i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9

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Effects of methane processing strategy on fuel

composition, electrical and thermal efficiency of
solid oxide fuel cell

Baofeng Tu a,*, Huiying Qi a, Yanxia Yin a, Tonghuan Zhang a, Di Liu a,

Shuna Han a, Fujun Zhang a, Xin Su a,**, Daan Cui b,***, Mojie Cheng c
a
Shandong University of Science and Technology, 579 Qianwangang Road, 266590, Qingdao, China
b
Marine Engineering College, Dalian Maritime University, 1 Linghai Road, 116026, Dalian, China
c
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, 116023, Dalian, China

highlights graphical abstract

Methane processing strategy is

investigated based on the ther-
modynamic equilibrium.

Fuel composition is calculated
under the thermodynamic equi-
librium condition.

Suitable O/C ratio from methane
pretreatment can depress carbon
deposition.

Effects of methane processing
strategy on electrical efficiency are
investigated.

Effects of methane processing
strategy on thermal efficiency are
investigated.

article info abstract

Article history: Natural gas is a cheap and abundant fuel for solid oxide fuel cell (SOFC), generally inte-
Received 10 April 2021 grating the SOFC system with methane pre-treating system for improving the stability of
Received in revised form SOFC. In this paper, the accurate effects of methane processing strategy on fuel compo-
14 May 2021 sition, electrical efficiency and thermal efficiency of SOFC are investigated based on the
Accepted 18 May 2021 thermodynamic equilibrium. Steam reforming of methane is an endothermic process and
Available online 11 June 2021 can produce 3 mol of H2 and 1 mol of CO from 1 mol of methane, and thus the electrical
efficiency of SOFC is high at the same O/C ratio and equivalent fuel utilization, whereas the
Keywords: thermal efficiency is low. On the contrary, partial oxidation of methane is an exothermal
Solid oxide fuel cell process and only produces 2 mol of H2 and 1 mol of CO from 1 mol of methane, and thus
Methane processing strategy the electrical efficiency of SOFC is low at the same O/C ratio and equivalent fuel utilization,

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: tubaofeng2019@163.com (B. Tu), suxin20090220@163.com (X. Su), cuidaan@dlmu.edu.cn (D. Cui).
https://doi.org/10.1016/j.ijhydene.2021.05.128
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
26538 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9

Fuel composition whereas the thermal efficiency is high. When the O/C ratio is 1.5, the electrical efficiency of
Electrical efficiency SOFC is 55.3% for steam reforming of methane, while 32.7% for partial oxidation of
Thermal efficiency methane. High electrical efficiency of SOFC can be achieved and carbon deposition can be
depressed by selecting suitable O/C ratio from methane pretreatment according to the
accurate calculation and analysis of effects of different methane processing strategies on
the electrical efficiency and thermal efficiency of SOFC.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Methane oxidation, especially partial oxidation of methane

Introduction
Excessive and inefficient use of fossil energy causes serious
environmental problems, and thus the requirements for
environmental issues are prompting an urgent need to
develop new energy conversion systems. Solid oxide fuel cell
(SOFC) has been considered to be one of the most efficient
energy conversion systems because of high efficiency and low
pollution. For relatively lower carbon intensity compared to
other fossil fuels, natural gas is rapidly becoming the
preferred fuel for power generation partly [1]. And thus nat-
ural gas is one of the most suitable fuels for SOFC. Methane is
a widely studied fuel for SOFC as its the main component of
natural gas. For avoiding serious carbon deposition, methane-
fueled SOFC system is generally integrated with methane pre-
treating system [2,3].
For methane pre-treating system, there are several pre-
treating technologies [4e7], for example, steam reforming of
methane (SRM), carbon dioxide reforming of methane (CRM),
autothermal reforming of methane (ARM), and so on. Steam
reforming of methane [8,9] is a process for producing the
syngas with high concentration of hydrogen as illustrated in
reaction (1), while SRM is an endothermic process, which
needs heat from outside or tail gas. When steam is excessive,
water-gas shift reaction (WGSR) would be promoted.
Steam reforming of methane:
CH4 þ H2O / CO þ 3H2, DH298 k ¼ 206 kJ/mol
Water-gas shift reaction:
CO þ H2O / CO2 þ H2, DH298 k ¼ 41 kJ/mol
Carbon dioxide reforming of methane:
CH4 þ CO2 / 2CO þ 2H2, DH298 k ¼ 247 kJ/mol
Reverse water-gas shift reaction (RWGSR):
CO2 þ H2 / CO þ H2O, DH298 k ¼ 41 kJ/mol
Carbon dioxide reforming of methane [10,11] is a green
route for producing hydrogen and carbon monoxide, which is
also an endothermic process, and needs heat from outside or
tail gas. When carbon dioxide is excessive, RWGSR would be
promoted.
(POM) [12] has been widely investigated, which is an exothermic
reaction as illustrated in reaction (5). The complete oxidation of
methane reaction (6) would be promoted in the case of excess
oxygen, which could release much more heat than POM.
Partial oxidation of methane:
CH4 þ 0.5O2 / 2H2 þ CO, DH298 k ¼ 36 kJ/mol (5)
Complete oxidation of methane:
CH4 þ 2O2 / CO2 þ 2H2O, DH298 k ¼ 802 kJ/mol (6)
Autothermal reforming of methane [13] is also investigated
extensively because it combines the endothermic steam
reforming process with the exothermic partial oxidation of
methane.
Methane reforming is a complex reaction process, and the
detailed reaction process has been researched much [14e17].
Different methane processing strategies may lead to the
different fuel compositions, thus affecting the performance
and efficiency of SOFC. The fuel with high H/C ratio can be
produced by SRM, while high concentration of CO can be
produced by CRM. CH4, CO, H2 and C can be electrochemically
oxidized at the interface between electrode and electrolyte,
however the electrochemical oxidation of H2 is a rapid process
[18,19], and thus the performance of SOFC is greatly affected
by fuel composition. On the other hand, more CO2 and H2O
(1) can lead to the decrease of cell performance [20].
Efficiency and stability are the most important indicators
for the application of SOFC. Carbon deposition is one of the
most serious problems for methane-fueled SOFC, which can
(2) lead to poor stability of SOFC. The carbon deposition for
methane fuel is mainly affected by two aspects: thermody-
namic process and kinetic process. For the kinetic process, it is
mainly by investigating the anti-carbon deposition materials
(3) along with structure and property to inhibit the speed of
carbon deposition, so as to achieve the purpose of inhibiting
carbon deposition, which has been researched in many liter-
atures [21e24]. For the thermodynamic process, it is mainly by
(4)
increasing the ratio of oxygen to carbon in the fuel to make the
fuel composition into the thermodynamic range without
carbon deposition, so as to achieve the purpose of inhibiting
carbon deposition. And thus carbon deposition can be
depressed with high ratio of H2O, CO2 and/or O2 for methane
pretreatment, but it may also lead to the decrease of electrical
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9 26539

