Energy Conversion and Management 270 (2022) 116199

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Novel ways for hydrogen production based on methane steam and dry
reforming integrated with carbon capture
Bosheng Su a, b, c, d, e, *, Yilin Wang a, Zhilong Xu a, Wei Han f, Hongguang Jin f,
Hongsheng Wang g, *
a
College of Marine Equipment and Mechanical Engineering, Jimei University, Xiamen 361021, China
b
Fujian Province Key Laboratory of Energy Cleaning Utilization and Development, Xiamen 361021, China
c
Fujian Province Cleaning Combustion and Energy Utilization Research Center, Xiamen 361021, China
d
Fujian Province Key Laboratory of Ocean Renewable Energy Equipment, Xiamen 361021, China
e
Fujian Province University key Laboratory of Ocean Renewable Energy Equipment, Xiamen 361026, China
f
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China
g
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan

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

Keywords: The combination of methane steam reforming technology and CCS (Carbon Capture and Storage) technology has
Hydrogen production great potential to reduce carbon emissions in the process of hydrogen production. Different from the traditional
Methane steam/dry reforming idea of capturing CO2 (Carbon Dioxide) in the exhaust gas with high work consumption, this study simulta­
Carbon dioxide reinjection
neously focuses on CO2 separation from fuel gas and recycling. A new hydrogen production system is developed
Carbon capture
Carbon deposition feature
by methane steam reforming coupled with carbon capture. Separated and captured high-purity carbon dioxide
Thermal performance analysis could be recycled for methane dry reforming; on this basis, a new methane-dry-reforming-driven hydrogen
production system with a carbon dioxide reinjection unit is innovatively proposed. In this study, the energy flow
and irreversible loss in the two newly developed systems are analyzed in detail through energy and exergy
balance analysis. The advantages are explored from the perspective of hydrogen production rate, natural gas
consumption and work consumption. In addition, in consideration of the integrated performance, an optimal
design analysis was conducted. In terms of hydrogen production, the new system based on dry reforming is
better, with an advantage of 2.41%; however, it is worth noting that the comprehensive thermal performance of
the new steam reforming system is better, reaching 10.95%. This study provides new ideas for hydrogen pro­
duction from a low carbon emission perspective and also offers a new direction for future distributed energy
system integration.

1. Introduction
An essential ongoing world’s challenge is to lower the emission of
greenhouse gases (GHGs) to settle the problems of climate change
caused by GHGs. To reach a target of a net zero emission of GHGs by
2050 is an urgent environmental objective for governments [1]. The
Intergovernmental Panel on Climate Change (IPCC) appeals to all na­
tions to prevent the estimate of 1.5 ◦ C of global warming from becoming
reality [2]. From all the GHGs including nitrous oxide (N2O), methane
(CH4), carbon dioxide (CO2), etc, emission of CO2 ranks top one through
human activities; therefore, it is generally believed that CO2 should be
captured first.
Countries around the world are actively designing policies to reduce
carbon emissions. The Chinese government has always paid great
attention to the impact of climate change on the country and society and
actively promoted the reduction of carbon emissions. In 2020, the
strategic goal of carbon peak by 2030 and carbon neutral by 2060 was
officially put forward. From human activities, the CO2 emissions
accounted for in the U.S. were predicted to be about 81.3 % of the
emissions, and globally CO2 is also the primary source with 65 % of all
emissions [3].
About 38 % of global power requirements are satisfied by coal-fired
power plants, and about 30 % of global CO2 emissions are caused by
them [4]. At present, coal and natural gas are widely used to produce

* Corresponding authors at: College of Marine Equipment and Mechanical Engineering, Jimei University, Xiamen 361021, China (B. Su).
E-mail addresses: subosheng@jmu.edu.cn (B. Su), wanghongsheng@whu.edu.cn (H. Wang).

