5–46.6%
(HTE: 75%) MPa, 700 ◦ C,
HTE of heat ↑: ↑: 22.30–50.61% without CCS)
exchanger: 0–90% 20.84–56.65% With/without CCS 36.7%/31.6% 33.46%/30.1%
(1273 K, HTE: (25 MPa, 700 ◦ C, 2
75%) wt%)
HTE of reactor and ↑: 8.58–52.5% ↑: 9.52–48.44%
SCWG of coal C: 6–20% (650 ◦ C, – ↑: 71.08–82.03%
preheater:
[68] 25 MPa)
10–100% (1273 K,
HTE: 75%) Integrated C: 6–20% (650 ◦ C, – ↑: 85.60–89.18%
SCWG of coal 25 MPa)
SCWG of C: 0.1–0.8 M ↓: ↑: 50.77–52.51%
and syngas
glucose [77] (650 ◦ C, 25 MPa, 97.62–82.55%
separation
HTE of reactor:
[69]
95%)
HTE of reactor: ↑: ↑: 55.10–68.28% T: Temperature P: Pressure C: Slurry concentration.
75–95% (650 ◦ C, 78.25–97.62% ↑: Increase with the increased in the sensitivity factor.
25 Mpa, 0.2 M, ↓: Decrease with the increased in the sensitivity factor.
1073 K heat
∩: Increase firstly and then decrease with the increased in the sensitivity factor.
resource)
Heat supply: Unchanged: 51.44%, 67.56%,
electricity, 1073 K, 95.30% 64.39% 2.2. Thermodynamic equilibrium of SCWG process
1273 K heat
resource (650 ◦ C,
Since Antal established the first thermodynamic model of SCWG to
25 Mpa, 0.2 M)
simulate the conversion of cellulose in SCW [81], numerous studies on
SCWG of T: 450-600 C ↑: 26–42% ↑: 32–49%
the thermodynamic equilibrium of SCWG have emerged. Equilibrium
◦

glucose [66] (TOC: 20 g⋅L− 1

isothermal case)
models which include stoichiometric and non-stoichiometric methods
T: 450-600 ◦ C ↑: 25–43% ↑: 31–50% were conducted to predict the equilibrium composition and thermody­
(TOC: 20 g⋅L− 1 namic limits as a guide for process design, evaluation, and improvement
adiabatic case) in the SCWG system.
C: 20–80 g⋅L-1 ↑: 25–41% ↑: 31–46%
(450 ◦ C, adiabatic
case) 2.2.1. The establishment of thermodynamic model
The non-stoichiometric equilibrium model which is based on mini­
SCWG of T: 500-560 C (25
◦
↑: ↑: 39.14–48.29%
biomass with Mpa, RFR: 32.43%) 45.23–63.67%
mizing Gibbs free energy and subjected to molar balance constraints is
external P: 23–25 MPa ↑: ↑: 36.69–40.13% suitable for reactions with less clear mechanism [6] and has been widely
recycle of (500 ◦ C, RFR: 44.07–46.41% used as a powerful tool to solve the chemical equilibrium in the reactor
liquid 32.43%) and the gas–liquid equilibrium in the high-pressure separator in the
residual [47] C: 2.78–2.95% ↓: 39.14–30.49%
↓:
SCWG process. As the thermodynamic equilibrium can never be ach­
(500 ◦ C, 25 MPa, 45.23–34.42%
RFR:32.43%) ieved, the results of the thermodynamic model represent the maximum
RFR: 0–600 kg⋅h− 1 ↑: ↑: 31.11–45.23% efficiency that can be possibly attained for a given feedstock in an ideal
(500 ◦ C, 25 Mpa) 22.88–39.14% system [82]. The SCWG process is complex, involving hydrolysis, py­
Solar-based T: 500-605 ◦ C (24 – ↑: 44.89–44.95% rolysis, tar reforming, water–gas shift reaction, methanation reaction,
SCWG of MPa, 15.2%, 10% reforming reaction [83–85]. The overall chemical reaction for biomass
algae [44] char) gasification in supercritical water can be expressed by the Eq. (12) [86].
C: 5.5–15.2% (24 ↑:
The equilibrium products of the biomass SCWG system are mainly
MPa, 605 ◦ C) 53.42–71.23%
Char rate: 10–20% – ↓: 32↑: composed of H2, CO2, CH4, and trace CO. In the gasification process,
(24 MPa, 15.2%, 26.71–50%.5–44.95% hydrocarbons are converted into the above gases mainly through the
605 ◦ C) Char rate: reactions (Eqs. (13)–(15)) [47]:
10–20% (24 MPa,
15.2%, 605 ◦ C)
1. Overall chemical reaction
Solar-based T: 500–1100 K (C – ∩: 39.3–51.7–29.6%
SCWG of ratio: 150) CHxOz + (2 − y)H2O → CO2 + (2 − y + x/2)H2 (12)
biomass [76] C ratio: 150–300 – ↑: 42.3–54.3%
(900 K) 2. Steam reforming
SCWG of oil With/without EnR 72.91%/ –
palm [78] (727 ◦ C, 30 MPa) 46.54%
Cx Hy Oz + (2x − z)H2 O ↔ xCO2 + (y/2 + 2x − z)H2 (13)

SCWG of water Heat exchanger ↑:64.8–78.6% –

hyacinth efficiency: 75–90% 3. Water gas shift reaction
[79] (600 ◦ C, 34.5 MPa)
CO + H2 O ↔ CO2 + H2 (14)
SCWG of black C: 10–20 wt% ↓: ↑: 39.26–42.59%
liquor [80] (700 ◦ C, 25 MPa, 79.29–76.25%
without
4. Methanation reaction
evaporation)
CO + 3H2 ↔ CH4 + H2 O (15)