efficiency. Therefore, the suitable ratio of H2O, CO2 and/or O2 Reactions (9-14) show the complete and partial electro-
for methane pretreatment is important for improving the chemical oxidation of methane. The electrochemical oxida-
stability and efficiency of SOFC. tion of C, H2 and CO is illustrated in reactions (15-17),
Methane-fueled SOFC has been widely investigated on respectively. The calculation of fuel utilization and electrical
carbon deposition, performance and efficiency [22,25e34], but efficiency is based on the reactions (1-17).
little work has been done to accurately compare the effects of Fig. 1 shows the schematic diagram of different methane
methane processing strategies on the efficiency of SOFC. And processing strategies for SOFC. Methane pretreatment, elec-
thus it is usually hard to quantitatively compare the effects of trochemical power generation and combustion of anode off-
methane processing strategies on the efficiency of SOFC.
Moreover, it is not convenient to analyze the efficiency of
SOFC from different methane processing strategies. In order
to accurately analyze the efficiency of SOFC from different
methane processing strategies, we have a novel design of Mo
for SOFC with pure methane as fuel and Mo0 for SOFC with pre-
treated methane as fuel, and thus the effects of methane
processing strategies on the efficiency of SOFC can be accu-
rately compared according to the results in this paper. On the
other hand, the fuel compositions are investigated according
to the thermodynamic equilibrium from different methane
processing strategies.

Calculation procedure

Thermochemical calculations are carried out using a program,

Gaseq (Version 0.79, Research by Chris Morley) [35]. The
operating temperature and pressures in our calculation are set
at 1073 K and 1 atm, respectively. CH4, H2O, CO2, O2, CO, H2
and C(S) are considered in our calculation [36,37]. Reaction (7)
shows the methane decomposition. CO disproportionated
reaction is illustrated in reaction (8). The fuel compositions
from different methane processing strategies are calculated
according to the reactions (1-8).

CH4 / C þ 2H2 (7)

2CO / CO2 þ C (8)

Electrochemical oxidation reactions [33]:

CH4 þ 4O2 / CO2 þ 2H2O þ 8e (9)

CH4 þ O2 / CO þ 2H2 þ 2e (10)

CH4 þ 2O2 / CO þ H2 þ H2O þ 4e (11)

CH4 þ 2O2 / CO2 þ 2H2 þ 4e (12)

CH4 þ 3O2 / CO þ 2H2O þ 6e (13)

CH4 þ 3O2 / CO2 þ H2 þ H2O þ 6e (14)

C þ O2 / CO þ 2e (15)