https://doi.org/10.1016/j.enconman.2022.116199
Received 7 June 2022; Received in revised form 29 August 2022; Accepted 30 August 2022
Available online 18 September 2022
0196-8904/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B. Su et al.
Fig. 1. Diagram of the traditional hydrogen production system based on methane steam reforming.
electricity [5], and the world’s current mainstream hydrogen produc­
tion technology is still coal and natural gas as raw materials [6].
Currently, about 60 million tonnes of hydrogen are produced each year;
while, approximately 96 % are obtained from the fossil fuel reforming
processes (18 % coal, 29 % liquid hydrocarbons and 49 % natural gas),
causing high indirect emission of CO2 [7]. Therefore, to reduce the
direct or indirect CO2 emissions, carbon capture technologies have been
developed for the chemical and processing industries. Carbon capture
and storage (CCS) has been proposed and identified as a feasible and
sustainable method to address the issues of climate change [8].
Hydrogen (H2) is identified as a clean fuel of the future due to its
characteristic of zero greenhouse gas emission. Renewable resources-
driven hydrogen production technologies have already been boosted
to achieve a sustainable energy cycle; however, due to the economical
and existing technical limitations, 80–85 % of H2 is mainly derived from
steam reforming [9]. In the near term, increasing the production of
hydrogen would likely be achieved via expanding the scale of hydrogen
production using methane steam reforming (MSR) technology [10].
However, due to its phase transition, the mid-temperature heat con­
sumption for water evaporation is very large. To protect catalysts from
performance degradation and life collapse, the required water should be
the deionized water, and the additional equipment cost and energy
consumption should also be considered [11].
Methane dry reforming (MDR) is capable of converting two types of
greenhouse gases (methane and carbon dioxide) into syngas, and
therefore is identified as a promising way to mitigate the greenhouse
effect [12]. Much work has been done in the field of methane dry
reforming technology. Rathod et al. [13] used biogas as raw material to
drive methane dry reforming reaction with a 16 m2 dish solar collector.
As the methane content in biogas is much higher than carbon dioxide,
the methane conversion rate is less than 60 %. To solve the problem of
low methane conversion rate, Sajjadi SM et al. [14] used a NieCu/Al2O3
nano-catalyst to conduct a dry reforming experiment of methane, and
the results showed that the conversion rate of CH4 and CO2 was the
highest at 850 ◦ C and the gas space speed was 24 L/g. Jin et al. [15] used
a commercial nickel-based catalyst to conduct a methane steam
reforming reaction experiment, and used Aspen Plus software to simu­
late, ensuring the accuracy of Aspen Plus software in simulating
methane steam and dry reforming reaction. Based on this, He et al. [16]
proposed a methane dry and steam reforming system for syngas pro­
duction based on moderate separation of carbon dioxide. By adjusting
the ratio of methane and carbon dioxide, the conversion rate of methane
can be effectively improved, reaching up to 93.62 %. Because the surface
of catalyst is easy to carbon deposition in methane dry reforming reac­
tion, the development of stable catalyst with high performance has
become a research hotspot. Although the special catalyst based on
precious metals can effectively alleviate the carbon deposition problem,
it is difficult to apply commercially in the near future due to its high
price [17]. Therefore, it is still limited to solving the carbon deposition
problem by improving the catalyst.
2
Energy Conversion and Management 270 (2022) 116199
Due to the coke formed during dry reforming reaction, addition of
water could dramatically lower the risk of catalyst carbon deposition
[18]. Han et al. [13] proposed a solar-driven methane dry and steam
reforming process; however, the progress of methane dry reforming is
weakened due to the addition of water steam. According to the studies of
Jin [19], the conversion rate of CO2 is only 20 % as the reaction tem­
perature, pressure and steam-to-carbon molar ratio reach 700 ◦ C, 1 bar
and 1, respectively.
Previous research [20] revealed that in the co-reforming of methane,
from the point of view of preventing carbon deposition, the appearance
of CO2 could seriously influence the required water steam. To avoid coke
formation, the existence of carbon dioxide in the reaction aggrandizes
the required water steam under a certain reaction temperature, while
the opposite effect is observed at temperatures higher than that tem­
perature [20]. In other words, if the reaction temperature is high
enough, the presence of carbon dioxide can reduce the water steam
consumption required for the reaction [21]. Yap et al. [22] indicated
that a gas mixture rich in carbon dioxide improved the carbon balance.
The reason is that the formation of hydrocarbons, known as precursors
of coke, is limited. Some possible reactions between solid carbon and
oxygen species from carbon dioxide splitting can remove the coke
formed on the surface of the catalyst; as a result, in the process of
methane dry reforming, a high molar ratio of carbon dioxide to methane
will also have a benign effect on increasing energy efficiency and can
effectively reduce the risk of carbon deposition [23]. Based on the above
feature, developing a new reforming process has great potential to in­
crease the conversion rate of carbon dioxide and reduce the risk of coke
formation during the reaction.
In this paper, a methane steam reforming hydrogen production sys­
tem combined with carbon capture is proposed to effectively reduce the
carbon emissions in the process of hydrogen production. On this basis,
an innovative method was proposed to effectively utilize the captured
carbon dioxide by increasing the carbon dioxide reinjection device and
constructing the methane dry reforming process with a high molar ratio
of carbon dioxide to methane. By introduction of a CO2 removal unit
(Selexol unit), part of separated CO2 can be reinjected into the reforming
reactor to maintain a high molar ratio of CO2 and CH4 for a very safe
operation without carbon deposition, and the remaining CO2 is pres­
surized and stored. CO2 that would originally be difficult to capture and
store is now used as a useful reactant. It provides a new idea for energy
system integration.
2. System configuration
The conventional hydrogen system is first introduced, and the
existing problems are listed. On this basis, the integration ideas of the
new systems are described. The system configuration will be discussed
further in detail.
B. Su et al.
Fig. 2. Diagram of the hydrogen production system based on methane steam reforming with carbon capture.
Fig. 3. Diagram of integration idea for the hydrogen production system based on methane dry reforming with moderate recycle of carbon dioxide.
2.1. Integration idea
Hydrogen production based on methane steam reforming has several
advantages, including no oxygen required and the highest hydrogen
selectivity, and it has already been industrialized with large-scale pro­
duction. The disadvantages include a huge consumption of ionized
water and mid-temperature heat for water evaporation and high emis­
sion of greenhouse gas (CO2). Fig. 1 shows the diagram of the integration
idea for the traditional hydrogen production system based on methane
steam reforming. The reaction in the main reactor and shift reactors can
be expressed respectively in Eq. (1) [21] and Eq. (2) [21].
To separate and purify hydrogen from gas mixtures, the Pressure
Swing Adsorption (PSA) system is often adopted after water gas shift
reactions. The unseparated gas also contains combustible gas types,
including H2, CO, CH4, etc. This part of the fuel gas is combusted directly
to first drive the methane steam reforming process, and then used for
steam generation.
Due to the problem of high emission of greenhouse gas, a new
methane-steam-reforming driven hydrogen production system with
carbon capture was developed in Fig. 2. Compared with the conven­
tional system in Fig. 1, a CO2 removal system is applied. CO2 is separated
by Selexol technology from the chemical unreacted gas mixture con­
taining H2, CO, CH4, and CO2. In fact, ionized water and mid-
temperature heat are still needed in the reactor for water evaporation.
As mentioned in the introduction, a large amount of carbon dioxide in
the methane dry reforming (shown in Eq. (3) [21]) has a large potential
3
Energy Conversion and Management 270 (2022) 116199
to ease the risk of carbon deposition.
Based on the feature, another new methane dry reforming process
based on a high molar ratio of CO2 and CH4 has a large potential to
improve hydrogen output by dry reforming reaction and subsequent
shift reaction. Though higher CO2/CH4 ratio lowers H2/CO ratio in
syngas; however, still a certain amount of H2 can be generated by sub­
sequent shift reaction (CO + H2O ↔ CO2 + H2). Fig. 3 presents the
integration idea for the hydrogen production system based on methane
dry reforming with moderate recycle of carbon dioxide. On the basis of
the system configuration in Fig. 2, the separated CO2 can be reinjected
into the reforming reactor to maintain a high molar ratio of CO2 and
CH4. In this way, CH4 reacts with CO2 instead of water steam, and two
types of greenhouse gas can be converted into syngas with a much lower
molar ratio of H2 and CO which is more proper for the hydrogen pro­
duction in the subsequent shift reactors. Chen et al. [24] pointed out that
a very high molar ratio of CO2 and CH4 can significantly lower the risk of
carbon deposition on the surface of the catalyst, Wang et al. [25] verified
the dry reforming reaction of methane with nickel-based catalyst, and
also concluded that a high molar ratio of CO2 and CH4 can significantly
reduce the carbon risk of the catalyst surface. Free of dependence on
deionized water in the new design, the mid-temperature heat for the
water evaporation can be saved. The newly developed designs will be
simulated, and their performances will be compared.
CH4 + H2O → CO + H2 (ΔH298 K = 206 kJ/mol) (1)
CO + H2O ↔ CO2 + H2 (ΔH298 K = − 41 kJ/mol) (2)
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Fig. 4. Flow chart of the two newly developed hydrogen production systems integrated with carbon capture and storage unit. (a) Based on steam reforming; (b)
based on dry reforming.

2.2. Flow chart of the new systems

CH4 + CO2 → 2CO + 2H2 (ΔH298 K = 247 kJ/mol)
(3)
The hydrogen production system based on methane steam and dry
reforming with carbon dioxide capture is represented in Fig. 4 (a) and
Fig. 4 (b), respectively. The numbers in Fig. 4 (a) and Fig. 4 (b) represent
the labels of different flow streams, corresponding to Table 3a and
Table 3b, respectively. Two obvious features should be emphasized in

4
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Fig. 5. Experimental equipment of methane co-reforming reactor.