6
J. Chen et al.
(1) Chemical equilibrium:
The chemical equilibrium is the forerunner and foundation of
chemical reaction. The maximum yield of the target product can be
calculated by the chemical equilibrium to measure the difference with
the actual reaction. At the fixed temperature (T) and pressure (P), when
the mixture system is in the state of chemical equilibrium, the Gibbs free
energy is minimal, which can be written as:
∑
n
G= μi ni
i=1
where µi and ni refer to the chemical potential and molar number of
components i, respectively, and µi is formulated as:
μi (T, P) = μ0i (T) + RTInfi
where μ0i (T) refers to the standard molar chemical potential, and R is the
ideal gas constant and fi means the partial fugacity.
(2) Gas-liquid equilibrium:
The gas–liquid equilibrium in a system means the equal fugacity of
each component in the gas and liquid phase. The main equilibrium
equation can be expressed as follow:
fig = fil
The detailed calculation methods can be found in [87,88], thus this
work will not go into detail.
There are various property methods to calculate thermodynamic
equilibrium, including the activity coefficient method, equation of state
(EOS) method, and ideal model method. Depending on the degree of
imperfection and operating conditions, EOS is more suitable than other
methods in the SCWG process to calculate the fugacity coefficients of
components.
2.2.2. Thermodynamic model validation
Eqs. (16)–(18) show that in the study of thermodynamic equilibrium,
the calculation of the thermodynamic properties of each species in the
SCWG system is very important. The thermodynamic properties can be
calculated by using EOS, such as Peng-Robinson (PR) and Soave-
Redlich-Kwong (SRK). Mixing rules are needed when these thermody­
namic properties interact with different components. The properties of
the supercritical fluid are very different from that of conventional fluid.
Especially, water is a kind of strongly polar material and its hydrogen
bond still exists even under supercritical conditions. Thus, it is very
difficult to select the thermodynamic EOS applicable to polar material.
There are many studies on comparing the effects of different property
methods on the prediction results. The Root-mean-square error (RMSE)
and Pearson’s correlation factor (R2) are used to evaluate the error be­
tween the model prediction results and the experimental data:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
√∑
√N ( )2
√ x
√j=1 exp,j
− x mod ,j
RMSE = (19)
N
∑ ∑
N xexp ⋅x mod − xexp × x mod
R2 = √[̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
] [ ∑
∑ ∑
N x2exp − ( xexp )2 × N x2mod − ( x mod )2
where xexp, xmod represent the value from the experimental results and
model prediction results respectively, and N represents the number of
data.
PR and SRK property methods with various mixing rules include
Modified Huron-Vidal (MHV2), Boston-Mathias modifications (BM),
Energy Conversion and Management 226 (2020) 113497
and Wong-Sandler. Withag et al. [89] indicated that all equilibrium
prediction models could give a prediction of H2 mole fraction within a
bandwidth of 3.5% in SCWG of 10 wt% methanol system. Similarly, the
correctness of various property methods with mixing rules, which were
used for calculating the theoretical H2, CO, CO2, and CH4 yields in
ethanol SCWG system, was verified and compared by Byrd et al. [90].
The comparison results are shown in Table 3.
The model needs to be validated by comparing the consistency be­
tween the model predictions and the experimental data. Antal et al. [92]
firstly used the thermodynamic equilibrium approach, including
(16) STANJAN (based on EOS with ideal gas assumption) and HYSIM (based
on PR EOS), to calculate the equilibrium yield of H2, CO2, CO, CH4, H2O,
and ethane. The results showed that STANJAN tends to overpredict the
equilibrium yield of H2 and underpredict the yield of CH4. To validate
the accuracy of the model (Duan EOS), Yan et al. [88] compared the
(17) predicted gas yields of glucose gasification in SCW with the experi­
mental data conducted by Kruse et al. [93], with an average error of
1.196%. Based on the PR EOS, Susanti et al. [94] compared experi­
mental gas yields and theoretical equilibrium yields from the gasifica­
tion of methanol, ethanol, glycerol, glucose, and some model
compounds of petroleum fuels at 25 MPa, 740 ◦ C, and residence time 60
s. The average error of H2 yield prediction was between 0.14 and 1.73
mol. Coincidentally, Voll et al. [39] validated their models based on the
experimental data from the studies of Tang and Kitagawa [95], Byrd
et al. [90,96], Yakaboylu et al. [97], and Taylor et al. [98]. The results
showed that the mean absolute error was between 0.008 and 0.606.
(18) Chakinala et al. [24] used the modified SRK EOS and verified the ac­
curacy of the simulation results of the SCWG of microalgae. Taking
operation parameters as influencing factors, Louw et al. [99] and Byrd
et al. [96] verified that the equilibrium syngas composition yields were
in good agreement with the experimental results. Meanwhile, Hantoko
et al. [37] adopted the same operating conditions in the glycerol SCWG
system as Byrd et al. [96] to verify the thermodynamic model. To better
predict gas yields and gas composition, Goodwin and Rorrer [100]
developed a xylose gasification kinetic model using a simplified reaction
mechanism. The main comparison results of the aforementioned SCWG
systems are shown in Fig. 3, and it indicates that the equilibrium pre­
dictions agree well with experimental results.
The global thermodynamic equilibrium method based on Gibbs free
energy minimization is still the mainstream method for predicting
product compounds. Most actual gasification systems cannot reach the
equilibrium state due to natural constraints. But some studies have
found that equilibrium compounds can be predicted more accurately by
adding additional constraints to the Gibbs free energy minimization
algorithms. Kangas et al. [101] introduced some process dependent
values (such as the amounts of carbon conversion (CC), tar, ammonia,
hydrogen, methane, and other hydrocarbons) as additional constraints
for modeling the conventional biomass gasification. Yan et al. [88]
successfully applied the CC efficiency into their equilibrium model as a
constraint to better predict gas production. To test the constrained
equilibrium method for the modeling of biomass SCWG system, Yaka­
boylu et al. [102] compared the experimental results with the predicted
results when the additional constraints such as carbon gasification ef­
ficiency (CE), hydrogen gasification efficiency (HE), and constrained
amounts for specific compounds were used. Fig. 4 shows the comparison
∑
Table 3
̅ (20) Comparison of various property methods for the theoretical gas yields calcula­
∑ ]
tion from ethanol SCWG [91]
Property method R2 RMSE [mol⋅mol− 1
ethanol]
PR 0.99 0.25
PR-BM 0.99 0.25
PR-MHV2 0.99 0.27
Predictive RKS 0.98 0.33
RKS-BM 0.99 0.25
RKS-MHV2 0.99 0.26
7
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Fig. 3. Comparison of the equilibrium results with the experimental gas yields of several SCWG systems. 1- SCWG of xylose [97,100] (25Mpa, 650 ◦ C, 4 wt%); 2-
SCWG of microalgae [24] (24 MPa, 600 ◦ C, 7.3 wt%, Ru/TiO2); 3- SCWG of corn starch (CS) & sawdust (SD) mixtures [92] (28 MPa, 685 ◦ C, 10.72 wt% SD + 4.01 wt
% CS); 4- SCWG of methanol [98] (27.6 MPa, 700 ◦ C, 15 wt%); 5- SCWG of ethanol [98] (27.6 MPa, 700 ◦ C, 15 wt%); 6- SCWG of glycerol [37,96] (24.1 MPa, 800 ◦ C,
15 wt%); 7- SCWG of coal (Yimin lignite) [8,13] (25 MPa, 650 ◦ C, 2 wt%).

of experimental results, the results of global thermodynamic equilibrium
and three cases with some constraints. It indicates that the models with
constraints have better prediction accuracy. Besides, it can be inferred
that the more additional constraints are, the better prediction accuracy.
2.2.3. Sensitivity analysis
The thermodynamic equilibrium of the chemical reaction depends
on operating parameters, such as temperature, pressure, and slurry
concentration. Therefore, a large number of parametric studies have
been carried out to investigate how different parameters affect the
thermodynamic and phase equilibrium in the SCWG systems
[40,41,103].
(i) Chemical equilibrium
Table 4 presents the results of parametric studies from numerous
literatures to indicate how different parameters affect the equilibrium
gas yields. The effect of the sensitive factors on GE, CGE, CE, CC, and
other performance indicators are also described.
The performance of the SCWG process depends largely on the reac­
tion temperature. Most studies have indicated that the yield of H2 and
CO2 increases while the yield of CH4 gradually decreases with an in­
crease in the temperature when chemical reactions reach equilibrium
[39,88,95,96,104–106]. Thermodynamically at lower reaction temper­
atures, H2 and CO2 readily react to form methane and water via the
methanation reaction. A higher temperature could limit the methana­
tion reaction and promote the water gas shift reaction, leading to low
CH4 and CO formation [41,88,107]. In addition, the high temperature
reduces the ion product of supercritical water. At this time, the behavior
of supercritical water is similar to high-temperature gas, which favors
free-radical reactions and hence improves the gas yields. However,
when the temperature exceeds the appropriate value where the yield of
H2 is near maximum [94], the further increase of temperature has no
effect on the equilibrium gas yields but increases the energy input
burden of the system. In the study from Lu et al. [41], the syngas pro­
duction stabilized and reached maximum output (88.62 mol/kg dry
biomass) when the temperature reached 923 K, and the peak yield of CO
appeared at about 823 K. In the case of lignin SCWG, 725 ◦ C was the
maximum reaction temperature required for equilibrium [86]. The ef­
fect of temperature on the mole fraction of gas products is roughly as the
same as the gas yields [37,38,44,108–110]. As the temperature in­
creases, the changes of CO2 mole fraction shows a downward trend

8
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

reactions via free radicals [56,112]. Pressure also affects the isobaric
heat capacity of water, which benefits to decrease the energy demand
for the SCWG system [50]. The influence of pressure on sub-and su­
percritical regions was discussed in detail by Basu and Mettanant [6],
from the aspects of ion mechanism and free radical mechanism. There­
fore, the effect of the pressure on the SCWG process is the result of
multiple positive effects and multiple reverse effects acting simulta­
neously, thus the comprehensive effect of pressure on SCWG is limited.
Biomass gasification in SCW is an endothermic reaction. When using
the external heat source for the reactor, the heat transfer efficiency and
energy efficiency of the reactor is low. The addition of less than stoi­
chiometric quantities of oxygen in the gasification process can enable
the reactor to obtain the heat from the situ exothermic oxidation reac­
tion and achieve the high heat transfer efficiency and GE [8]. In general,
the amount of oxygen added during gasification can be measured by
equivalence ratio (ER), defined as [41]:

ER = (weight oxygen/weight dry biomass)/(stoichiometric/biomass ratio)(21)