H2 þ O2 / H2O þ 2e (16) Fig. 1 e Schematic diagram of different methane

processing strategies for SOFC. (a), SRM; (b), CRM; (c), POM;
CO þ O2 / CO2 þ 2e (17) (d), ARM.
26540 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9

gas are the main processes for methane-fueled SOFC. POM,
power generation process and combustion of anode off-gas
are exothermic processes, while SRM and CRM are endo-
thermic processes. Anode off-gas combustion can provide the
heat for SRM or CRM.
Lower heating values (LHVs) of methane and other fuels
are used to calculate the fuel utilization and electrical effi-
ciency. The electrical efficiency (hel) is calculated according
to the heating value (DH), fuel flow rate (mf) and electrical
power output as illustrated in Eq. (18) [35,38]. Operating
voltage (V) of a cell is set at 0.8 V. The current (I) is calcu-
lated according to the fuel conversion, Faraday's law and
reactions (9-17). The performance of SOFC system is
assumed to be good, which can meet our calculation
conditions.
hel ¼ Wout =LHVCH4 ¼ I  V=ðmf  DHÞ
We also defined equivalent fuel utilization (Ue) for SOFC
integrated with methane processing system. At one Ue, the
real fuel utilization (Ur) of SOFC with the fuel from methane
pretreatment can be calculated according to that the Mo0 of
SOFC with the fuel from methane pretreatment is approxi-
mately equal to Mo (Mo' ¼ Mo±0.001) of SOFC with pure
methane as fuel. Ur is related to the electrical efficiency (hel) by
Eq. (24). Current efficiency (hI) is set at 100% in this work. hV is
the voltage efficiency, where V is the operating voltage of a cell
and Erev is the Nernst potential of SOFC.
hel ¼ Ur  hI  hV ¼ Ur  hI  V=Erev (24)
Table 1 shows the fuel compositions, efficiency and Mo of
SOFC with pure methane as fuel at different fuel utilizations
and 1073 K. The electrical efficiency increases apparently with
the increase of fuel utilization, whereas the thermal efficiency
(18)
decreases apparently as shown in Table 1.

hth ¼ Q out =LHVCH4 ¼ Q out =ðmf  DHÞ (19)

Results and discussion
hloss ¼ Q loss =LHVCH4 ¼ Q loss =ðmf  DHÞ (20)

All the operating temperatures are set at 1073 K, and the
heat released to the environment (Qloss) is assumed to be 5% of
total energy (LHVCH4) for all the methane processing systems
integrated with SOFC system in this work, and thus the
thermal efficiency loss (hloss) is 5%. The heat for SRM or CRM
can be supplied by anode off-gas combustion, and thus
methane reforming and anode off-gas combustion can be
regarded as the internal process. hth can be calculated ac-
cording to Eq. (21).
hth ¼ 1  hel  hloss
The fuel utilization (U) of SOFC is calculated according to
Eq. (22), where mu is the fuel for power generation and mi is
the full fuel input.
U ¼ mu =mi
As illustrated in Eq. (23), Mo for SOFC with pure methane as
fuel and Mo0 for SOFC with pre-treated methane as fuel are
defined, which are the ratio of oxygen in H2O and CO2 of the
anode off-gas and all the oxygen after completely oxidizing
the anode off-gas except the oxygen in CO.
Mo ðMo 0 Þ ¼ ðMH2O þ 2  MCO2 Þ=ðMH2O þ 2  MCO2 þ MCO
þ MH2 þ 4  MCH4 þ 2  MC Þ
Effects of SRM on fuel composition and efficiency of SOFC
Conventionally, SRM is a cheap and efficient method to pro-
duce syngas, which has an advantage of high hydrogen pro-
duction. Fig. 2(a) shows the equilibrium products from SRM at
different MH2O/MCH4 ratios. When the MH2O/MCH4 ratio is
below 1.05, solid carbon (C(S)) can be formed according to the
thermodynamic equilibrium results. Whereas when the MH2O/
MCH4 ratio is beyond 1.05, C(S) can't be formed as shown in
Fig. 2(a). When the MH2O/MCH4 ratio is 1, the fuel from SRM is
(21) composed of 0.7% CO2, 2.2% H2O, 2.4% CH4, 0.5% C(S), 22.6% CO
and 71.6% H2. When the MH2O/MCH4 ratio increases to 2, the
fuel is composed of 4.2% CO2, 16.0% H2O, 0.2% CH4, 0% C(S),
15.6% CO and 63.9% H2, where the concentrations of CO2 and
H2O increase apparently. The concentration of hydrogen is
(22) higher than 50% when the MH2O/MCH4 ratio increases from 0 to
3. Tu et al. [20] have researched the fuel composition and cell
performance from SRM at different MH2O/MCH4 ratios and
1023 K. The concentration of hydrogen is high, which is
consistent with our calculated result, and thus the cell per-
formance is affected a little from SRM. High H2 ratio in the fuel
from SRM is good for the cell performance [39], and high MH2O/
MCH4 ratio is helpful for depressing carbon deposition, which
(23)
may decrease the efficiency of SOFC. And thus it is important