the new system. Firstly, the typical temperature of the methane dry
Table 1
reforming process exceeds 870 ◦ C [26], and the extremely high reaction
Catalyst composition and proportion.
temperature will cut the lifespan of the costly reformer and the catalyst;
Major ingredient Unit Value as a result, operating and maintenance costs will rise significantly. The
NiO ≥% 14.5 new system has great potential to protect the reformer and the applied
CaO ≤% 10 catalyst by lowering the reaction temperature and keeping the hydrogen
Al2O3 ≥% 71 production rate constant. In the conventional methane steam reforming
SiO2 0.1
process, the generated CO2 is discharged directly into the atmosphere
≤%
K2O + NaO ≤% 0.1
Fe2O3 ≤% 0.1 environment without consideration of recycling. Thus, the proposed
Loss on ignition ≤% 5 design in Fig. 4 (a) is developed to overcome the problems. Furthermore,
in the new design, an innovative CO2 recycle unit is developed and
applied in the methane dry reforming (shown in Fig. 4 (b)). The sepa­
rated CO2 in the new design can be adopted as the reactant, which can be
converted into syngas by methane dry reforming, and excessive CO2 can
be stored by further compression.
The new design in Fig. 4 (b) includes three subsystems, and their
functions are syngas production, hydrogen production and CO2 recycle,
respectively. The syngas production adopted in the new design consists
of a dry reformer and two heat exchangers. The residual combustible gas
from the production process and additional CH4, if necessary, are burned
with preheated air outside the reaction tubes, and the released thermal
energy is absorbed by the reforming reaction occurring inside the re­
action tubes. The hydrogen production system mainly consists of a two-
stage shift reactor (shown in Eq. (2)) and a Pressure Swing Adsorption
(PSA) unit. Carbon monoxide (CO) in the syngas from dry reformer is
converted to hydrogen in the two-stage shift reactor. The generated H2 is
purified in the PSA unit. The ability to completely adsorb impurities
Fig. 6. Comparison of experimental data and simulation data. allows the production of hydrogen with very high purity (>99.9 %). The
unseparated gas mixture from the PSA is ducted into a CO2 removal unit
which adopted a physical absorption way called the Selexol, and this
Table 2 way obeys Henry’s law [27]. The generation of a total pure 100 % CO2
Model description and key parameters in the system simulation.
from the Selexol process is impossible due to the selectivity of different
Module Parameter Value types of gas. However, the existing Selexol technologies are capable of
Dry reforming Reaction temperature [ C]
◦
750 separating CO2 with a molar ratio above 99 % [24]. In this study, it is
Reaction pressure [bar] 5 assumed that the CO2 separated from the CO2 removal unit is identified
Molar ratio of CO2/CH4 3.4 as a pure CO2 stream. A portion of the separated CO2 is compressed and
Water gas shift reaction High shift temperature [◦ C] 335
recycled into the reformer to create an environment with a high molar
Low shift temperature [◦ C] 200
Molar ratio of H2O/CO 1.8 ratio of CO2 and CH4. The surplus CO2 is further compressed for storage.
Pressure swing adsorption Hydrogen purity [%] 99.99 Due to the strong endothermic characteristics in methane dry reaction,
Recovery rate [%] 85 the required thermal energy in the reforming process is met by the
Selexol process Carbon dioxide purity [%] 99.99
combustion of the unconverted fuel gas from the CO2 removal unit.
Recovery rate [%] 100
Separation efficiency [%] 0.2
When unconverted fuel gas cannot satisfy the heat demand in the
Heat exchanger Heat transfer temperature difference [◦ C] reformer, additional natural gas from the local grid is used to supple­
Liquid-liquid 10 ment it.
Liquid-gas 20
Gas-gas 30
Furnace temperature [◦ C] 1300

5
B. Su et al.
Fig. 7. Flow chart of the newly developed hydrogen production systems integrated with carbon capture in simulation software Aspen Plus. (a) Based on steam
reforming; (b) based on dry reforming.
3. Mathematical modeling
For modeling the complicated chemical and power system, a flexible
and full-featured software ASPEN PLUS is adopted in this study. The
section discusses the assumption and adopted tools for the simulation of
the new system in detail. Then, several evaluation criteria are listed.
3.1. Dry reforming model
Methane dry reforming converts CH4 and CO2 into syngas under high
temperatures, and this is the key process in the whole system. Reformer
can be simulated based on the chemical equilibrium by minimizing
Gibbs free energy subject to atom balance constraints [28]; therefore,
Gibbs’ equilibrium reactor in Aspen Plus is adopted. In fact, methane dry
reforming plays a dominant role in the reformer; however, numerous
side reactions also occur. Without presetting any known chemical re­
actions, all potential and possible compositions were considered by the
6
Energy Conversion and Management 270 (2022) 116199
model. The model is useful when temperature and pressure are known
and reaction stoichiometry is unknown, which are the basic character­
istics in the reformer; therefore, the performance of the reformer can be
reflected more realistically by this model.
To validate the model adopted in this study, an experiment of
methane co-reforming process was conducted. Fig. 5 shows a small
experimental platform designed for the methane component trans­
formation process. The experimental platform has three inlets and two
outlets, including two inlet gas and one inlet liquid. Before and after the
experiment, the experimental pipeline needs to be purged. Therefore,
nitrogen or argon gas is used to purge the pipeline in this experiment.
During the experiment, the dissolved methane was mixed with ionized
water after the preheater, and then the gas mixture was heated together
in the carburetor and then entered the reactor. Methane reforming oc­
curs with the help of the catalyst and under high-temperature condi­
tions. After cooling in the condenser, the high-temperature reaction gas
is separated into one liquid outlet and one gas outlet in the gas–liquid
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Table 3a
Key points parameters in the hydrogen production systems integrated with carbon capture and storage unit based on steam reforming.
Stream Temperature Pressure Mass Molar fraction
flow rate
[◦ C] [bar] [kg/h] CO2 CH4 H2O CO H2 O2 N2

1 25 5 59.39 0% 100 % 0% 0% 0% 0% 0%
2 25 5 57.75 0% 100 % 0% 0% 0% 0% 0%
3 25 5 1.64 0% 100 % 0% 0% 0% 0% 0%
4 25 5 162.14 0% 0% 100 % 0% 0% 0% 0%
5 153.10 5 162.14 0% 0% 100 % 0% 0% 0% 0%
6 153.10 5 162.14 0% 0% 100 % 0% 0% 0% 0%
7 335 5 162.14 0% 0% 100 % 0% 0% 0% 0%
8 237.86 5 219.89 0% 28.57 % 71.43 % 0% 0% 0% 0%
9 730 5 219.89 0% 28.57 % 71.43 % 0% 0% 0% 0%
10 750 5 219.89 6.23 % 3.17 % 25.95 % 9.93 % 54.72 % 0% 0%
11 319.03 5 219.89 6.23 % 3.17 % 25.95 % 9.93 % 54.72 % 0% 0%
12 395.83 5 219.89 12.95 % 3.17 % 19.23 % 3.21 % 61.44 % 0% 0%
13 200 5 219.89 12.95 % 3.17 % 19.23 % 3.21 % 61.44 % 0% 0%
14 200 5 219.89 15.90 % 3.17 % 16.28 % 0.27 % 64.38 % 0% 0%
15 89.68 5 219.89 15.90 % 3.17 % 16.28 % 0.27 % 64.38 % 0% 0%
16 25 5 219.89 15.90 % 3.17 % 16.28 % 0.27 % 64.38 % 0% 0%
17 25 5 52.78 0% 0% 100 % 0% 0% 0% 0%
18 25 5 167.11 18.87 % 3.76 % 0.65 % 0.31 % 76.41 % 0% 0%
19 26.87 5 20.54 0% 0% 0% 0% 100 % 0% 0%
20 26.87 5 146.57 53.82 % 10.74 % 1.85 % 0.90 % 32.69 % 0% 0%
21 26.87 5 16.32 0% 23.27 % 4% 1.94 % 70.79 % 0% 0%
22 26.58 5 17.96 0% 26.24 % 3.84 % 1.87 % 68.05 % 0% 0%
23 25 1.01 901.46 0% 0% 0% 0% 0% 21 % 79 %
24 463.50 1.01 901.46 0% 0% 0% 0% 0% 21 % 79 %
25 750 1.01 919.42 2.25 % 0% 9.97 % 0% 0% 12.90 % 74.88 %
26 483.51 1.01 919.42 2.25 % 0% 9.97 % 0% 0% 12.90 % 74.88 %
27 81.40 1.01 919.42 2.25 % 0% 9.97 % 0% 0% 12.90 % 74.88 %
28 26.87 5 130.25 100 % 0% 0% 0% 0% 0% 0%

Table 3b
Key points parameters in the hydrogen production systems integrated with carbon capture and storage unit based on dry reforming.
Stream Tem- Pressure Mass Molar fraction
perature flow rate
[◦ C] [bar] [kg/h] CO2 CH4 H2O CO H2 O2 N2