The isothermal energy analysis on the SCWG of glycerol process

showed that when ER is 0.2, the SCWG process was exothermic in the
whole temperature range (400–1200 ◦ C). When ER is from 0 to 0.5, Lu
Fig. 4. Comparison of the model prediction results with the experimental re­ et al. [41] demonstrated that the increasing amounts of oxygen addition
sults of glucose SCWG (28 MPa, 600 ◦ C, 0.6 M, residence time:50 s). Constraints caused the rapid decline in the yields of H2 and CH4. This conclusion was
for: Case 1: CE = 0.673; Case 2: CE = 0.673, HE = 0.913, constant amount of
unanimously reached by refs [113–115].
hydrogen = 2.63; Case 3: CE = 0.673, HE = 0.913, constant amount of
In addition to the aforementioned operating parameters, some other
methane = 0.71; (modified from ref [102]).
sensitivity factors are mentioned in Table 4. Freitas et al. [108,109]
proved that the addition of CO2 and CH4 as co-reactants was an effective
[89,95]. Notably, the H2 yield increased from 5.40% at 400 ◦ C to
way to increase the H2/CO molar ratio of syngas from the microalgae
38.95% at 600 ◦ C in sewage sludge SCWG system [37]. The thermody­
gasification in SCW. In the integrated SCWG system of sewage sludge for
namic analysis on SCWG of diosgenin solid waste [38] showed that the
power and hydrogen production [71], the addition of lignite increased
H2 fraction increased from 26.08% to 40.14% and CO2 decreased from
the concentration of oxygen in the feedstock of the SCWG process, which
45.90% to 27.89%, while the molar fraction of CO, CH4 changed slightly
caused a negative effect on H2 concentration. A similar trend was re­
when the reaction temperature increased from 500 ◦ C to 650 ◦ C.
ported by Adnan and Hossain [116] in the co-gasification of Indonesia
Although high feedstock concentration is preferable for high energy
coal and microalgae. Yan et al. [88] briefly examined the impact of the
efficiency, both equilibrium calculations and experimental results have
elemental composition of biomass and suggested that high molar ratio of
shown that the changes of the concentration is inversely proportional to
C/O in the feedstock benefits to getting the high yield of H2. Louw et al.
the gas yields during SCWG [37,41,44,47,88,107]. The yield of H2 and
[91] investigated the effect of biomass composition (carbon, hydrogen
CO2 decreases gradually, while the yield of CH4 and CO increases
and oxygen content) on the thermodynamic gas yields from SCWG under
remarkably with an increase in the feedstock concentration. The above
various operating conditions, and stated that a high H2 yield could be
phenomenon can be attributed to the Le Chateleir’s principle for the
obtained in the SCWG of biomass with low C/H ratio and low oxygen
water–gas shift and methanation reactions. The high concentration
content [71].
means low moisture in the feedstock, which promotes the reverse re­
From the thermodynamics perspective, the complete biomass gasi­
action of Eq. (14) and the methanation reaction of Eq. (15), then the
fication in SCW can be achieved to produce H2 and CO2 as the only
yield of the above-mentioned gas product changes [111]. In the SCWG of
gaseous products at a sufficiently long residence time. The study on the
black liquor system [80], H2 fraction in the gas product decreased from
reaction residence time of the SCWG system in near-equilibrium state is
55.72% to 41.99% when the concentration increased from 10 wt% to 20
aimed to obtain the maximum hydrogen production while ensuring the
wt% at 700 ◦ C. The trend was also proved in the SCWG of coal system
economic feasibility of the system. Generally, the reactor size increases
[8]. As the concentration increased from 4 wt% to 24 wt%, the fraction
with the increase of residence time. Although the increase of residence
of H2 decreased from 63.02% to 52.15%. Meanwhile, a biomass slurry
time may increase gas yields, it also aggravates the economic burden of
with high concentration is more difficult to gasify compared with the
equipment. Hence, the equipment cost of the reactor should be consid­
biomass with low slurry concentration. and the uncomplete gasification
ered when choosing the appropriate residence time for reaching the
usually brings the plugging problem of the SCWG system [29,52].
chemical equilibrium. The experimental results show that the contents
According to the chemical equilibrium movement theorem, the three
of H2 and CH4 in gas phase increased with the increase of reaction time,
reactions (Eqs. (13)–(15)) are all inhibited under high pressure, result­
due to the reforming of C2-C3 components to methane and hydrogen
ing in a decrease in the mole fraction of H2 and CO and an increase in the
production via the water–gas shift reaction [24], and more CH4 was
mole fraction of CO2 and CH4 [88]. However, the change of gas fraction
formed via methanation and hydrogenation [106,117]. In the contin­
is small as the change of pressure [39,97,109]. Those findings were
uous SCWG system of 2 wt% coal, Guo and Jin [8] illustrated that the
verified by Hawaii Natural Energy Institute and SKLMP experimental
long residence time will increase the gas yields, but it will lead to poor
data [77]. The same trend was also obtained in the work of
heat transfer, high coking risk of the reactor, and additional mainte­
[37,88,89,110,111]. Some studies have shown that the effect of high
nance cost of the reactor. Based on the experiments, some studies have
pressure on the chemical equilibrium was complex. With the increase of
determined the moderate residence time to balance the risks of plugging
pressure, the properties of water, such as density, static dielectric con­
with high gas yields. Van Bennekom et al. [118] suggested that the
stant, and ion product also increase. Therefore, the rates of the ion re­
optimal residence time of SCWG of glycerol and methanol mixture was
actions increase, which is in favor of gas production from the hydrolysis
40 s. In this case, the higher CE and lower chances of reactor plugging
reaction and water gas shift reaction. On the other hand, higher pressure
could be obtained. Cao et al. [119] demonstrated that the prolongation
restrains free-radical reactions, which in turn inhibits gas formation

9
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Table 4
Thermodynamic equilibrium analysis on SCWG with various sensitivity factors.
Feedstock EOS Software Sensitivity factor and range Syngas composition Performance Refs
indicator
H2 CO CO2 CH4.

Biomass UNIFAC, – T: 673–1073 K ⇑ ∩. ↑ ↓ na. [41]

SRK- C: 0–30 wt% ⇓ ↑ ↓ ↑ na.
MHV2 Oxygen ER: 0–0.5 ↓ na na. Energy
requirement:↓
Paper sludge PR-BM Aspen plus C: 2.5–20 wt% ↓ ≅ ↓ ↑ GE:∩ CE:∩ HE:∩ EnR: [99]
∩
Sewage sludge PR Aspen Plus T: 400-600 C ◦
⇑ ↑ ≅ ↓ LHV:↓ CGE:↑ CC:↓ [37]
P: 25–35 MPa ≅ ↓ ≅ ≅ LHV:≅ CGE:↑ CC:↓
C: 10–40 wt% ↓ ≅ ≅ ↑ LHV:↑ CGE:↑ CC:↑
Diosgenin solid waste PR-BM Aspen Plus T: 500-650 ◦ C ⇑ ↑ ↓ ⇓ HE: ⇑ CE: ⇑ [38]
1
Flow ratio: 20:60–50:60 g⋅min− ↓ ≅ ≅ ↑ HE: ⇓ CE: ↓
Addition ratio of black liquor: ↑ ↓ ≅ ≅ HE: ⇑ CE: ≅
0–18 wt%
Mass C of K2CO3: 0–0.9 wt% ↑ ↓ ⇑ ↓ HE: ∪ CE: ↑ HE: ∪ CE:
↑
Sugarcane bagasse Virial GAMS with the CONOPT T: 773.15–1073.15 K ↑ ↑ ↓ ⇓ [108]
solver C of Co-reactant (CO2): 15–35 wt% ↓ ↑ ↑ ↓
Microalgae PR, HKF Matlab T: 200-600 ◦ C ⇑ na. ↑ ↓ [97]
P: 25–30 MPa ↓ ≅ ≅ ≅
C: 10–30% ⇑ na. ↑ ↓
Microalgae RKS Matlab T: 400-700 ◦ C ⇓ ≅ ↓ ↑ GE:⇑ [24]
Microalgae Virial GAMS with the CONOPT T: 703.15–1103.15 K ⇑ na. ∩ ∩ [109]
solver P: 24–30 MPa ≅ na. na. na.
C: 5–20 wt% ⇓ ≅ ≅ ↑ H2/CO molar ratio: ↓
Co-reactant addition: CO2, CH4 ↓ na. na. na.
Microalgae PR Matlab T: 400-1200 ◦ C ⇑ ⇑ ∩ ∩ na. [110]
C: 0–100 wt% ∩ ≅ ∩ ∩
P: 0–500 MPa ⇓ ↓ ↑ ↑
Algae PR Aspen Plus T: 500-640 ◦ C ⇑ ≅ ↓ ↓ na. [44]
C: 4–16% ⇓ ≅ ≅ ↑ CE:↑
Xylose PR – C: 4–24 wt% ⇓ ≅ ↑ ↑ CGE: ⇓ [100]
Glucose Duan Aspen Plus T: 650-1050 ◦ C ⇑ ⇑ ↑ ↓ GE:↑ HHV:↓ CGE:↑ [88]
P: 20–35 Mpa ↓ ⇓ ↑ ↑ GE: ≅ HHV: ≅
CGE:≅
C: 0.1–1 M ⇓ ≅ ↓ ↑ GE:↓ HHV:↓ CGE:↓
Glucose PR – T: 600-767 ◦ C ↑ na. na. na. CE:↓ TOC:⇑ [94]
C: 1.8–15 wt% ↓ na. na. na. CE: ≅ TOC:⇑
Glucose PR LINGO T: 900–1020 K ⇑ ≅ ↓ ↓ H2O yield:↓ [95]
Glucose PR T: 900–1025 K ↑ ≅ ≅ ↓ na. [39]
Cellulose PR T: 650–710 K ↑ na. ≅ ≅ na. [39]
Cellulose SRKMHV2 Aspen Plus T: 200–900 ◦ C ⇑ ↑ ↓ ⇓ na. [89]
C: 5–20 wt% na. na. na. na. TE:⇑
Methane PR LINGO T: 825-975 ◦ C ⇑ ≅ ≅ ⇓ na. [95]
C: 15–45 wt% ⇓ ≅ ≅ ⇑ na.
Methanol PR GAMS with the CONOPT T: 825–975 K ⇑ ≅ ≅ ⇓ na. [39]
solver C: 15–45 wt% ⇓ ≅ ≅ ⇑
Methanol SRKMHV2 Aspen Plus T: 200–900 ◦ C ⇑ ↑ ≅ ⇓ na. [89]
P 100–400 bar ↓ ≅ ≅ ↑ na.
C: 5–20 wt% na. na. na. na. TE:⇑
Ethanol PR T: 975–1075 K ⇑ ≅ ≅ ↓ na. [39]
C: 5–20 wt% ⇓ ≅ ↓ ↑
Glycerol PR Matlab T: 400-1200 ◦ C ⇑ ⇑ ∩ ∩ HHV: ↓ [110]
C: 0–100 wt% ∩ ↑ ∩ ∩ na.
P: 0–500 MPa ⇓ ↓ ↑ ↑ na.
Glycerol PR T: 975–1075 K ↑ ≅ ≅ na. na. [39]
C: 5–40 wt% ⇓ ≅ ↓ ↑
Glycerol PR CHEMCAD T: 700-800 ◦ C ↑ ≅ ≅ ≅ na. [96]
C: 0–40 wt% ⇓ ≅ ≅ ↑
Glycerol SRK Matlab T: 550-650 ◦ C ⇑ ≅ ↑ ↓ GE:⇑ [24]
Glycerol & methanol mixtures PR Aspen Plus T: 450-600 ◦ C ⇑ ↑ ↑ ↓ [104]
C: 10–25 wt% ⇓ ↑ ↓ ↑
Lignite coal & Sewage sludge PR Aspen Plus T: 500-700 ◦ C ↑ na. na. na. GY:↑ [71]
mixtures C: 10–30 wt% ↓ ≅ ≅ ↑ GY:↓
Lignite coal addition: 0–50% ↓ ≅ ↓ ↑ na.
Coal – – T: 600-700 ◦ C ↑ ↑ ↓ ↓ CE:↑ GE:⇑ [8]
C: 4–24 wt% ↑ ∩ ↓ ↓ HE:⇑ CGE:↑
Flow rate: 3, 5, 7 kg⋅h− 1 ⇑ ∩ ↑ ↑ CE:∩ GE:∩