Table 1 e Fuel compositions, electrical efficiency, thermal efficiency and Mo of SOFC with pure methane as fuel at 1073 K
and different fuel utilizations.
Fuel utilization H2O (%) CO2 (%) CO (%) H2 (%) CH4 (%) C(S) (%) Electrical efficiency Thermal efficiency Mo
65% 35.1 18.3 15.1 31.6 0 0 50.0% 45% 0.6056
70% 39.6 20.5 12.9 27.1 0 0 53.8% 41.2% 0.6683
75% 44.0 22.6 10.7 22.6 0 0 57.7% 37.3% 0.7282
80% 48.5 24.8 8.5 18.1 0 0 61.5% 33.5% 0.7867
85% 53.0 27.0 6.4 13.6 0 0 65.4% 29.6% 0.8425
90% 57.6 29.1 4.2 9.1 0 0 69.2% 25.8% 0.8970
95% 62.1 31.2 2.1 4.6 0 0 73.1% 21.9% 0.9489
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
Fig. 2 e Fuel composition (a), real fuel utilization (b), electrical efficiency (c) and thermal efficiency (d) from SRM for SOFC at
different MH2O/MCH4 ratios and1073 K.
to select suitable MH2O/MCH4 ratio for high efficiency and good
stability of SOFC from steam reforming of methane.
Fig. 2(b), (c) and (d) show the Ur, electrical efficiency and
thermal efficiency of SOFC with SRM at different MH2O/MCH4
ratios. When the Ue is high, the Ur and electrical efficiency are
high and decrease slowly with the increase of MH2O/MCH4
ratio, whereas the thermal efficiency is low as illustrated in
Fig. 2. When the Ue is low, the Ur and electrical efficiency are
low and decrease rapidly with the increase of MH2O/MCH4 ratio,
whereas the thermal efficiency is high and increases rapidly
with the increase of MH2O/MCH4 ratio. The Ur, electrical effi-
ciency and thermal efficiency are 87.4%, 67.2% and 27.8% at
90% Ue and the MH2O/MCH4 ratio of 1, respectively. When the
MH2O/MCH4 ratio increases to 2, the Ur and electrical efficiency
decrease to 84.8% and 65.2% at 90% Ue, whereas the thermal
efficiency increases to 29.8%. When the MH2O/MCH4 ratio in-
creases to 3, the Ur and electrical efficiency decrease to 82.3%
and 63.3% at 90% Ue, whereas the thermal efficiency increases
to 31.7%. The Ur, electrical efficiency and thermal efficiency
are 61.6%, 47.4% and 47.6% at 70% Ue and the MH2O/MCH4 ratio
of 1, respectively. When the MH2O/MCH4 ratio increases to 2,
the Ur and electrical efficiency decrease rapidly to 53.3% and
41% at 70% Ue, whereas the thermal efficiency increases
rapidly to 54%. When the MH2O/MCH4 ratio increases to 3, the
Ur and electrical efficiency decrease rapidly to 44.9% and
34.5%, whereas the thermal efficiency increases rapidly to
60.5% at 70% Ue.
Solid carbon is disadvantageous for the stability of catalyst
and SOFC, which can be avoided when the ratio of steam to
26541
methane is suitable. The syngas produced by SRM has high
hydrogen concentration, and thus the performance of SOFC is
little affected by SRM. The electrical efficiency and thermal
efficiency are little affected at high Ue, whereas greatly
affected at low Ue with the increase of MH2O/MCH4 ratio.
Effects of CRM on fuel composition and efficiency of SOFC
Carbon dioxide reforming of methane is a green route for
producing syngas. The syngas produced by CRM has a low
MH2/MCO ratio of ca.1. The fuel compositions from CRM are
shown in Fig. 3(a), which are 2.8% CO2, 2.7% H2O, 1.0% CH4,
4.4% C(S), 42.8% CO and 46.2% H2 at the MCO2/MCH4 ratio of 1
and 1073 K. When the MCO2/MCH4 ratio is below 1.25, C(S) can
be formed according to the thermodynamic equilibrium re-
sults. Whereas when the MCO2/MCH4 ratio is beyond 1.25, C(S)
can't be formed as shown in Fig. 3(a). With the increase of
MCO2/MCH4 ratio, the reaction (4) is promoted, so the ratio of
MH2/MCO is less than 1 when the ratio of MCO2/MCH4 is larger
than 1. The concentration of H2 decreases rapidly to 32.1% at
the MCO2/MCH4 ratio increasing to 2, whereas the concentra-
tion of CO increases to 47.6%. When the MCO2/MCH4 ratio in-
creases to 3, the concentrations of CO2 and H2O increase to
22.7% and 10.7%, whereas the concentration of H2 decreases
rapidly to 22.6% and the concentration of CO decreases to
44.0%. Tu et al. [20] have researched the fuel composition and
cell performance from CRM at different MCO2/MCH4 ratios and
1023 K. The fuel with high MCO/MH2 ratio can be produced by
CRM, especially at the ratio of MCO2/MCH4 larger than 1, which
26542 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
Fig. 3 e Fuel composition (a), real fuel utilization (b), electrical efficiency (c) and thermal efficiency (d) from CRM for SOFC at
different MCO2/MCH4 ratios and1073 K.
is consistent with our calculated result. The fuel from CRM
may cause the occurrence of limited current densities and the