1 25 5 71.33 0% 100 % 0% 0% 0% 0% 0%
2 25 5 57.75 0% 100 % 0% 0% 0% 0% 0%
3 25 5 13.58 0% 100 % 0% 0% 0% 0% 0%
4 24.75 5 596.43 77.27 % 22.73 % 0% 0% 0% 0% 0%
5 728.18 5 596.43 77.27 % 22.73 % 0% 0% 0% 0% 0%
6 750 5 596.43 29.29 % 1.31 % 10.50 % 39.95 % 18.95 % 0% 0%
7 88.09 5 596.43 29.29 % 1.31 % 10.50 % 39.95 % 18.95 % 0% 0%
8 25 5 182.89 0% 0% 100 % 0% 0% 0% 0%
9 153.10 5 182.89 0% 0% 100 % 0% 0% 0% 0%
10 154 5 182.89 0% 0% 100 % 0% 0% 0% 0%
11 25 5 65.63 0% 0% 100 % 0% 0% 0% 0%
12 154 5 65.63 0% 0% 100 % 0% 0% 0% 0%
13 154 5 248.52 0% 0% 100 % 0% 0% 0% 0%
14 335 5 248.52 0% 0% 100 % 0% 0% 0% 0%
15 401.48 5 844.83 38.64 % 0.81 % 24.06 % 4.26 % 32.23 % 0% 0%
16 337.26 5 844.83 38.64 % 0.81 % 24.06 % 4.26 % 32.23 % 0% 0%
17 200 5 844.83 38.64 % 0.81 % 24.06 % 4.26 % 32.23 % 0% 0%
18 200 5 844.83 42.57 % 0.81 % 20.13 % 0.32 % 36.17 % 0% 0%
19 100.60 5 844.83 42.57 % 0.81 % 20.13 % 0.32 % 36.17 % 0% 0%
20 25 5 844.83 42.57 % 0.81 % 20.13 % 0.32 % 36.17 % 0% 0%
21 25 5 716.90 52.95 % 1.01 % 0.66 % 0.40 % 44.98 % 0% 0%
22 25 5 127.93 0% 0% 100 % 0% 0% 0% 0%
23 25 5 22.46 0% 0% 0% 0% 100 % 0% 0%
24 25 5 694.44 85.72 % 1.63 % 1.07 % 0.65 % 10.93 % 0% 0%
25 25 5 15.44 0% 11.44 % 7.48 % 4.57 % 76.51 % 0% 0%
26 25 5 29.02 0% 33.39 % 5.63 % 3.44 % 57.54 % 0% 0%
27 25 1.01 1335.94 0% 0% 0% 0% 0% 21 % 79 %
28 505 1.01 1335.94 0% 0% 0% 0% 0% 21 % 79 %
29 750 1.01 1364.96 2.58 % 0% 9.12 % 0% 0% 13.15 % 75.15 %
30 525.14 1.01 1364.96 2.58 % 0% 9.12 % 0% 0% 13.15 % 75.15 %
31 83.83 1.01 1364.96 2.58 % 0% 9.12 % 0% 0% 13.15 % 75.15 %
32 25 5 679.01 100 % 0% 0% 0% 0% 0% 0%
33 25 5.50 679.01 100 % 0% 0% 0% 0% 0% 0%
34 25 5.50 538.68 100 % 0% 0% 0% 0% 0% 0%
35 25 5.50 140.33 100 % 0% 0% 0% 0% 0% 0%

7
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Fig. 8. Sankey diagrams of energy and exergy flows. (a) Energy flow of the new steam reforming system; (b) exergy flow of the new steam reforming system; (c)
energy flow of the new dry reforming system; (d) exergy flow of the new dry reforming system.

separator. The gas outlet pressure can be controlled by the valve opening
and closing. Finally, the gas product composition is analyzed by a mass
spectrometer (Omnistar GSD 320) and chromatograph (GC-7890A). The
methane steam reforming reaction proceeds over one type of commer­
cial Ni-based catalyst, and its detailed compositions are summarized in
Table 1.
The experimental results obtained in this study and simulation re­
sults based on Gibbs’ equilibrium reactor in Aspen Plus were compared
in Fig. 6. The conversion rate corresponding to each point in the figure is
obtained by averaging 17 data after experimental stabilization. The re­
action temperature and pressure are 750 ◦ C and 1 bar, respectively.
Experimental data of CH4 agree well with the theoretical value as the
steam-to-carbon molar ratio (SC) rises from 1 to 6. However, experi­
mental data of CO2 can not be matched well with the theoretical value as
SC is 1. The relative error at this point reaches 24.86 %. But the
experimental data of CO2 agree well as SC rises from 2 to 6. On the
whole, the average relative errors for CH4 and CO2 reach 0.2 % and 5.8
%, respectively. An interesting phenomenon appears that CH4 conver­
sion rates in the experiment are larger than those in the simulation. It
can be explained by the applied catalyst because the adopted catalyst is
designed for methane steam reforming. Thus, methane steam reforming
is strengthened; meanwhile, methane dry reforming is weakened when
this type of catalyst is adopted. In the simulation, methane dry reforming
still occupies a large proportion in the Gibbs equilibrium reactor. It is
worth noting that efficient conversion in dry reforming demands a
higher reaction temperature than that in the steam reforming. In this
way, the experimental methane conversion rate is a little higher. To sum
up, the simulation results based on Gibbs’ equilibrium reactor can be
accepted with confidence.
For stable and safe operation of dry reformer, excessive CO2 is

8
B. Su et al.
Fig. 8. (continued).
needed. It can be found that the critical ratio of CO2 and CH4 (CC) is 2.2
for methane dry reforming without carbon deposition at a temperature
and pressure of 750 ◦ C and 1 bar [24]. Higher pressures for methane
reforming can reduce the possibility of coke formation at all tempera­
tures [20]. In this study, the reaction pressure depends on the pressure of
the natural gas in the pipeline (5 bar [29]). Thus, a very safe molar ratio
of CO2 and CH4 at 3.4 is selected in this study.
3.2. Water gas shift reaction model
The water gas shift (WGS) reaction converts H2O and CO into CO2
and H2, as shown in Eq. (2). Catalyst activity is generally higher at
higher temperatures; however, due to the characteristic of equilibrium
limited and moderately exothermic of the WGS [30], CO conversion rate
9
Energy Conversion and Management 270 (2022) 116199
is dependent on the reaction temperature, and more CO can be con­
verted at lower temperatures [31].
Two-stage reactors with inter-bed cooling are always applied for
WGS [32]. In the first-stage reactor, an adiabatic reaction occurs, and
the reaction temperature is relatively high and controlled by the gas
mixture of reactants. The first-stage reaction is designed for quick con­
version. On this basis, the second-stage shift reaction proceeds under the
isothermal condition for further conversion, and the reaction tempera­
ture is much lower compared with that in the first-stage shift reactor.
The stoichiometric reactor and the equilibrium reactor can be applied to
simulate the quick conversion and further conversion. The temperatures
for the first-stage and second stage shift reactors are 335 ◦ C and 200 ◦ C,
respectively.
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Table 4 this study, the generated syngas at a pressure of 5 bar is piped into the
Performance comparison between two newly developed designs for hydrogen PSA unit to produce pure hydrogen, where approximately 85 % [34] of
production. hydrogen is separated with a purity of 99.99 % [26].
Performance Steam reforming Dry reforming Gas purification methods include chemical absorption, membrane
integrated with CCS integrated with separation, water scrubbing, biofilters and pressure swing absorption,
CCS etc [35]. Thermal energy, electricity or mechanical energy are the
Conversion Methane 83.59 % 91.83 % driving energy for different CO2 removal ways. Selexol is a type of
rate Carbon dioxide – 46.28 % physical absorption technology which obeys Henry’s law, and it is
Consumption Natural gas (as 57.75 57.75
applied for CO2 removal in this study. In the Selexol process, it indicates
reactants) [kg/h]
Natural gas (as 1.64 13.58 that the purification ability is positively associated with the impurity’s
fuels) [kg/h] partial pressure [36]. Therefore, the feedstock gas is firstly compressed
Work [kW] 30.61 73.05 to high pressure, and then goes into the absorption column. Finally, it is
Production H2 production [kg/ 20.54 22.46 decompressed by vacuum in a series of flash drums. The energy con­
h]
High purity CO2 130.26 140.33
sumption for CO2 removal in syngas typically includes the electricity for
[kg/h] the syngas compression, CO2 compression and pumps, and refers to
[37]. The SEP model in the Aspen Plus is used for CO2 removal by setting
the removal rate of the carbon dioxide. The engineering cases were
referenced for determining the removal rate of the impurities.
CO2 separation efficiency (ηsep) influences the consumed work, and it
is expressed as:
Wsep,theo
ηsep = (4)
Wsep