T: Temperature; P: Pressure; C: Slurry concentration;

k: The slope Note: 1/4 < |k| < 1 ↑: increasing; ↓: decreasing; |k| > 1 ⇑: increasing; ⇓: decreasing; |k| < 1/4 ≅ : not sensitive to changes; na.: not available;
∩: Increase firstly and then decrease; ∪: Decrease firstly and then increase;

10
J. Chen et al.
of the reaction time can improve GE and H2 yield in the black liquor
SCWG system. However, when the reaction time exceeded 30 min and
the reaction reached the equilibrium state, the H2 yield decreased
slightly while the CH4 yield increased from 7.76 to 9.71 mol/kg.
Although the reaction time has little impact on the hydrogen generation
reactions at equilibrium, it can still affect some hydrogen-consuming
reactions, like methanations (Eq. (15)) which generate CH4.
In addition to optimizing the process parameters, reactor configu­
ration, and reaction environment, using heterogeneous and homoge­
neous catalysts in the SCWG process is also an effective way to achieve
high GE and equilibrium gas yields [77,99,120]. Effective catalysts have
been widely demonstrated in practice to enhance the water–gas shift
activity in hot compressed water by scissoring the C–C and C–H bonds
and promote the methanation reaction [24,53,120]. Minowa and Ogi
[121] firstly proposed the gasification mechanism of cellulose in sub and
supercritical water with the Ni catalyst and indicated that Ni promoted
the gasification of water-soluble products into H2 and CO2. Adamu et al.
[122] verified the enhancement of glucose gasification by Ni/La2O3-
Al2O3 towards the thermodynamic extremum under supercritical water
conditions. Chakinala et al. [24] studied the effects of different hetero­
geneous catalysts on gas composition and concluded that high H2 yield
(10 mol/kg algae) and complete algae gasification were obtained with
Ru/TiO2 catalyst. Heterogeneous catalysts are also beneficial to the
SCWG. Cao et al. [38] found that plenty of alkalis in the black liquor,
including K2CO3, NaOH, Na2CO3, and NaHCO3, accelerated the water­
–gas shift reaction in SCWG of diosgenin solid waste. Based on the
experimental results of SCWG of glycerol and methanol mixtures, Reddy
et al. [104] proposed that the activity order of alkali catalysts promoting
water–gas shift reaction was: K2CO3 > NaOH > KOH > Na2CO3. The
highest H2 yield (24.8 mmol⋅g− 1), total gas yields (1.24 g⋅L− 1), and CE
(96.7%) were achieved in the presence of 0.5 wt% K2CO3. The similar
significant effect of the K2CO3 catalyst was also demonstrated in refs
[24,38,123].
When studying the effect of various process conditions on gas yields,
the inter-dependent impacts of process conditions should also be
considered. Generally, the gas yield in the SCWG process increases with
temperature and residence time. However, some studies indicated that
high temperature with long residence time might cause re-
polymerization of intermediate products and an increase in tar and
char formation [23,45,124]. To obtain the high gas yields under the
conditions of high temperature and long residence time, using metals as
the reactor materials and adding catalysts are good options [53,124].
The studies show that using of Inconel reactor is beneficial to sup­
pressing the repolymerization, inhibiting the formation of tar and char
and increasing gas yields [85]. Contrarily, at high temperature with long
residence time, gas yields in the stainless steel reactor might not always
increase or can even decrease as the temperature increases [84,85]. It is
worth mentioning that the biomass structure and constituents will affect
the gasification characteristics of biomass. Susanti et al. [94] investi­
gated the gasification characteristics of biomass model compounds such
as methanol, ethanol, glucose, and glycerol, as well as model compounds
of petroleum fuels under different temperature and concentration con­
ditions. The comparison results revealed that the simple oxygenated
hydrocarbons were easier to be gasified compared with long-chain hy­
drocarbons under identical conditions. The increase trends of gas yields
differed significantly with increasing temperature and decreasing con­
centration. The gas yields resulting from long-chain hydrocarbon feed­
stock were more sensitive to the changes in operating conditions. The
reaction routes and the operating conditions required for biomass SCWG
will be different due to the biomass constituent and structure. Some
related studies on the molecular dynamics and chemistry have been
carried out [125,126]. Hu et al.[51] reviewed the underlying mecha­
nism and kinetics of biomass model compounds and summarized the
basic reaction pathway of biomass components during SCWG treatment.
Rodriguez Correa and Kruse [127] conducted a similar study. Safari
et al. [27,128] revealed the effect of feedstock type with different
11
Energy Conversion and Management 226 (2020) 113497
biomass structure on gas yields and the hydrogen yield of SCWG sys­
tems. Table 4 shows the variation degree of gas yields from different
biomass types with the changes of operating conditions.
From the above analysis, it can be concluded that the operating pa­
rameters play a significant role in the SCWG process. Although the re­
sults of the above studies are slightly different due to different
equilibrium conditions and various feedstock, the overall trend is
consistent and can be summarized as follows: (1) High operating tem­
peratures boost the yield of H2 and CO2 and reduce the yield of CH4. The
yield of CO is very low, and it first increases and then decreases with
increasing temperature. (2) With the increase of feedstock concentra­
tion, the yield of H2 and CO2 decreases gradually and the yield of CH4
and CO increases. (3) Pressure has much less effect on chemical equi­
librium than temperature. With the increase of pressure, the yield of H2
and CO decreases and the yield of CH4 and CO2 changes little.
(ii) Gas-liquid equilibrium
The high-pressure separator in the SCWG system can be used to
initially separate the products. Due to the different solubility of CO2 and
other gases in water, the enrichment of CO2 and purification of H2 can be
realized by adjusting the phase equilibrium which is affected by the
operation parameters of high-pressure separator [40]. Feng et al. [40]
presented the phase behavior and phase equilibria in the reactor and
separator. And the favorable operating conditions and the trends of
product distribution were revealed. Considering the effects of feedstock
concentration and temperature, Letellier et al. [103] used the mass
balance as well as physical equilibrium equations of species between
liquid and gas phases to simulate the separator. Based on the modified
universal functional activity coefficient (UNIFAC) model, SRK EOS, and
MHV2 mixing rule, Lu et al. [41] established a high-pressure gas–liquid
equilibrium model to study the effects of pressure, temperature, and
water recycled ratio on the gas–liquid equilibrium. By using the PR EOS,
Marias et al. [42] explored the effect of working temperature, the initial
composition of the vinasse, and air supply on the composition of solid,
liquid, and gas products in the output of separator. Similarly, Yakaboylu
et al. [97] studied the phase behavior of different elements (carbon,
chlorine, potassium, nitrogen, sodium, phosphorus, sulfur, silicon)
under different conditions of temperatures, pressures, and dry matter
concentrations.
Numerous results of phase equilibrium in the high-pressure separator
showed that the increase of pressure and temperature is beneficial to
improve the hydrogen purity in the gas phase. As shown in Fig. 5, with
the increase of pressure, the mole fraction of H2 gradually increases, but
the mole fraction of CH4 remains unchanged. The reason is that the
Henry constant of CH4 is higher than that of H2, and it cannot be
completely separated from hydrogen in the separator [41]. Contrary to
the effect of pressure, the molar fraction of H2 in the gas phase decreases
as the increase in temperature [103].
Generally, to realize the enrichment of CO2 and the purification of H2
with low energy consumption, the separation of CO2 and H2 can be
promoted by optimizing the operating parameters of the separator.
However, the variation trend of the purity of H2 in the gas phase with the
operating temperature and pressure is opposite to recovery ratio of H2.
Therefore, the hydrogen purity and recovery ratio should be taken into
consideration comprehensively when selecting the operating parame­
ters of the high-pressure separator. Moreover, according to the predicted
results of the model, some further treatment is needed to obtain high-
purity hydrogen, such as pressure swing adsorption and membrane
separation.
3. Environmental life cycle assessment of SCWG process
Recently, many studies have committed to building an efficient
SCWG process for getting hydrogen-rich combustible gases while mini­
mizing the environmental impacts associated with SCWG processes.
J. Chen et al.
Fig. 5. Effects of operation pressure on molar composition of the gas leaving the separator at 298 K: (a) gas composition and hydrogen recovery ratio in gas phase,
(b) gas composition in liquid phase. (adopted from [41]).
3.1. Environmental life cycle assessment methods
The LCA has been widely used in recent years to investigate the
potential environmental impacts of the entire life cycle stages from raw
material acquisition to final waste management, and identify the po­
tential for environmental improvements to facilitate industrial decision-
making towards sustainable resource management.
In the late 1960s and early 1970s, LCA has been officially defined by
the International Organization for Standardization. LCA consists of four
interrelated steps as follows [129]:
(i) Goal and scope definition. Determining the system boundary is
the prerequisite for LCA. In LCA, the entire life cycle of a product
from cradle to grave is usually taken as the system boundary of
the research. However, because the entire life cycle of a product
covers many contents and a large span of time and space, some
studies limit the system boundary to hydrogen generation, that is,
the analysis from cradle to gate. If the use stage of hydrogen is
included, it is defined as cradle-to-grave analysis.
(ii) Life cycle inventory for collecting and compiling all of the rele­
vant inputs and outputs related to production [130]. Different
software (Gabi [131], Simapro [132,133], LCAiT [134], etc.) are
used for the inventory data collection. All inventory data
collected must be converted into functional units, with the goal of
standardizing the inputs and outputs of each unit. Functional
units also provide the possibility of comparing environmental
benefits between different systems. The most common functional
unit is the amount of H2 produced, which can be measured by
weight, energy or, volume. However, in some cases, the quanti­
fied electricity generated from H2 can also be used as the func­
tional unit in SCWG systems.
(iii) Life cycle impact assessment (LCIA). LCIA methodology sim­
plifies hundreds of flows traversing the system boundary into
several environmental areas of interest to systematically evaluate
the environmental impacts. There are several LCIA methods, such
as Eco-indicator 99 & 95 [133], EPS 2000, CML [131–133], and
Impact 2002.
The environmental performance indicator was calculated based on
the life cycle analysis (LCA) method to assess the environmental impacts
which are associated with a product, process, or service over its entire
life cycle. Generally, the mid-point impact categories include [135]:
Global warming potential (GWP) that can be normalized to CO2 equiv­
alent emissions; Eutrophication potential (EP) used as a measure of
phosphorus and nitrogen; Acidification potential (AP) which is attrib­
uted to the acid formed by the reaction of SOx, NOx, and NH3 with water
12
Energy Conversion and Management 226 (2020) 113497
vapor; Abiotic depletion potential (ADP); Ozone layer depletion poten­
tial (ODP); Photochemical oxidation potential (POFP); Winter smog
potentials (WSP), etc. And the end-point categories include Human
Health (HHE), Ecosystem Quality (EQ), Climate Change (CC), and
Resource Scarcity (RS) [46].
In addition to the above ecological indicators, it is worth pointing out
that the indicators of cumulative energy demand (CED) and cumulative
exergy demand aimed to detect the use of energy in each stage of a life
cycle can be used as a supplement to environmental performance
indicators.
(iv) Interpretation of the results and overall assessment.
3.2. Environmental life cycle assessment results
Following the principles and framework of ISO 14040 Environ­
mental management (ISO, 2006)-Life cycle assessment, many studies
have assessed the environmental impact of SCWG systems. Due to the
difference in key technologies and objectives of various SCWG systems,
system boundaries, target products, functional units, and operating
conditions (temperature, pressure, slurry concentration, heating
methods, etc.) will be different, which have a great effect on the LCA
results. To improve the environmental benefits of the SCWG process,
many sensitivity analyses have been conducted to classify and quantify
the uncertainties in the LCA of the SCWG process [136]. Table 5 sum­
marizes the effect of some sensitivity factors on environmental perfor­
mance. Two impact categories, GWP and AP, are selected as indicators
to measure environmental emissions.
The sensitivity analysis on the LCA in the Solar-based SCWG system
[46] and ISCWGC-HPP system [13] were conducted by our previous
studies. Fig. 6 depicts the environmental impact of the two SCWG sys­
tems at various stages of their life cycle in different scenarios. In both
systems, the GWP and AP were mainly derived from the operation stage,
and the GWP decreases with the increase in the reactor temperature and
biomass concentration. In the ISCWGC-HPP system, the adoption of CCS
decreased the GWP from 0.66 kg CO2-eq/(kW⋅h) to 0.058 kg CO2-eq/
(kW⋅h) at 700 ◦ C, 15 wt% and 25 MPa [13]. However, in the solar-
powered SCWG pilot plant, the application of CCS effectively reduced
the GWP but increased power consumption and the overall environ­
mental impact of the system. Contrary to the above two systems, in the
SCWG system with external recycle of liquid residual [47], the increase
of slurry concentration resulted in a slight increase in GWP and stan­
dardized GWP, by 7.26% and 7.59%, respectively. Similarly, the high
pressure was also regarded as a negative factor, which aggravated the
value of GWP. The influence of temperature on GWP was consistent with
our previous studies [13,46]. Taking the change of production input
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Table 5
Evaluation studies of LCA on SCWG from recent literatures.
Technology Functional Software or LCIA Impact category Sensitivity factors System Results and remark
unit (FU) database methodology boundary