decrease of cell performance.
The Ur and electrical efficiency of SOFC with CRM are high
and decrease slowly with the increase of MCO2/MCH4 ratio at
high Ue, whereas the thermal efficiency is low and increases
slowly at high Ue as illustrated in Fig. 3. The Ur, electrical ef-
ficiency and thermal efficiency are 85.3%, 65.6% and 29.4% at
90% Ue and the MCO2/MCH4 ratio of 1, respectively. When the
MCO2/MCH4 ratio increases to 2, the Ur and electrical efficiency
decrease to 80.5% and 61.9% at 90% Ue, whereas the thermal
efficiency increases to 33.1%. When the MCO2/MCH4 ratio in-
creases to 3, the Ur and electrical efficiency decrease to 75.8%
and 58.3% at 90% Ue, whereas the thermal efficiency increases
to 36.7%.
The Ur and electrical efficiency are low and decrease
rapidly with the increase of MCO2/MCH4 ratio at low Ue,
whereas the thermal efficiency is high and increases rapidly
as illustrated in Fig. 3. The Ur, electrical efficiency and thermal
efficiency are 57.1%, 43.9% and 51.1% at 70% Ue and the MCO2/
MCH4 ratio of 1, respectively. When the MCO2/MCH4 ratio in-
creases to 2, the Ur and electrical efficiency decrease rapidly to
44.5% and 34.2% at 70% Ue, whereas the thermal efficiency
increases rapidly to 60.8%. When the MCO2/MCH4 ratio in-
creases to 3, the Ur and electrical efficiency decrease rapidly to
31.9% and 24.5% at 70% Ue, whereas the thermal efficiency
increases rapidly to 70.5%.
Carbon deposition can be avoided when suitable propor-
tion of CO2 is used for methane reforming. CRM can produce
the syngas with high CO ratio. The electrical efficiency and
thermal efficiency are little affected at high Ue, while greatly
affected at low Ue with the increase of MCO2/MCH4 ratio.
Effects of POM on fuel composition and efficiency of SOFC
Partial oxidation of methane is a simple process and
exothermic reaction. In the case with excess methane, mainly
the reaction (5) occurs. But in the case with excess oxygen, the
complete oxidation of methane would occur, which is highly
exothermic and attractive for fast heat-up applications [40].
The fuel with the MH2/MCO ratio of ca. 2 can be produced by
POM. When the MO2/MCH4 ratio is below 0.53, C(S) can be
formed according to the thermodynamic equilibrium results,
while when the MO2/MCH4 ratio is beyond 0.53, C(S) can't be
formed as illustrated in Fig. 4(a). The fuel from POM is
composed of 2.7% CO2, 5.0% H2O, 0.9% CH4, 0% C(S), 30.4% CO
and 61.1% H2 at the MO2/MCH4 ratio of 0.6. When the MO2/MCH4
ratio increases to 1.0, the fuel is composed of 11.6% CO2, 21.9%
H2O, 0.1% CH4, 0% C(S), 21.8% CO and 44.8% H2, where the
concentrations of CO2 and H2O increase apparently. Tu et al.
[20] have researched the fuel composition and cell perfor-
mance from POM. The cell performance from POM with oxy-
gen varies a little with the increase of MO2/MCH4 ratio. High
MO2/MCH4 ratio is helpful for depressing carbon deposition.
However with the increase of MO2/MCH4 ratio, the concentra-
tions of CO2 and H2O increase and the concentrations of CO
and H2 decrease apparently, which may decrease the effi-
ciency of SOFC, and thus it is important to select suitable MO2/
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
Fig. 4 e Fuel composition (a), real fuel utilization (b), electrical efficiency (c) and thermal efficiency (d) from POM for SOFC at
different MO2/MCH4 ratios and 1073 K.
MCH4 ratio for high efficiency and good stability of SOFC from
partial oxidation of methane.
Both the Ur and electrical efficiency of SOFC with POM
decrease rapidly with the increase of MO2/MCH4 ratio, whereas
the thermal efficiency increases rapidly as shown in Fig. 4. The
Ur, electrical efficiency and thermal efficiency are 65%, 50.0%
and 45.0% at 90% Ue and the MO2/MCH4 ratio of 0.5, respec-
tively. When the MO2/MCH4 ratio increases to 1, the Ur and
electrical efficiency decrease rapidly to 40% and 30.8% at 90%
Ue, whereas the thermal efficiency increases rapidly to 64.2%.
When the Ue is 70% and the MO2/MCH4 ratio is 0.5, the Ur,
electrical efficiency and thermal efficiency are 45%, 34.6% and
60.4%, respectively. The Ur and electrical efficiency decrease
rapidly to 20% and 15.4% at 70% Ue, whereas the thermal ef-
ficiency increases rapidly to 79.6% at the MO2/MCH4 ratio
increasing to 1.
High oxygen ratio can increase the O/C ratio in the fuel,
which is helpful for depressing carbon deposition, but it may
result in the complete oxidation of methane and lead to the