where Wsep and Wsep,they are the actual work and theoretic work for CO2
separation, respectively.
In a gas mixture, work consumption for CO2 separation can be
determined by the following expression [38]:
x⋅lnx + (1 − x)⋅ln(1 − x)
Wsep = − R⋅T0 Fsep (5)
x⋅ηsep

where T0 is ambient temperature (298.15 K); Fsep is the mole flow rate of
the separated CO2, mol/s. R is the gas constant, 8.314 J/(mol K); x is the
molar concentration of CO2 to be separated.
The expression in Eq. (5) is capable of estimating the work con­
sumption for CO2 separation; but an implicit assumption exists that CO2

Table 5
Fig. 9. Carbon deposition feature in the methane dry reforming reaction. Transcurrent point of molar ratio of CO2 to CH4 for methane conversion rate.
Reaction temperature (◦ C) Demarcation point (CC)
3.3. Gas separation model
650 2.89
700 2.55
Hydrogen from gaseous mixtures is always separated and purified 750 2.36
from gaseous mixtures by pressure swing adsorption (PSA) technology, 800 2.26
which has already become a commercially viable technology [33]. In 850 2.16

Fig. 10. CH4 conversion ability in the newly-developed systems. (a) Based on steam reforming process; (b) based on dry reforming reaction.

10
B. Su et al.
Fig. 11. (a) CO2 conversion ability and heating value increase in the newly-developed dry reforming system integrated with carbon capture and storage; (b) CO2
conversion ability coupling with carbon deposition analysis.
in a gas mixture can be separated completely; which is a departure from
reality. Separation rate (K) is introduced in this study:
FCO2
K=
FCO2 ,theo
where FCO2 and FCO2,theo denote the actual amount of CO2 separation
and theoretic amount of CO2 separation, respectively.
According to the basic thermodynamic derivation, an improved
formula can be applied to estimate the actual CO2 separation work [24].
K is set to 0.9, and ηsep is set to 0.3 for Selexol based separation process
[38].
x⋅(1 − K)⋅ln[x⋅(1 − K)] − x⋅lnx − (1 − x⋅K)⋅ln(1 − x⋅K)
Wsep = R⋅T0 Fsep
x⋅K⋅ηsep
3.4. Heat transfer model and compression model
In this study, heat exchangers are assumed to be adiabatic, and heat
loss interactions with the outside are avoided [39]. The MheatX model
in Aspen Plus is applied to simulate the heat transfer process between
two kinds of fluids. The minimum temperature approach is set to 10 ◦ C,
15 ◦ C and 20 ◦ C for liquid–liquid, liquid–gas and gas–gas heat transfer
processes, respectively [40].
Compr model in Aspen Plus is applied to pressurize the fluid to the
required pressure. Compressors are under isentropy conditions, and an
isentropic efficiency of 0.80 is adopted in this study. Table 2 summarizes
the models and required parameters in the system simulation.
4. Results and discussion
The simulation results are presented first. The energy and exergy
balance analysis will be conducted to validate the accuracy of the
simulation. Hydrogen production performances between the proposed
system and conventional hydrogen production system based on methane
steam reforming are compared to show the advantages of the new
design. On this basis, the performance effects of key parameters in the
new design are checked. Finally, an economic analysis is given to show
the technology’s feasibility.
4.1. Simulation results
4.1.1. Model framework
The newly developed two hydrogen production designs, including a
methane steam reforming and a methane dry reforming, are simulated
Energy Conversion and Management 270 (2022) 116199
by Aspen Plus software. The detailed process of model establishment is
shown in Fig. 7. The parameters required by Aspen Plus to simulate the
two new processes are feed stream including CH4, H2O, CO2 to the
(6) process (vapor fraction, pressure, temperature, composition and flow
rate); design conditions for heat exchangers (minimum heat transfer
temperature difference and some stream temperature); operating con­
ditions for reactors (pressure, heat duty or temperature); key parameters
(steam-to-carbon molar ratio; CO2 recirculating ratio, gas-steam molar
ratio in shift reactors).
Table 3a and Table 3b show the key parameters specification in the
system simulation. The temperature, pressure, mass flow rate and molar
fraction of each stream in the new system are presented.
4.1.2. Energy and exergy balance
(7) To show the detailed energy and exergy conversion process in the
proposed two systems, unsimplified Sankey diagrams of energy and
exergy flows are presented in Fig. 8.
Fig. 8 (a) and (c) present the Sankey diagram of energy analysis of
the proposed systems. The heat input of methane are 825.46 kW and
991.40 kW in the steam and dry reforming system, respectively. And the
value is determined by input fuel mass flow rate (kg/s) and its lower
calorific value (kJ/kg). The energy loss mainly occurs in the following
components: PSA, CO2 separator, isothermal reactor and flue gas loss.
Since the water–gas shift reaction is exothermic, there is heat loss in the
isothermal reactor. They are 6.08 kW (0.71 % of the input energy) and
15.91 kW (1.49 % of the input energy) in the steam and dry system,
respectively. In the separation process, the loss of heat converted from
work is inevitable, they reach 30.61 kW (3.58 % of the input energy) and
73.05 kW (6.86 % of the input energy) in steam and dry reforming
system, respectively. However, the flue gas loss reaches 16.53 kW and
26.14 kW, which accounts for 1.93 % and 2.46 % of the input energy in
the steam and dry system, respectively. This shows that the two pro­
posed systems are reasonable in energy utilization. It can be found that
the relative error for the energy balance in the two designs is lower than
0.1 %.
For every device of the system, the total enthalpy input is equal to the
total enthalpy output, whereas the total exergy input is not equal to the
total output as some available energy is destroyed by both internal and
external irreversibility during the process of energy conversion and
transfer. Fig. 8 (b) and (d) present the Sankey diagram of exergy analysis
of the proposed systems based on the second law of thermodynamics,
indicating the exergy destruction and loss to reveal the irreversibility in
each process.
The exergy efficiencies of the steam reforming system and dry
reforming system are 80.06 % and 70.49 %, respectively. The total
11
B. Su et al. Energy Conversion and Management 270 (2022) 116199

Fig. 12. Hydrogen production and natural gas consumption in newly-developed steam and dry reforming processes. (a) Steam reforming; (b) dry reforming at 650
◦
C; (c) dry reforming at 700 ◦ C; (d) dry reforming at 750 ◦ C; (e) dry reforming at 800 ◦ C; (f) dry reforming at 850 ◦ C.