ISCWGC-HPP [13] 1 kW⋅h of net SimaPro, CML, ECO- GWP, AP, ADP, T: 600 ◦ C -700 ◦ C Cradle-to- GWP: 0.058–0.95 kg CO2-eq/FU
power output Ecoinvent Indicator 99 ODP, EP, POFP, C: 2–15 wt% gate AP: 3.13 × 10− 4-1.14 × 10− 3
database NOx Without/With CCS kg SO2-eq/FU
High temperature, slurry
concentration and adopt of CCS
are beneficial to decrease the
GWP
Solar-based SCWG of 1 kg H2 SimaPro, CML-IA, ReCiPe GWP, ADP, AP, Heat method: solar, Cradle-to- GWP: − 2.46–10.95 kg
biomass [46] Ecoinvent Endpoint, EP, ODP, POFP, electricity, heat supply/ grave CO2-eq/FU
database CED, HH, EQ, RS treatment of methane. AP: 0.074–0.193 kg SO2-eq/FU
C: 0.1–0.8 wt% High concentration and adopt
Without/With CCS of CCS are beneficial to
decrease the GWP.
SCWG of biomass with 1 kg H2 – GWP T: 500-560 ◦ C Cradle-to- Standardized GWP: 6.48 ×
external recycle of C: 2.78–2.95% gate 10− 3-3.52
liquid residual [47] P: 21–26 MPa Increase of temperature,
decrease of slurry
concentration and pressure
could decrease GWP
SCWG of sewage 1 g H2 Umberto – GWP, AP, EP, – Cradle-to- GWP: 0.7 g CO2-eq/FU
sludge [137] CED gate AP: 0.1 g SO2-eq/FU
SCWG of microalgae 1 MJ H2 – – GHG Change in input factors Cradle-to- GWP: 13.11–19.69 kg CO2-eq/
[138] of production: ±10% gate FU
SCWG of glycerol 1 kg H2 SimaPro CML 2000 GWP, ADP, ODP, – Cradle-to- GWP: 3.77 kg CO2-eq/FU
[132] AP, EP, POFP, grave AP: 1.24 × 10− 2 kg SO2-eq/FU
CED

Fig. 6. Impact assessment results of the GWP and AP during the life cycle of SCWG (a:redrawn from [46]; In the 1–8 case, the heating method of reactors and
preheater, treatment methods of methane, and whether to use CCS are different. b:redrawn from [13]; In the A-H process, the temperature, feedstock concentration,
and whether to use CCS are different).