rapid decrease of electrical efficiency of SOFC.
Effects of ARM on fuel composition and efficiency of SOFC
SRM is an endothermic process, while POM is an exothermic
process, and thus ARM is also one of the most promising
methods for combining the endothermic process and
exothermic process. Fig. 5(a) shows the equilibrium products
from ARM at 1073 K. When the MH2O/MCH4 ratio (MH2O/MO2 ¼ 2/
1) is below 0.53, the ratio of C(S) decreases apparently,
26543
whereas the concentration of CO increases apparently with
the increase of MH2O/MCH4 (MH2O/MO2 ¼ 2/1) ratio. When the
MH2O/MCH4 ratio (MH2O/MO2 ¼ 2/1) is beyond 0.53, C(S) can't be
formed according to the thermodynamic equilibrium results,
while the concentrations of H2 and CO decrease and the
concentrations of CO2 and H2O increase gradually with the
increase of MH2O/MCH4 (MH2O/MO2 ¼ 2/1) ratio. The fuel from
ARM is composed of 1.0% CO2, 2.3% H2O, 2.2% CH4, 1.1% C(S),
25.6% CO and 67.9% H2 at the MH2O/MO2/MCH4 ratio of 0.5/0.25/
1. When the MH2O/MO2/MCH4 ratio increases to 1/0.5/1, the fuel
is composed of 6.6% CO2, 18.6% H2O, 0.1% CH4, 0% C(S), 18.4%
CO and 56.4% H2 as shown in Fig. 5(a). High MH2O/MO2/MCH4
ratio is helpful for depressing carbon deposition. However the
concentrations of CO2 and H2O increase rapidly and the con-
centrations of CO and H2 decrease rapidly with the increase of
MH2O/MO2/MCH4 ratio, which may decrease the efficiency of
SOFC, and thus it is important to select suitable MH2O/MO2/
MCH4 ratio for high efficiency and good stability of SOFC from
ARM. For ARM, the combined methane reforming of CRM and
POM has also been investigated [21], which has similar char-
acteristics with the combined methane reforming of SRM and
POM except for the fuel composition.
Both the Ur and electrical efficiency of SOFC with ARM
decrease rapidly, whereas the thermal efficiency increases
rapidly with the increase of MH2O/MCH4 (MH2O/MO2 ¼ 2/1) ratio
as shown in Fig. 5. The Ur and electrical efficiency are 76.2%
and 58.6% at 90% Ue and the MH2O/MO2/MCH4 ratio of 0.5/0.25/1,
which decrease to 62.4% and 48% at the MH2O/MO2/MCH4 ratio
increasing to 1/0.5/1, whereas the thermal efficiency increases
26544 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
Fig. 5 e Fuel composition (a), real fuel utilization (b), electrical efficiency (c) and thermal efficiency (d) from ARM for SOFC at
different MH2O/MO2/MCH4 ratios and 1073 K.
from 36.4% to 47% at 90% Ue with the increase of MH2O/MO2/
MCH4 ratio from 0.5/0.25/1 to 1/0.5/1. The Ur and electrical ef-
ficiency decrease rapidly to 48.6% and 37.4%, whereas the
thermal efficiency increases to 57.6% at 90% Ue when the
MH2O/MO2/MCH4 ratio increases to 1.5/0.75/1. When the Ue is
70% and the MH2O/MO2/MCH4 ratio is 0.5/0.25/1, the Ur, elec-
trical efficiency and thermal efficiency are 53.3%, 41% and
54%, respectively. The Ur and electrical efficiency decrease
rapidly to 36.6% and 28.1%, whereas the thermal efficiency
increases to 66.9% at 70% Ue when the MH2O/MO2/MCH4 ratio
increases to 1/0.5/1. The Ur and electrical efficiency decrease
rapidly to 19.9% and 15.3%, whereas the thermal efficiency
increases to 79.7% at 70% Ue and the MH2O/MO2/MCH4 ratio
increasing to 1.5/0.75/1.
Effects of methane processing strategy on carbon deposition,
O/C and H/C ratios
The fuel composition is important for the performance and
stability of SOFC. The O/C ratio in the fuel is important for
avoiding carbon deposition. C(S) can be formed when the O/C
ratio is lower than 1.1, and can't be formed when the O/C ratio
is larger than 1.2 at 1073 K according to the thermodynamic
equilibrium results. The electrochemical oxidation reaction of
H2 at the interface between electrode and electrolyte is a rapid
reaction [18,19], and thus the H/C ratio from methane pre-
treatment is important for the performance of SOFC. Fig. 6
shows the O/C and H/C ratios from different methane pro-
cessing strategies. SRM has the highest H/C ratio at the same
O/C ratio, while CRM has the lowest H/C ratio as shown in
Fig. 6. The O/C ratio from CRM is lower than 2 because there is
one carbon atom in the molecule of CO2. The H/C ratio from
POM is 4, which doesn't change with the increase of O/C ratio.
The H/C ratios from SRM and ARM increase with the increase
of O/C ratio, whereas the H/C ratio from CRM decreases with
the increase of O/C ratio.
Effects of methane processing strategy on electrical efficiency
and thermal efficiency of SOFC
The electrical efficiency is one of the most important in-