exergy losses of the two are 181.66 kW (the relative error is 2.46 %) and
335.03 kW (the relative error is 2.82 %), respectively. The exergy losses
can be divided into four parts. The first part is the exergy destruction and
loss in the furnace. They are 80.07 kW (44.08 % of the total exergy loss)
and 114.02 kW (34.03 % of the total exergy loss) in the steam and dry
reforming system, respectively. The exergy loss in combustion process is
the biggest in both systems, whereas the dry reforming system is 33.95
kW larger than the steam reforming system since the dry reforming
system consumes more methane to meet the heat demand of the reac­
tion. The second part includes the exergy destruction and loss during the
process of heat rejection to the condenser and heat exchange to the heat
exchanger. They are 49.29 kW (contains 1.39 kW exergy loss of the flue
gas) and 83.91 kW (contains 2.09 kW exergy loss of the flue gas) in the
steam and dry reforming system, respectively. Exergy destructions of

12
B. Su et al.
Fig. 13. Integrated performance of the newly-developed steam reform­
ing processes.
Fig. 14. Integrated performance of the newly-developed dry reform­
ing processes.
this part are larger in the dry reforming system since the dry reforming
system adopts more heat exchangers. The third part includes the exergy
destruction and loss of the reactors. They are 26.73 kW and 72.46 kW in
the steam and dry reforming systems, respectively. Exergy loss in the dry
reforming system is bigger due to its larger reaction heat required and
consumption of water. The fourth part includes all the exergy destruc­
tion and loss in the remaining components, including the mixer, PSA and
CO2 separator. Compared with the dry reforming system, this part of the
exergy loss of the steam reforming system is 39.07 kW lower than the
steam reforming one. More CO2 should be separated in the dry
reforming system.
It is observed that for the same reaction exergy input (834.72 kW),
the H2 exergy output of the steam and dry reforming systems are 711.79
kW and 778.28 kW, respectively. Although the exergy output (H2) in the
dry reforming system is 66.49 kW more than that in the steam reforming
system; however, its exergy efficiency is 9.57 percentage points lower.
This difference is mainly due to in the dry reforming system, more
methane is involved in combustion reaction, more separation work is
13
Energy Conversion and Management 270 (2022) 116199
input and more substances are involved in more heat exchange pro­
cesses, leading to more irreversible losses. In summary, the dry
reforming system is less suitable for hydrogen production than the steam
reforming system.
4.1.3. Performance comparison
Steam reforming has been already widely used for hydrogen pro­
duction all over the world. However, water consumption and corre­
sponding heat for water evaporation are of concern. Guided by the idea
of global carbon neutrality, the utilization of CO2 has become a focus of
attention. Therefore, studies focusing on dry reforming got a lot of
attention in recent years, in which abundant studies conducted designs
of high activity and feasible catalysts based on non-noble metal and
reactors. Nevertheless, the thermal performance comparison between
complete hydrogen production processes based on steam reforming and
dry reforming is rare, let alone the performance comparison between the
two processes integrated with CCS.
The hydrogen production process based on steam reforming inte­
grated with CCS proceeds at a condition of 750 ◦ C, 5 bar and 2.5 (molar
ratio of Steam-to-Carbon, SC). According to previous studies, a value of
CC at 2.2 will ensure a stable operation of dry reforming at a reaction
temperature of 750 ◦ C without carbon deposition on the surface of the
catalyst [24]. In this study, the dry reforming one proceeds at a condi­
tion of 750 ◦ C, 5 bar and 3.4 (molar ratio of Carbon dioxide-to-Carbon in
CH4, CC).
Methane and carbon dioxide conversion rates are compared in
Table 4. The results of the reforming reactions are obtained based on the
principle of restricted chemical equilibrium. The methane conversion
rate reached in the new steam reforming process is 83.59 %, while it
reaches 91.83 % in the dry reforming process. The reason is that a large
amount of CO2 is recycled into the methane dry reformer. Besides, the
CO2 conversion rate in the dry reforming reaches 46.28 %. The hydrogen
production rate in the dry reforming process is 22.46 kg/h, which is
1.92 kg/h (9.35 %) higher than that in the steam reforming one. The
results indicate that the proposed process based on the dry reforming
unit achieves the improved conversion ability of reactive material.
Though hydrogen production rate in the dry reforming process is
higher, the natural gas and work consumption between the two newly
developed systems needs to be considered. Compared with the steam
reforming, dry reforming absorbs more heat for the transformation of
substance. Under the same condition of input methane as reactants, the
required methane for afterburning as fuels is much higher (13.58 kg/h),
and this value in the new steam reforming one is only 1.64 kg/h. The
strong heat absorption characteristics and high carbon dioxide content
are the main reasons for this difference. The work consumption pri­
marily comes from three parts: hydrogen separation, carbon dioxide
separation and carbon dioxide circulation. Work consumption in dry
reforming process reaches 73.05 kW; however, it is only 30.61 kW in the
steam reforming process. In fact, the increased work consumption in the
dry reforming is caused by the separation of more CO2 and the demand
for CO2 circulation. The final high purity CO2 in the new dry reforming
process is 140.33 kg/h, which is larger than that (130.26 kg/h) in the
new steam reforming system.
By preliminary performance comparison, the dry reforming process
integrated with CCS has advantages of hydrogen production and CO2
capture ability; however, the dry reforming one consumes more fuels for
afterburning and works for CO2 separation and circulation. In-depth
comparisons and overall performance require further exploration, and
the analysis will be presented in the next section.
4.2. Carbon dioxide utilization
4.2.1. Carbon deposition feature
Under high-temperature conditions, carbon dioxide as a type of
oxidizing agent has the ability to reduce the risk of carbon deposition in
methane dry reforming [22]. The reason is that carbon dioxide can be
B. Su et al.
decomposed into oxygen at high temperatures, thereby alleviating car­
bon deposits in the methane reforming reaction [20]. The model applied
to research the carbon deposition feature in this study is derived from
Ref. [23], and it has already been validated in the previous study [24].
To avoid the carbon deposition in the dry reforming reaction, some
principles can be summarized in Fig. 9. High reaction temperature will
ease the mitigation of carbon accumulation on the surface of the cata­
lyst, and also the high molar ratio of CO2 to CH4 (CC) is helpful to reduce
the risk of carbon deposition. At low temperatures, the required amount
of carbon dioxide to avoid carbon deposition rises significantly. As the
reaction temperature is lowered from 750 ◦ C to 650 ◦ C, the critical CC
rises from 3.4 to 12.2. The reason for this phenomenon is that the hy­
drogenation reaction is active at low temperatures, and the carbon di­
oxide reacts with the hydrogen in the product to form solid carbon and
water steam.
4.2.2. Methane and carbon dioxide conversion ability
Steam reforming reaction proceeds at a fixed SC at 2.5, and the
methane conversion rate rises from 55.49 % to 97.12 % as the reaction
temperature increases from 650 ◦ C to 850 ◦ C, as shown in Fig. 10 (a). As