13
J. Chen et al.
factors as a sensitive factor, Pankratz et al. [138] concluded that the
GHG emission range of the SCWG of microalgae system was between
13.11 and 19.69 kg CO2-eq/kg H2. Galera and Gutiérrez Ortiz [132]
evaluated the environmental performance of supercritical water
reforming of glycerol for hydrogen and electricity production. The re­
sults showed that the CO2 emission of the process was only 3.77 kg CO2-
eq/kg H2.
Besides the sensitivity analysis, the dominance analysis has also been
adopted to identify the dominant units or subsystems that have the
greatest potential environmental impacts on the SCWG system. Domi­
nance analysis can also provide optimization methods for improving
system environmental performance. Through the dominance analysis,
Gasafi et al. [137] identified the hot spots related to environmental
impacts in the SCWG of sewage sludge process chain. The analysis
showed that GWP mainly came from the additional heat supply during
the gasification process, and the process of producing blending agent in
the dewatering step was the main source of the AP. Aiming to reduce the
complexity of the research, Gasafi [139] conducted further Pareto-
dominance analysis of the SCWG system of sewage sludge. Fig. 7
shows the normalized impact results of human toxicity potential being
plotted versus the GWP potential. It is indicated that the sewage sludge
gasification process, natural gas production pre-chain, and the con­
struction process were the main environmental emission sources of the
system. Therefore, those phases should be given priority in life cycle
assessment to improve the ecological compatibility of the whole system.
Especially, the storage, transportation, and distribution of hydrogen
to the end-user also affect the environmental impact and the cost of
hydrogen production. Demir et al. [140] conducted a detailed perfor­
mance and cost evaluation study on the whole life cycle of hydrogen
from generation to final consumption. Wulf et al. [141] presented a LCA
of three hydrogen supply chain architectures. However, the existing life
cycle studies on the SCWG systems rarely extend the assessment scope to
the utilization and consumption stage of hydrogen after leaving the
system.
3.3. Comparison with other technologies for hydrogen production
In this section, GWP and AP are selected as the typical environmental
impact indicators, and a comparison link between different hydrogen
production systems is established with the function unit of 1 kg H2.
The environmental performance comparison results of SCWG to
Fig. 7. Pareto-dominance analysis on the SCWG of sewage sludge system (adopted from [139]).
14
Energy Conversion and Management 226 (2020) 113497
other hydrogen production technologies and the energy supply mode of
systems are presented by boxplot in Fig. 8. It can be seen that the GWP of
the SCWG system is generally less than the average value of 1.78 kg
CO2-eq/kg H2 [13,132,137,138]. The maximum and minimum values of
GWP in the Solar-based SCWG of biomass system [41] are 10.95 kg
CO2-eq/kg H2 and − 2.46 kg CO2-eq/kg H2, respectively [46]. The large
gap of GWP in the different cases of the solar-based SCWG system is
caused by the way of handling the by-product methane and whether to
use a CCS unit. From the GWP perspective, the traditional biomass
gasification technology [4,131,142] is comparable to SCWG technology.
However, the GWP generated from traditional fossil fuel gasification
process is as high as 11.30 kg CO2-eq/kg H2 [135], 18 kg CO2-eq/kg H2
[143], 19.75 kg CO2-eq/kg H2 [4], or even 29.33 kg CO2-eq/kg H2 [144],
losing the competitiveness with SCWG process. Compared with other
hydrogen production technologies, the average value of GWP and AP of
the steam reforming process is the highest. GWP and AP generated by
steam reforming systems vary widely, whether in the systems based on
biomass feedstock such as sugarcane juice [145], biomethane [133],
bioethanol [133], or in the systems based on fossil fuel including
methane [133,142,144], ethane [144], naptha [144], natural gas, and
ethanol [146–150]. Additionally, the auto-thermal reforming process
for hydrogen production [133,150,151], also has a significant environ­
mental impact.
Besides the feedstock type, the energy supply mode of the system also
affects the environmental performance of the hydrogen production
system. International Energy Agency indicated that greenhouse gas
emissions could be obviously reduced via replacing fossil fuel by
renewable energies, such as nuclear, wind, solar energy, photovoltaic,
and hydropower [152]. Thermochemical water decomposition pro­
cesses driven by nuclear, solar, and wind energy are the most remark­
able methods for large-scale hydrogen production, and also have the
acceptable environmental performance. As shown in Fig. 8, the average
GWP of water electrolysis and water-splitting systems is 1.35 and 2.32
kg CO2-eq/kg H2 respectively, and the average value AP of those two
systems is also within the acceptable range. In detail, water electrolysis
processes, whether driven by nuclear [146,153], wind [146,147], or
solar power [135,146,147,154], have excellent environmental perfor­
mance. However, its environmental performance is still slightly inferior
to that of the water-splitting technology. The minimum CO2 emission of
the water-splitting system is close to zero [146,148]. The value of GWP
in other thermochemical water splitting systems, such as the system
J. Chen et al.
Fig. 8. Comparison of environmental performance among various hydrogen production technologies.
using CdZnS or ZnO as catalysis [154], Cu-Cl or S-I cycle [135,146,147],
are approximately around 0.5 kg CO2-eq/kg H2.
The above discussion shows that the average GWP and AP generated
by water-splitting technology for hydrogen production are the lowest
compared with other hydrogen production technologies. The water-
splitting technologies have excellent environmental benefits. The
steam reforming has poor environmental performance due to its highest
averaged GWP and AP. The environmental competitiveness of SCWG is
significantly higher than that of steam reforming and auto-thermal
reforming but inferior to water electrolysis, water-splitting, and con­
ventional gasification technologies.
4. Techno-economic analysis of SCWG process
The process of SCWG has attracted extensive attention in recent
years due to its high energy conversion efficiency and environmental
benefit. Meanwhile, the SCWG can directly deal with wet materials,
thereby eliminating the capital-intensive drying step. To promote large-
scale development and commercialization of SCWG, further economic
evaluation is required. Techno-economic analysis (TEA) can be used to
evaluate the economic feasibility from both technical and economic
perspectives and assess the profitability and optimize the costs of the
SCWG system. The common software, Hysys or UniSim, can be used for
plant design and its economic and sensitivity analysis [155].
To evaluate the competitiveness of the SCWG hydrogen production
process, the hydrogen production cost (HPC) is compared between
different SCWG systems and traditional hydrogen production processes.
To eliminate currency value differences due to the inflation rate between
different years, this review updated the collected HPC data with 2019
US$ based on the US Consumer Price Index Data.
4.1. General review of economic analysis
The first economic analysis on the SCWG plant was published by
General Atomics in 1997. The HPC of a SCWO pilot plant under the
conditions of 20% and 40% dry matter content at the throughput of
5625 kg⋅h− 1 sewage sludge was studied [48]. In 1999, Amos [156] used
a complex membrane technology purification device to purify the
15
Energy Conversion and Management 226 (2020) 113497
product gas from starch waste SCWG plant. The economic analysis re­
sults showed that the membrane unit accounted for more than 35% of
the equipment cost. Since then, many studies on the economic evalua­
tion of SCWG process have been conducted. In the economic evaluation
on SCWG plant with the throughput of 1 dry-t/d water hyacinth, the
initial cost of SCWG process components was considered, but the
transportation cost, OC and labor cost of the product gas were ignored
by Matsumura [79]. Gasafi et al. [45] found that those cost categories
which were ignored by Matsumura would significantly affect the final
economic results of sewage sludge SCWG plants. In their economic
analysis, the total revenue requirement (TRR), which is the sum of the
total capital investment (TCI), minimum return on investment (ROI),
fuel cost (FC) and operation and maintenance costs (OMC), was adopted
to determine the HPC of the sewage sludge SCWG plant.
Similarly, Lu et al. [76] also used TRR to analyze the HPC of solar-
driven biomass SCWG with a treatment capacity of 1 t/h. Do et al.
[157] adopt the economic values such as ROI, payback period, and in­
ternal rate of return (IRR) to calculate the TCI and total production cost
(TPC) of bio heavy-oil from the treatment of sewage sludge in super­
critical and subcritical water. To determine the feasibility of SCWG of
black liquor from a pulp mill, Özdenkçi et al. [158] evaluated the
profitability of five energy production scenarios based on the net present
value (NPV) and IRR. Besides the aforementioned cost categories, the
manufacturing cost [155], depreciation cost [35], construction costs of
the SCWG plant [76,159,160] were also considered by many economic
evaluation studies. The details of the cost composition of the SCWG
system are shown in Table 6.
In addition to those economic evaluation methods mentioned above,
the common analysis methods also include life cycle cost [161], analytic
hierarchy process, or Fuzzy analytic hierarchy process [162,163],
exergo-economic [164–167], and a discounted cash flow analysis [168].
4.2. Sensitivity analysis
Sensitivity analysis is the most common method of uncertainty
analysis on economic evaluation. By analyzing the effects of sensitivity
factors on the cost of SCWG plants, it is possible to make a correct
judgment on the optimal design of the plant from an economic
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

Table 6
Economic analysis on different SCWG systems.
Feedstock Base Target Capacity Cost categories Sensitivity factors Results and remarks
year products
Indicator Positive factor Negative factor