dicators for the application of SOFC. Fig. 7 shows the electrical
efficiency of SOFC from different methane processing strate-
gies at different O/C ratios and 1073 K. The electrical effi-
ciencies of SOFC from all the methane processing strategies
decrease with the increase of O/C ratio as shown in Fig. 7,
which decrease slowly for SRM, while rapidly for POM. For
CRM, the electrical efficiency decreases slowly at low O/C
ratio, while rapidly at high O/C ratio, especially at low Ue.
Table 2 shows the electrical efficiency of SOFC from
different methane processing strategies at different O/C ra-
tios. As shown in Table 2, the electrical efficiencies are 67.2%
for SRM, 65.6% for CRM, 50% for POM and 58.6% for ARM at the
O/C ratio of 1.0 and 90% Ue. When the O/C ratio increases from
1 to 1.5, the electrical efficiency is decreased by only 0.9% to
66.3% for SRM, whereas for POM the electrical efficiency is
decreased by 9.6% to 40.4% at 90% Ue. For CRM, the electrical
efficiency is decreased by 7.3% to 58.3% when the O/C ratio
increases from 1 to 1.5 at 90% Ue. The electrical efficiencies are
43.9% for CRM, 47.4% for SRM, 34.6% for POM and 41% for ARM
at the O/C ratio of 1.0 and 70% Ue. When the O/C ratio in-
creases from 1 to 1.5, the electrical efficiencies are decreased
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
Fig. 6 e O/C and H/C ratios from different methane processing strategies.
by 3.3% to 44.1% for SRM and decreased by 9.6% to 25% for POM
at 70% Ue. While for CRM, the electrical efficiency is decreased
by 19.4% to 24.5% at 70% Ue. When the O/C ratio is 1.5, the
electrical efficiencies are 55.3% for SRM, 40.9% for CRM, 32.7%
for POM and 44% for ARM at 80% Ue. The electrical efficiency is
SRM > ARM (MH2O:MO2 ¼ 2:1) > CRM > POM at the O/C ratio of
1.5 and 80% Ue.
One mole of methane can produce 3 mol of H2 and 1 mol of
CO through SRM, whereas 1 mol of methane can produce
2 mol of H2 and 1 mol of CO through POM, and only H2O and
CO2 can be produced by complete oxidation of methane. And
thus the electrical efficiency from POM is lower much than
that from SRM at the same O/C ratio. One mole of methane
can produce 2 mol of H2 and 2 mol of CO through CRM. While a
molecule of CO2 contains one carbon atom, and thus more CO2
should be used for the same O/C ratio than H2O. So the elec-
trical efficiency from CRM is lower than that from SRM at the
same O/C ratio, especially at high O/C ratio.
The effect of methane processing strategy on thermal ef-
ficiency of SOFC is opposite to that on electrical efficiency. As
shown in Fig. 8, the thermal efficiency increases with the in-
crease of O/C ratio, increasing slowly for SRM, while rapidly
for POM. For CRM, the thermal efficiency increases slowly at
low O/C ratio, while rapidly at high O/C ratio with the increase
of O/C ratio, especially at low Ue. Table 3 shows the thermal
26545
efficiency of SOFC from different methane processing strate-
gies at different O/C ratios. As shown in Table 3, the thermal
efficiencies are 37.6% for SRM, 40.4% for CRM, 52.7% for POM
and 45.2% for ARM at the O/C ratio of 1.0 and 80% Ue. When the
O/C ratio increases to 1.5, the thermal efficiencies are 39.7%
for SRM, 54.1% for CRM, 62.3% for POM and 51% for ARM at 80%
Ue. The thermal efficiency is POM > CRM > ARM (MH2O:MO2-
¼ 2:1) > SRM at the O/C ratio of 1.5 and 80% Ue.
The electrical efficiency and thermal efficiency of SOFC are
apparently different from different methane processing stra-
tegies. When the Ue of SOFC system can reach a high value, for
example 90%, the system can achieve high electrical effi-
ciencies from different methane processing strategies, which
are 58.3% for CRM, 66.3% for SRM, 40.4% for POM, and 53.3% for
ARM at the O/C ratio of 1.5. On the contrary, the thermal ef-
ficiency is low at high Ue. With the decrease of Ue, the changes
in electrical efficiency and thermal efficiency are significantly
different from different methane processing strategies. The
electrical efficiencies decrease to 24.5% for CRM, 44.1% for
SRM, 25% for POM and 34.6% for ARM at the O/C ratio of 1.5
when the Ue decreases to 70%. Whereas the thermal effi-
ciencies increase apparently, which are 50.9% for SRM, 70.5%
for CRM, 60.4% for ARM, and 70% for POM at the O/C ratio of 1.5
and 70% Ue. The electrical efficiencies of SOFC from CRM and
POM are lower than 30%, whereas the thermal efficiencies of
26546 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9