for the dry reforming one, CC is a key parameter which significantly
affects the conversion ability of methane and carbon dioxide and the
sustainable operation since it determines whether the carbon deposition
occurs. The CH4 conversion rate firstly increases at a faster rate as CC
rises from 1 to 3, and then increases slightly as CC rises from 3 to 7, as
shown in Fig. 10 (b).
For a fixed reaction temperature from 650 ◦ C to 850 ◦ C, the trans­
current points of CC are 2.89, 2.55, 2.36, 2.26 and 2.16, respectively, as
presented in Table 5. It means that the CH4 conversion ability in the dry
reforming one, compared with the newly-developed steam reforming
process, is stronger as CC is bigger than the transcurrent point. It in­
dicates that high reaction temperatures have a better effect on the CH4
conversion rate in the dry reforming one.
As for the CO2 conversion ability, higher CC lowers its conversion
rate, as shown in Fig. 10; however, the heating value of product in­
creases since higher CC boosts the CH4 conversion rate. As CC rises from
1 to 7, the range of heating value growth rate increases from
10.46–30.14 % to 24.97–37.07 %, shown in Fig. 11 (a). In fact, a larger
heating value growth rate means better reaction performance; however,
the issues of carbon deposition should be considered. Fig. 11 (b) presents
the relationship between reaction parameters and CO2 conversion rate
coupling with carbon deposition analysis. Higher reaction temperature
and higher CC are helpful for mitigation of carbon deposition risks, and
also intensify the reaction performance. Yet, benefit capture at the same
time, the costs should also be considered including natural gas after­
burning and work consumption.
4.3. Hydrogen production and natural gas consumption
The optimal hydrogen production in the newly developed steam and
dry reforming processes reaches 23.80 % and 24.37 %, respectively, as
shown in Fig. 12. By conducting an optimal design, the dry reforming
one can generate more H2. The natural gas is required as the reaction
temperature increases to some value. When the reaction temperature
increases to 739 ◦ C, the required natural gas starts to rise from 0 to
10.58 kg/h at a temperature of 850 ◦ C. As for the dry reforming one, the
critical CCs for additional natural gas afterburning are 5.15, 3.12, 1.80,
1.01 and 0.93, respectively for a reaction temperature of 650 ◦ C, 700 ◦ C,
750 ◦ C, 800 ◦ C and 850 ◦ C, shown in Fig. 12. The maximum value of
afterburning-natural gas consumption in the dry reforming one reaches
22.13 kg/h, while it is only 10.58 kg/h in the steam reforming one.
4.4. Integrated thermal performance
For the two hydrogen production processes, the costs include natural
gas and work consumption. By integrating with the carbon capture
14
Energy Conversion and Management 270 (2022) 116199
technology, the two systems also achieve the generation of high purity
CO2. To evaluate the integrated performance of the proposed two sys­
tems, work consumption is converted to the equivalent natural gas.
Then, power efficiency (55 %) of typical combined cycles is adopted to
convert the work to natural gas. As for the increased high purity CO2
generation in the dry reforming system, the detailed transformational
rule is to convert the increased high purity CO2 generation to the work
saved. On this basis, the costs for hydrogen production can be uniformly
expressed as natural gas consumption. Thus, the integrated performance
(IP) can be expressed as:
mH2
IPs = (8)
mng + mng,work
mH2
IPd = (9)
mng + mng,work − mng,CO2
where IPs and IPd indicate the integrated performance of the steam
reforming and dry reforming system, respectively. mH2, mng, mng, work
and mng, CO2 indicates the actual natural gas consumption as reactants
and fuel, equivalent natural gas consumption from work consumption
and equivalent natural gas consumption from increased high purity CO2
generation.
The value of IP drops means that hydrogen production can be ach­
ieved with less cost and advanced performance. Integrated performance
of the new steam reforming process increases significantly since reaction
temperatures rise to 750 ◦ C, as a result of which, IPs drop from 4.47 kg
(H2)/ kg (CH4) to 3.08 kg (H2)/ kg (CH4). The further improvement of
reaction temperature is not capable of producing hydrogen effectively.
As reaction temperature increases from 750 ◦ C to 850 ◦ C, IPs drop from
3.08 kg (H2)/ kg (CH4) to 3.01 kg (H2)/ kg (CH4), as shown in Fig. 13.
Fig. 14 indicates that the integrated performance of the newly-
developed dry reforming processes at variable reaction parameters. It
is worth noting that carbon deposition analysis is presented since stable
operation is the premise of integrated performance pursuit. The optimal
parameters range is at temperatures from 769 ◦ C to 850 ◦ C and CC from
1.4 to 2.8. Higher reaction temperature with low CC is capable of
improving the integrated performance. However, low CC is very prone
to catalyst carbon deposition problems. The parameter selection prin­
ciple is given in this study for hydrogen production based on dry
reforming integrated with CC: higher reaction temperature with a lower
and safe CC; it can be found in Fig. 14 that the optimal integrated per­
formance without carbon deposition reaches 3.38 (H2)/ kg (CH4).
By conducting an optimal design and a carbon deposition analysis,
hydrogen production systems coupled with CCS based on steam
reforming have a better integrated thermal performance (10.95 %)
compared with the dry reforming one. However, dry reforming process
may be proper to apply into the distributed energy systems due to its
higher heat absorption characteristics. The different types of thermal
energy in energy systems have large potential to satisfy the heat con­
sumption in the dry reforming; therefore, it can be considered in the
future study.
5. Conclusions
To solve the problems of high carbon emission in the conventional
reforming methods for hydrogen production, two new hydrogen pro­
duction systems integrated with carbon capture are developed based on
a steam reforming process and a dry reforming process coupled with
carbon dioxide reinjection. Detailed mathematical models are estab­
lished, and the key model of reformer was validated. The predicted re­
sults were further validated by conducting an energy and exergy balance
analysis. On this basis, the reforming reaction conversion ability,
hydrogen production capability, natural gas and work consumption are
obtained. Some conclusions can be drawn as follows:
B. Su et al.
(1) In consideration of the stable operation, the issues of carbon
deposition in the steam reforming can be efficiently solved by
adding water steam; however, the molar ratio of CO2 to CH4 is a
key parameter affecting the carbon deposition. High temperature
is capable of converting CH4 efficiently without carbon deposi­
tion at a smaller molar ratio of CO2 to CH4.
(2) New dry reforming process produces more hydrogen; however,
more natural gas is needed for afterburning. The maximum value
of afterburning-natural gas consumption in the dry reforming one
reaches 22.13 kg/h, while it is only 10.58 kg/h in the steam
reforming one.
(3) Work consumption and high purity CO2 generation are also two
factors affecting the integrated performance. Carry out reason­
able equivalent conversion of various costs, and a comprehensive
evaluation criterion of hydrogen production cost is given to
compare the performance of the two new designs. The integrated
performance of the new steam reforming is 3.01; while it reaches
3.38 in the dry reforming. From the comprehensive perspective of
hydrogen production and carbon capture and storage, steam