SCWG of 2017 Bio 100 t/d Lifetime: 20 year ROI, economic Plant capacity (20–100 t/ TCI > TPC The updated net
sewage heavy-oil TCI: 15.1 M$ potential d), minimum bio heavy-
sludge [157] TPC: 2.1 M$/yr Sewage sludge treatment oil selling price:0.95
ROI: 5.7%/yr credit > Bio heavy-oil $/L
Payback period: price
9.63 yr
SCWG of 2007 H2 5 t/d Lifetime: 20 year HPC Learning effect, Sludge EPC > Interest on debt > Updated HPC range:
sewage Direct cost: 8.5 revenue Operating labor > Energy 3.91–10.72 $/GJ
sludge [49] M€ price
Indirect cost: 3.5
M€
Carrying charges:
1.76 M €
FC: 0.65 M€
OMC: 0.42 M€
SCWG of 2011 H2/CH4 481 kg/h Fixed capital Annual net Feed concentration, – Annual net income
sewage H2 yeild investment: 53.4 income Sewage treatment will be the highest at
sludge [155] M$ incentives (550 $/t-dry), 3.78 $/kg H2 selling
TCI: 64.06 M$ H2 selling price price.
SCWG of 2011 H2 579 kg/h TCI: 6.21 M$ Annual net Feed concentration (15, – Updated profitable
glucose [155] H2 yeild Direct income 25 wt%) H2 selling price: 5.68
manufacturing H2 selling price (0–8 $/kg for 15 wt%,
costs: 12.87 M$ $/kg) 4.32 $/kg for 25 wt
Indirect %.
manufacturing
costs: 3.34 M$
Annual general
expenses: 19.13 M
$
SCWG of algal 2016 H2 2000 dry Lifetime:20 years HPC Capacity (500–5000 t/ Biomass cost, IRR, Updated HPC range:
biomass t/d Total EPC: 56.2 M day), Production yield, 4.78–5.0 $/kg at
[159] $ 2000 t/d capacity.
TCI: 277.8 M$
Installed capital
cost: 169.6 M$
Solar-driven 2016 Algae-to- 7600 t/yr Lifetime: 30 years Levelized cost – Cost of algae > Discount Updated levelized
SCWG + FT of liquid of fuel TCI, OC, of fuel rate > FT unit > syngas cost of fuel as low as
algae [169] fuel Penalty cost for storage 2.60 $/L gasoline
CO2 emissions equivalent
SCWG of 2012 SNG 86,500 t/d Construction SNG Feed concentration > Construction cost > Updated SNG cost:
microalgae costs: 14,360 €/ha production Harvesting concentration Electricity cost > CO2 79–129 $/GJ
[160] Labor costs: cost > Biomass productivity uptake
27,342 €/ha/yr
TPC: 97,931
€/ha/yr
SCWG of 2014 SNG 1 kg/h Indirect cost, OC, Break-even – The enzyme for bagasse The break-even SNG
sugarcane SNG yield Depreciation cost prices for SNG, hydrolysis costs (4.24, price is lower than
biorefinery electricity 10.14 $/kg), Percentage 32.40 $/MWh is
residues[35] of bagasse (50%, 70%, profitable
80%)
SCWG integrate 2016 Energy, 800 k adt Lifetime: 25 year Minimum pulp Reactor temperature – The minimum
pulp mill of Pulp pulp/yr TCI, OMC selling price (450 ◦ C, 600 ◦ C), Feed updated profitable
black liquor concentration selling price: 691,
[170] 692 $/adt pulp
SCWG on CHP- 2018 CHP, H2 100 t/h Lifetime: 20 year HPC Temperature (600, Chemical loss (0–20%), Updated HPC range:
Inc-700 of black EPC: 9.7–13.5 M€ 700 ◦ C), Reactor material Change in CHP price 1.74–4.65 $/kg
black liquor liquor TCI: 64.9–47.8 M€ (stainless steel, inconel) (±20%)
[158] inlet Total OC: NPV IRR (0.06–0.09), Chemical loss (0–20%) Updated maximum
61.8–59.1 M€ Lifetime (0–20 year) NPV: 46.78 M$
Total Revenue: Change in CHP price
65.7–72.0 M€/yr (±20%)
Solar-driven 2010 H2 1 t/h Lifetime: 20 year HPC Treatment capacity TCI > Interest rate > Updated HPC range:
SCWG of wet EPC: 3.495 × 106 (1–10 t/h), Operation Biomass feedstock > 6.60–4.31 $/kg.
biomass [76] RMB time > By-product CH4 Labor & administration >
Installed costs: Electricity
2.823 × 106 RMB
Indirect
costs:2.614 × 106
RMB
OC: 1.24 × 106
RMB
SCWG of coal 2015 H2, power 2000 t/d – HPC – Updated HPC range:
[171] 0.94–1.52 $/kg
(continued on next page)

16
J. Chen et al.
Table 6 (continued )
Feedstock Base Target Capacity Cost categories Sensitivity factors
year products
Indicator
Rate of ROI
perspective. A key evaluation indicator in economic analysis is the ex­
pected cost of the final product. The previous economic sensitivity
analysis studies regarding the SCWG of various feedstocks like sewage
sludge, algal biomass, and black liquor are summarized in Table 6. The
table also gives the final product price and the sensitivity factors
affecting the final product cost of SCWG systems.
Sewage sludge has been considered as a promising biomass resource
for producing renewable and sustainable fuels. Do et al. [157] per­
formed a TEA for bio heavy-oil production process from the treatment of
100 t/d sewage sludge in super- and sub-critical water. The sensitivity
analysis showed that the increase of plant capacity, sewage sludge
treatment credit, and the sales price of bio-heavy oil had a positive effect
on the economic potential and ROI, while they had a negative impact on
TCI and TPC. According to the sensitivity analysis results of Gasafi et al.
[49], the equipment cost (EPC) is the most negative sensitivity factor
affecting HPC, and the increase in EPC will lead to a sharp increase of
hydrogen cost. A 50% increase in equipment costs would increase HPC
by 72%, and the updated HPC range for this system is estimated as
3.91–10.72 $/GJ. Their studies also showed that the learning effect and
sludge revenue could reduce the HPC. If the industry or the government
gives certain incentives to the collection and treatment of sewage
sludge, the benefits from gasified sewage sludge will be even greater.
The incentives for sewage treatment were also suggested in the study of
Al-Mosuli et al. [155]. In a SCWG plant with a hydrogen production
capacity of 481 kg/h, when the sewage treatment reward exceeded 550
$/t-dry (updated to 593.96 $/t-dry), an updated annual net income was
up to 7,624,573 $ at the hydrogen selling price of 3.78 $/kg. The author
also illustrated that the annual net income of the plant increased with
the increase in the feed concentration in a SCWG of glucose system as
well as in a SCWG of sewage system [155].
As shown in Table 6, there are also many economic analysis studies
on the treatment of algal biomass in SCW. The economic study on algae
SCWG system [159] showed that the HPC dropped sharply as the plant
capacity increased from 500 to 5000 t/d firstly, then flattened out at the
capacity of 2000 t/d which gave an updated HPC value of 4.78–5.0
$/kg. This trend was the result of the trade-off between capital, raw
materials, and labor cost, signifying the economies of scale. The studies
on other positive factors showed that a 20% increase in product yield led
to 0.81 $/kg decrease in the product cost. It is worth noting that the HPC
can be greatly reduced when the payment from the producer of CO2 is
considered. Rahbari et al. [169] indicated that the feedstock cost had the
most significant effect on the cost of liquid fuel from a solar-driven
SCWG-reforming of algae and Fischer-Tropsch (FT) processes, and the
updated levelized cost of liquid fuel was as low as 2.6 $/L of gasoline-
equivalent. Brandenberger et al. [160] performed the TEA of synthetic
natural gas (SNG) production process via catalytic SCWG of microalgae.
It is concluded that the feed concentration had the most significant effect
on the SNG production cost. Under optimistic hypothetical conditions,
the updated cost range of SNG was 79–129 $/GJ when the microalgae
treatment capacity of the SCWG plant was 86,500 t/d. However, it is still
higher than the current natural gas price [172]. Thus, the current
technology of processing wet microalgae into SNG via SCWG does not
seem economically attractive. The high-cost requirements in the SCWG
17
Energy Conversion and Management 226 (2020) 113497
Results and remarks
Positive factor Negative factor
Throughput capacity
(100, 500, 1000, 2000 t/
d)
Heat supply (Industrial – The heat supply of
waste heat < Natural gas electricity has the
< Solar concentrating < highest rate of ROI:
Particle oxidant < 5.5 year
Electricity)
of microalgae system may come from extracting microalgae before the
gasification process. Albarelli et al. [173] indicated that the economic
benefit of direct microalgae SCWG in a microalgae-sugarcane bio­
refinery is higher by 7.15% than that of a biorefinery considering low-
pressure solvent extraction prior to SCWG. Albarelli et al. [35] also
suggested that the coupling sugarcane biorefinery with the SCWG pro­
cess would significantly reduce the SNG production costs. When the
production capacity of the plant was 1 kg/h SNG, the production cost of
SNG will be reduced to approximately 10.8–29.16 $/MWh.
The TEA of sewage sludge and algae SCWG shows that the plant
capacity and feedstock concentration are the important sensitive factors.
Moreover, other operating conditions of the SCWG system also have a
great impact on the cost of the end products. In the SCWG of black li­
quor, the reaction temperature was studied in the refs [170,158].
Magdeldin et al. [170] found that the minimum profitable selling price
of the product from the SCWG of 50% weak black liquor was 691 $/air-
dried ton (adt) of pulp for the 450 ◦ C reactor case and 692 $/adt for the
600 ◦ C reactor case. Besides the reactor temperature, the influence of the
reactor material was studied by Özdenkçi et al. [158]. It is indicated that
using Inconel reactor materials were beneficial to reduce the HPC, but
the increase of energy prices and chemical loss have a negative effect on
NPV and HPC. Additionally, the operation time as the most positive
factor was mentioned by Lu et al. [76] in the study of a solar-driven
SCWG system. As shown in Fig. 9, a 30% increase in operation time
leads to a 21% decrease in HPC. In the coal SCWG system, SKLMF
analyzed the influence of various heat supply modes on the rate of ROI,
and reported that the most economical heating method was the utili­
zation of industrial waste heat. The minimum HPC was 0.111 $/Nm3
(updated to 0.94 $/kg) when the maximum throughput capacity is 2000
t/d [171]. Meanwhile, in the SCWG of water hyacinth process [79],
when the heat exchanger efficiency increased from 75% to 90%, HPC
decreased by about 0.004 $/MJ.
Fig. 9. Effects of different component cost on HPC in solar-driven SCWG of wet
biomass system (adopted from [76]).
J. Chen et al. Energy Conversion and Management 226 (2020) 113497