Fig. 7 e Electrical efficiency of SOFC from different methane processing strategies at different O/C ratios and 1073 K. (a) 70%
Ue, (b) 80% Ue, (c) 90% Ue.

be formed according to the thermodynamic equilibrium re-

sults and the electrical efficiency doesn't decrease too much,
Table 2 e Electrical efficiency of SOFC from different
methane processing strategies at 1073 K. which is conducive to the operation of SOFC.
For all the methane processing strategies, there are ad-
Ue 70% 80% 90%
vantageous and disadvantageous points, so according to the
Processing strategy O/C effects of different methane processing strategies on the sta-
SRM 1 47.4 57.4 67.2
bility and efficiency of SOFC, a better strategy could be found
1.5 44.1 55.3 66.3
2 41 53.3 65.2
for the operation of SOFC system. High electrical efficiency of
CRM 1 43.9 54.6 65.6 SOFC can be achieved from SRM at the same O/C ratio and Ue.
1.5 24.5 40.9 58.3 When the SOFC system can operate at high fuel utilization,
2 / / / the electrical efficiency of SOFC system can reach high for
POM 1 34.6 42.3 50 most of the methane processing strategies. While when the
1.5 25.0 32.7 40.4
SOFC system can't operate at high fuel utilization, SRM may be
2 15.4 23.1 30.8
the best processing strategy for high electrical efficiency. The
ARM 1 41 49.8 58.6
1.5 34.6 44.0 53.3 electrical efficiency from POM is low. However, POM is the
2 28.1 38.1 48 preferred method for mobile fuel cell system because it is a
simple and rapid process.

SOFC from CRM and POM are higher than 70% at the O/C ratio
of 1.5 and 70% Ue.
High ratio of H2O, CO2 and/or O2 for methane pretreatment
can depress carbon deposition, but it may reduce the electrical
efficiency [41e43]. On the contrary, low ratio of H2O, CO2 and/
or O2 can result in high electrical efficiency, however, carbon
deposition may occur and affect the stability of SOFC [44], and
thus suitable proportions of H2O, CO2 and/or O2 for methane
pretreatment are very important for high electrical efficiency
and good stability of SOFC. When the O/C ratio is 1.5, C(S) can't
Conclusions
Suitable O/C ratio for methane pretreatment can improve the
stability and efficiency of SOFC. When the O/C ratio is larger
than 1.2, solid carbon can't be formed at 1073 K according to
the thermodynamic equilibrium results. For all the methane
processing strategies, the electrical efficiency decreases with
the increase of O/C ratio, whereas the thermal efficiency in-
creases with the increase of O/C ratio at the same Ue. The
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9 26547

Fig. 8 e Thermal efficiency of SOFC from different methane processing strategies at different O/C ratios and 1073 K. (a) 70%
Ue, (b) 80% Ue, (c) 90% Ue.

(MH2O:MO2 ¼ 2:1) > CRM > POM. Partial oxidation of methane is

Table 3 e Thermal efficiency of SOFC from different an exothermic process, and thus high thermal efficiency of
methane processing strategies at 1073 K. SOFC can be achieved from POM. When the O/C ratio is 1.5 and
Ue 70% 80% 90% the Ue is 80%, the thermal efficiency is POM > CRM > ARM
(MH2O:MO2 ¼ 2:1) > SRM.
Processing strategy O/C High ratio of H2O, CO2 and/or O2 for methane pretreatment
SRM 1 47.6 37.6 27.8 can depress carbon deposition, but it may reduce the electrical
1.5 50.9 39.7 28.7 efficiency, and thus suitable proportions of H2O, CO2 and/or O2
2 54 41.7 29.8 for methane pretreatment are very important for high elec-
CRM 1 51.1 40.4 29.4 trical efficiency and good stability of SOFC. When the O/C ratio
1.5 70.5 54.1 36.7
is 1.5, C(S) can't be formed according to the thermodynamic
2 / / /
equilibrium results and the electrical efficiency doesn't
POM 1 60.4 52.7 45
1.5 70 62.3 54.6 decrease too much, which is conducive to the operation of
2 79.6 71.9 64.2 SOFC.
ARM 1 54 45.2 36.4
1.5 60.4 51 41.7
2 66.9 56.9 47 Declaration of competing interest

The authors declare that they have no known competing

electrical efficiency is high and decreases slowly with the in-
financial interests or personal relationships that could have
crease of O/C ratio at high Ue for SRM, and decreases rapidly at
appeared to influence the work reported in this paper.
low Ue. For POM, the electrical efficiency decreases rapidly
with the increase of O/C ratio, whereas the thermal efficiency
increases rapidly.
Steam reforming of methane is an endothermic process, Acknowledgments
and thus high electrical efficiency of SOFC can be achieved at
the same O/C ratio and Ue. When the O/C ratio is 1.5 and the Ue The authors gratefully acknowledge the financial support
is 80%, the electrical efficiency is SRM > ARM from the Natural Science Foundation of Shandong Province,
26548 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 6 5 3 7 e2 6 5 4 9
China (Grant No. ZR2020KE035) and Chris Morley for Gaseq
program.
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