reforming is more efficient. Yet, dry reforming absorbs more heat,
and may be very adaptive for energy systems development,
especially CHP/CCHP, which can be considered in future studies.
CRediT authorship contribution statement
Bosheng Su: Conceptualization, Methodology, Software, Writing –
original draft. Yilin Wang: Investigation, Software, Data curation,
Writing – review & editing. Zhilong Xu: Writing – review & editing. Wei
Han: Writing – review & editing. Hongguang Jin: Writing – review &
editing. Hongsheng Wang: Conceptualization, Methodology.
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.
Data availability
Data will be made available on request.
Acknowledgments
The authors gratefully acknowledge the support of the National
Natural Science Foundation of China (Grant No. 52006089, No.
51906179 and No. 51876108) and the Natural Science Foundation of
Fujian, China (Grant No. 2020J05142), the Scientific Research Foun­
dation of Jimei University (Grant No. ZQ2019022) and the Scientific
Research Foundation of Fujian Province Education Department (Grant
No. B19263).
References
[1] GCCSI. Global status of CCS report. GCCSI 2020.
[2] IPCC. Calentamiento global de 1.5 ◦ C. IPCC 2019.
[3] EPA. Overview of Greenhouse Gases. EPA 2018.
[4] Iea G. Energy and CO2 Status Report. Global IEA 2018.
[5] Liu C, Han W, Wang Z, Zhang N. Proposal and Assessment of an Engine-Based
Distributed Steam and Power Cogeneration System Integrated with an Absorption-
Compression Heat Pump 2020;29:15.
[6] Liu C, Han W, Wang Z, Zhang N. A New Cleaner Power Generation System Based
on Self-Sustaining Supercritical Water Gasification of Coal; 2021.
[7] Guerra OJ, Eichman J, Kurtz J, Hodge B-M. Cost Competitiveness of Electrolytic
Hydrogen. Joule 2019;3(10):2425–43.
[8] Rubin ES, Davison JE, Herzog HJ. The cost of CO2 capture and storage. Int J
Greenhouse Gas Control 2015;40:378–400.
[9] Khor SC, Jusoh M, Zakaria ZY. Hydrogen production from steam and dry reforming
of methane-ethane-glycerol: A thermodynamic comparative analysis. Chem Eng
Res Des 2022;180:178–89.
15
Energy Conversion and Management 270 (2022) 116199
[10] Hashim SS, Somalu MR, Loh KS, Liu S, Zhou W, Sunarso J. Perovskite-based proton
conducting membranes for hydrogen separation: A review. Int J Hydrogen Energy
2018;43(32):15281–305.
[11] Minutillo M, Perna A, Sorce A. Green hydrogen production plants via biogas steam
and autothermal reforming processes: energy and exergy analyses. Appl Energy
2020;277:115452.
[12] Zhao X, Joseph B, Kuhn J, Ozcan S. Biogas Reforming to Syngas: A Review.
iScience 2020;23(5):101082.
[13] Su B, Han W, Chen Y, Wang Z, Qu W, Jin H. Performance optimization of a solar
assisted CCHP based on biogas reforming. Energy Convers Manage 2018;171:
604–17.
[14] Sajjadi SM, Haghighi M, Rahmani F. Dry reforming of greenhouse gases CH4/CO2
over MgO-promoted Ni–Co/Al2O3–ZrO2 nanocatalyst: effect of MgO addition via
sol–gel method on catalytic properties and hydrogen yield 2014;70:111-24.
[15] Su B, Lin F, Ma J, Huang S, Wang Y, Zhang X, et al. System integration of multi-
grade exploitation of biogas chemical energy driven by solar energy. Energy 2022;
241:122857.
[16] Su B, Han W, He H, Jin H, Chen Z, Zheng J, et al. Using moderate carbon dioxide
separation to improve the performance of solar-driven biogas reforming process.
Appl Energy 2020;279:115693.
[17] Gao Y, Jiang J, Meng Y, Yan F, Aihemaiti A. A review of recent developments in
hydrogen production via biogas dry reforming. Energy Convers Manage 2018;171:
133–55.
[18] González JJ, Da Costa-Serra JF, Chica A. Biogas dry reforming over Ni–Ce catalyst
supported on nanofibered alumina. Int J Hydrogen Energy 2020;45(40):20568–81.
[19] Su B, Han W, Zhang X, Chen Y, Wang Z, Jin H. Assessment of a combined cooling,
heating and power system by synthetic use of biogas and solar energy. Appl Energy
2018;229:922–35.
[20] Annesini M, Piemonte V, Turchetti L. Carbon formation in the steam reforming
process: A thermodynamic analysis based on the elemental composition. Chem Eng
Trans 2007;11:21–6.
[21] Su B, Han W, He H, Jin H, Chen Z, Yang S. A biogas-fired cogeneration system
based on chemically recuperated gas turbine cycle. Energy Convers Manage 2020;
205:112394.
[22] Yap D, Tatibouët J-M, Batiot-Dupeyrat C. Catalyst assisted by non-thermal plasma
in dry reforming of methane at low temperature. Catal Today 2018;299:263–71.
[23] Van herle J, Maréchal F, Leuenberger S, Membrez Y, Bucheli O, Favrat D. Process
flow model of solid oxide fuel cell system supplied with sewage biogas. J Power
Sources 2004;131(1-2):127–41.
[24] Su B, Han W, He H, Jin H, Chen Z, Zheng J, et al. Using moderate carbon dioxide
separation to improve the performance of solar-driven biogas reforming process.
Appl Energy 2020;279:115693.
[25] Wang S, Lu GQ, Millar GJ, Fuels. Carbon dioxide reforming of methane to produce
synthesis gas over metal-supported catalysts: State of the art 1996;10:896-904.
[26] Wei H, Hongguang J, Rumou L. A Novel Multifunctional Energy System for CO2
Removal by Solar Reforming of Natural Gas. J Sol Energy Eng 2011;133:041004 (8
pp.).
[27] Lampert K, Ziebik A, Stanek W. Thermoeconomical analysis of CO2 removal from
the Corex export gas and its integration with the blast-furnace assembly and
metallurgical combined heat and power (CHP) plant. Energy 2010;35(2):1188–95.
[28] Li S, Jin H, Gao L. Cogeneration of substitute natural gas and power from coal by
moderate recycle of the chemical unconverted gas. Energy 2013;55:658–67.
[29] Zhang N, Wang Z, Lior N, Han W. Advancement of distributed energy methods by a
novel high efficiency solar-assisted combined cooling, heating and power system.
Appl Energy 2018;219:179–86.
[30] Jin S, Byun H, Lee C-H. Enhanced oxygen mobility of nonreducible MgO-supported
Cu catalyst by defect engineering for improving the water-gas shift reaction. J Catal
2021;400:195–211.
[31] Bian L, Wang L, Duan C, Cai C, Song X, An S. Co-free La0.6Sr0.4Fe0.9Nb0.1O3-δ
symmetric electrode for hydrogen and carbon monoxide solid oxide fuel cell. Int J
Hydrogen Energy 2019;44(60):32210–8.
[32] Trimm DL. Minimisation of carbon monoxide in a hydrogen stream for fuel cell
application. Appl Catal A 2005;296(1):1–11.
[33] Ullah Khan I, Hafiz Dzarfan Othman M, Hashim H, Matsuura T, Ismail AF, Rezaei-
DashtArzhandi M, et al. Biogas as a renewable energy fuel – A review of biogas
upgrading, utilisation and storage. Energy Convers Manage 2017;150:277–94.
[34] Tong L, Bénard P, Zong Yi, Chahine R, Liu K, Xiao J. Artificial neural network
based optimization of a six-step two-bed pressure swing adsorption system for
hydrogen purification. Energy AI 2021;5:100075.
[35] Kadam R, Panwar NL. Recent advancement in biogas enrichment and its
applications. Renew Sustain Energy Rev 2017;73:892–903.
[36] Zhang Y, Ahn H. The implications of choice between sour and sweet shift on
process design and operation of an IGCC power plant integrated with a dual-stage
selexol unit. Energy 2019;173:1273–84.
[37] Lampert K, Ziebik A. Comparative analysis of energy requirements of CO2 removal
from metallurgical fuel gases. Energy 2007;32(4):521–7.
[38] Li S, Jin H, Gao L, Zhang X. Exergy analysis and the energy saving mechanism for
coal to synthetic/substitute natural gas and power cogeneration system without
and with CO2 capture. Appl Energy 2014;130:552–61.
[39] Xu C, Liu Y, Zhang Q, Xin T, Zhao R, Wang M, et al. Thermodynamic analysis of a
novel biomass polygeneration system for ammonia synthesis and power generation
using Allam power cycle. Energy Convers Manage 2021;247:114746.
[40] Su B, Han W, He H, Jin H, Chen Z, Yang S. A biogas-fired cogeneration system
based on chemically recuperated gas turbine cycle. Energy Convers Manage 2020;
205:112394.