In brief, the factors affecting the economic benefit of the SCWG the energy supply modes directly affect its HPC. It can be seen that HPC
systems can be categorized into two major categories. One category is of systems based on hydroelectricity [190,196,197] and geothermal
about system characteristics, including system capacity, production energy [198–201] are lower than that of wind [165,202–206] and solar
yield, and operating conditions. Among them, the system capacity, energy [207–212] systems. The reason is that power produced by wind
feedstock concentration, and reaction temperature are widely regarded and solar energy is intermittent, which increases the cost of the pro­
as positive factors. Another category of factors is the economic factors duced electricity and reduces the economic benefits of water electrolysis
involved in the operation of the system. Besides the cost categories technology. In conclusion, the HPC of water electrolysis systems driven
involved in guaranteeing the basic operation of the plant, the economic by hydroelectricity and geothermal energy is comparable to that of
benefits of the SCWG systems also depend on the financial measures of SCWG systems.
the government. Especially, in the SCWG technology of sewage sludge, it
is necessary to guide public funds to participate in the construction and 5. Challenges and opportunities
operation of the SCWG system to achieve the goal of energy conserva­
tion, emission reduction, and development of the circular economy. The SCWG system is an energy-intensive process for which thermo­
dynamic analysis can determine the source, cause, and degree of energy
loss. As discussed above, in the SCWG system, the reactor, preheater,
4.3. Comparison with other technologies for hydrogen production
and heat exchanger are proved to have a significant contribution to the
exergy destruction. Therefore, in the future development of the SCWG
The large-scale application of SCWG technology depends on its cost
system, it is necessary to strengthen the thermal integration network of
competitiveness compared with traditional hydrogen production
the system to reduce exergy or energy loss. Although the sensitivity
methods [174,175]. To find out the possibility of using wet biomass
analysis can determine which of operation factors are sensitive to the
energy as a renewable energy source, Matsumura [79] compared SCWG
energy efficiency, exergy efficiency, and thermodynamic equilibrium,
technology with bio-methanation technology from an economic
each factor of the actual system optimization process needs to be opti­
perspective. The evaluation results showed that the HPC of SCWG
mized and selected according to the performance objectives of the sys­
technology was 0.01 $/MJ lower than that of bio-methanation tech­
tem. To determine a preferred choice, maybe a more detailed
nology. According to the cost range of disposal sewage sludge, Gasafi
environmental analysis or techno-economic analysis of the SCWG sys­
et al. [49] determined that SCWG was more cost-effective than elec­
tem should be conducted.
trolysis (updated to 45.62 $/GJ) when the sewage sludge revenue
So far, there are few environmental LCA studies on the SCWG pro­
exceeded 105.46 $/t dry matter. When the sewage sludge revenue once
cess. Especially, there is a lack of sensitivity and uncertainty analysis of
exceeded 358.81 $/t dry matter, the cost competitiveness of the SCWG
LCA, and most of the existing literatures fail to further explain the
system was comparable to that of natural gas reforming (updated to
robustness of the LCA results. Moreover, the environmental impact of
11.6 $/GJ).
the system largely depends on the operating parameters, so how to find
Fig. 10 shows the updated HPC of different systems for hydrogen
the balance between production benefit and environmental performance
production. It can be seen that the cost of SCWG technology is between
is a challenge for the future development of the SCWG technology.
0.94 and 6.6 $/kg [49,76,155,159,171], and the average HPC is 3.81
Finally, few studies have assessed the potential or real social impacts of
$/kg, slightly higher than that of pyrolysis technology (3.33 $/kg)
the process. Therefore, the combination of LCA with social life cycle
[176,177], thermochemical Cu-Cl water-splitting cycle (3.27 $/kg)
assessment is expected to be applied in the SCWG system to improve the
[178–182] and S-I water-splitting cycle (3.45 $/kg) [4,183–186], but
social environment and economic benefits, and provide guidance for the
lower than that of solar thermal based hybrid sulfur cycle [187–189].
future comprehensive sustainability assessment [213,214].
Due to the wide HPC range of steam reforming
Meanwhile, the economic feasibility analysis of the SCWG plant is a
[4,167,176,178,190,191], conventional gasification of biomass
crucial step in making sound decisions for commercial applications.
[164,167,191–193] and conventional gasification of fossil fuels
However, according to the recently published papers, there is still
[191,194,195], it is hard to determine the cost competitiveness of SCWG
relatively little information about its commercial viability, especially in
technology over those systems. However, in terms of the average HPC,
the SCWG of fossil fuel process. The economic sensitivity analysis shows
SCWG technology is cost-competitive. For water electrolysis technology,

Fig. 10. Comparison of the HPC among different hydrogen production technologies.

18
J. Chen et al.
that the economic benefits of the system not only depend on the system
characteristics, but also on the economic factors related to the operation
of the system. In addition to the controllable factors including system
capacity, product yield and operating parameters, the economic benefits
of the SCWG system also depend on the implementation of national
incentives for clean energy production, as well as the market prices of
raw materials, fuel consumption of the process, and the final products.
Thus, the SCWG system should also have the ability to resist external
economic risks.
To realize the energy conservation, emission reduction, and devel­
opment of the circular economy in the SCWG process, the adoption of
renewable energy is a good option in the future. However, the technical
difficulties of producing hydrogen from SCWG technology driven by
renewable energy sources need to be further investigated. Meanwhile, in
the development of SCWG technology, main obstacles, including plug­
ging, catalyst deactivation, and corrosion, also need to be solved ur­
gently. Currently, the salt deposition is a major issue causing catalyst
deactivation and plugging in the SCWG process. This issue can be alle­
viated by increasing the heating rate via mixing biomass with high
temperature preheated water at the reactor entrance [84]. Additionally,
the fluidized bed reactor has been proved to be an effective solution to
inhibit the plugging caused by char formation [215–218]. Other studies
used the phenol and bimetallic catalysts to suppress repolymerization to
decrease char formation [26,219]. To remove the inorganic salt depo­
sition and prevent plugging, some studies separated salts prior to the
reactor or separated the solids in a vertical reactor [17,220]. In addition,
the catalyst deactivation is an inevitable problem. Some measures to
prevent the catalyst from deactivation include using alumina and
magnesia as a catalyst support and using bimetallic catalysts (such as
ruthenium and cobalt) [221]. The methods for reducing corrosion
include selecting reactor materials that are resistant to corrosion (such
as stainless steel and Nickel alloys) and maintaining high temperatures
(e.g. 600 ◦ C or more) [127,222]. Besides, some contents in the feedstock
will also lead to corrosion. For example, the alkaline composition and
sulfide leads to dealloying, and the salt fouling leads to under-deposit
corrosion. To choose the suitable solutions for the challenges
mentioned above, the economic and environmental performance of the
problem-solving methods should also be studied to improve economic
benefits and enhance the attractiveness of industrial applications.
6. Conclusions
Since SCWG is an effective process for hydrogen production, this
study investigates the SCWG process from the thermodynamic, eco­
nomic, and environmental viewpoints. This study is expected to provide
suggestions for further optimization and improvement of SCWG tech­
nology to meet the need for sustainable, economical, and efficient
hydrogen production. Through sensitivity analysis, the factors affecting
the comprehensive performance of the SCWG system are determined. To
compare the competitiveness of SCWG technology with other hydrogen
production technologies, the GWP and AP of the environmental in­
dicators as well as the updated hydrogen production cost of the eco­
nomic indicator are selected to compare the environmental and
economic benefits of SCWG technology with other hydrogen production
technologies. The main findings of this study can be summarized as
follows:
(1) The thermodynamic analysis in this work includes the energy and
exergy efficiencies analysis and the thermodynamic equilibrium
analysis. There are some feasible approaches for improving the
energy and exergy efficiencies such as increasing reaction tem­
perature, slurry concentration, and heat transfer efficiency of
each component. Integrating the external circulation and energy
recovery system with the SCWG system is also an effective
method for improving energy efficiency. Moreover, the thermo­
dynamic equilibrium analysis shows that temperature, reaction
19
Energy Conversion and Management 226 (2020) 113497
time, and feed concentration are the main factors that affect the
thermodynamic equilibrium of SCWG reactions.
(2) According to the sensitivity analysis of LCA of SCWG systems, the
increase of temperature and slurry concentration is in favor of
reducing the environmental burden. The average of GWP and AP
generated in the SCWG process for hydrogen production are 1.78
kg CO2-eq/kg H2 and 17.88 kg SOx-eq/kg H2, respectively.
Compared with other hydrogen production technologies, the
overall environmental performance of the SCWG process is at a
medium level, without significant advantages.
(3) The techno-economic analysis results show that the increase of
system capacity, feedstock concentration, and reaction tempera­
ture are favorable to decrease the HPC. Meanwhile, the economic
benefits of SCWG systems also depend heavily on the financial
measures of the government. The average HPC calculated from
various SCWG systems is 3.81 $/kg, which is comparable with
other hydrogen production systems.
In the future, more high-quality environmental and tech-economic
studies and energy saving and emission reduction technology [223,
224] should be carried out to optimize the operational parameters and
improve the SCWG processes. Compared with other hydrogen produc­
tion technologies, the competitiveness of SCWG technology should be
further enhanced to promote its large-scale commercialization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by National Natural Science
Foundation of China under the research grant of 52076071, Key Projects
of Hunan Province Science and Technology Plan (NO. 2018SK2019) and
Fundamental Research Funds for the Central Universities.
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