Applied Energy 173 (2016) 80–91

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Combined steam and carbon dioxide reforming of methane and side

reactions: Thermodynamic equilibrium analysis and experimental
application
Won-Jun Jang a, Dae-Woon Jeong a, Jae-Oh Shim a, Hak-Min Kim a, Hyun-Seog Roh a,⇑, In Hyuk Son b,
Seung Jae Lee c,⇑
a
Department of Environmental Engineering, Yonsei University, 1 Yonseidae-gil, Wonju, Gangwon 220-710, Republic of Korea
b
Energy Lab., Samsung Advanced Institute of Technology (SAIT), Samsung Electronics Co. Ltd, Gyeonggi-do 443-803, Republic of Korea
c
Marine Research Institute, Samsung Heavy Industries Co. Ltd, Gyeongsangnam-do 656-710, Republic of Korea

h i g h l i g h t s

Selected variables have a significant influence on yields of synthesis gas.

(CO2 + H2O)/CH4 affects the temperature which can achieve the maximum conversion.

Coke is formed at low temperatures even with excess oxidizing agent.

The occurrence of RWGS becomes critical in real chemical reactions.

Equilibrium conversions are maintained for 500 h without detectable deactivation.

a r t i c l e i n f o a b s t r a c t

Article history: Thermodynamic equilibrium analysis of the combined steam and carbon dioxide reforming of methane
Received 24 December 2015 (CSCRM) and side reactions was performed using total Gibbs free energy minimization. The effects of
Received in revised form 26 February 2016 (CO2 + H2O)/CH4 ratio (0.9–2.9), CO2:H2O ratio (3:1–1:3), and temperature (500–1000 °C) on the equilib-
Accepted 6 April 2016
rium conversions, yields, coke yield, and H2/CO ratio were investigated. A (CO2 + H2O)/CH4 ratio greater
than 1.2, a CO2:H2O ratio of 1:2.1, and a temperature of at least 850 °C are preferable reaction conditions
for the synthesis gas preparation in the gas to liquid process. Simulated conditions were applied to the
Keywords:
CSCRM reaction and the experimental data were compared with the thermodynamic equilibrium results.
Thermodynamic equilibrium analysis
Combined steam and carbon dioxide
The thermodynamic equilibrium results were mostly consistent with the experimental data, but the
reforming of methane reverse water gas shift reaction rapidly occurred in the real chemical reaction and under excess oxidizing
Side reactions agent conditions. In addition, a long-term stability test (under simulated conditions) showed that the
Coke equilibrium conversion was maintained for 500 h and that the coke formation on the used catalyst
H2/CO ratio was not observed.
Reverse water gas shift Ó 2016 Published by Elsevier Ltd.

1. Introduction interest with regard to the discovery of abundant shale gas

The production of alternative liquid fuel is an important issue
because the transport system plays a key role in economy and
industry [1]. A gas to liquid (GTL) technology is an attractive tech-
nology for the production of transportable liquid fuel using
methane [2–5]. Recently, the GTL technology has gained renew
⇑ Corresponding authors.
E-mail addresses: hsroh@yonsei.ac.kr (H.-S. Roh), sj0514.lee@samsung.com
(S.J. Lee).
reserves [6,7]. In general, GTL technology consists of three steps:
reforming, Fischer–Tropsch synthesis, and upgrading. The reform-
ing is an important step in the GTL technology because it is the
most expensive process among the three steps and also has the lar-
gest part of the energy conversion in the entire process [8,9].
Reforming in GTL technologies is aimed at producing the synthesis
gas with an H2/CO ratio of below 2.0 for Fischer–Tropsch synthesis
[10]. Methane can be converted into the synthesis gas via
reforming with different oxidizing agents such as H2O (Eq. (1)),
O2 (Eq. (2)), and CO2 (Eq. (3)) [11]:

http://dx.doi.org/10.1016/j.apenergy.2016.04.006
0306-2619/Ó 2016 Published by Elsevier Ltd.
 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91 81

Steam reforming of methane ðSRMÞ : CH4 þ H2 O ! CO þ 3H2 ;
DH0298 ¼ 206 kJ=mol
Partial oxidation of methane ðPOMÞ : CH4 þ 1=2O2 ! CO
þ 2H2 ; DH0298 ¼ 38 kJ=mol
Carbon dioxide reforming of methane ðCDRÞ : CH4 þ CO2 !
2CO þ 2H2 ; DH0298 ¼ 248 kJ=mol
The POM can produce synthesis gas with an H2/CO ratio of 2.0.
However, it is difficult to control the process due to the presence of
hot spots and the risk of explosions [12,13]. Moreover, the POM
requires an air separation unit (ASU), which significantly impacts
the costs of a reforming plant [14]. Due to these drawbacks of
the POM, combined steam and carbon dioxide reforming of
methane (CSCRM), where H2O is partially substituted by CO2, has
been considered as an alternative method for the production of
synthesis gas with an H2/CO ratio of 2.0 [15–17].
The CSCRM can produce the synthesis gas with flexible H2/CO
ratios. The H2/CO ratio of the synthesis gas produced via the
CSCRM can be controlled by changing the composition of the feed
gas (H2O, CO2, and CH4). However, the CSCRM is a complex reac-
tion because two reforming reactions (Eqs. (1) and (3)), secondary
reactions (Eqs. (4) and (5)), and coke formation reactions (Eqs. (6)
and (7)) occur simultaneously. The reaction pathway of the CSCRM
strongly depends on the reaction conditions such as the feed com-
position, temperature, and pressure. Thus, it is necessary to inves-
tigate the effects of reaction conditions on the performance to
enable direct use of synthesis gas in downstream applications.
Water gas shift ðWGSÞ : CO þ H2 O ! CO2 þ H2 ;
DH0298 ¼ 41 kJ=mol
Reverse water gas shift ðRWGSÞ : CO2 þ H2 ! CO þ H2 O;
DH0298 ¼ 41 kJ=mol
Methane decomposition : CH4 ! C þ 2H2 ; DH0298 ¼ 75 kJ=mol ð6Þ
Boudouard reaction : 2CO ! C þ CO2 ; DH0298 ¼ 172 kJ=mol ð7Þ
Thermodynamic analysis is a useful tool that can serve as a
guide for experimental studies [18–20]. In addition, it can offer
ideas about the availability of reaction conditions in complex
chemical reactions. Hence, numerous studies about the thermody-
namic analysis for the reforming of methane have been reported
[21–25]. Li et al. conducted the thermodynamic analysis for the
autothermal reforming of methane and reported that the rate of
coke formation should be taken into consideration to find the
proper reaction conditions [23]. It has been reported that excess
ð1Þ steam is effective for inhibiting coke formation, but the excess
steam increases the cost of the operating process. Özkara-
Aydinoǧlu reported that the H2/CO ratio of synthesis gas can be
ð2Þ modified by changing the relative concentration of H2O and CO2,
the temperature, and the pressure [24]. Jafarbegloo et al. compared
results of thermodynamic analysis with experimental data to ver-
ð3Þ
ify the applicability of simulation results in the CDR reaction [25].
However, previous researches have focused on the positive effect
of steam addition or on the relationship between H2O:CO2 ratio
of reactant gas and H2/CO ratio of product gas. Thus, the studies
have not provided systematic and deep understanding about the
prerequisite for the CSCRM reaction. Inhibiting the coke formation
and maintaining the H2/CO ratio of 2.0 should be preferentially
taken into account for the stable operation of process and down-
stream application. Chein et al. claimed the importance of finding
carbon free operating condition in the reforming reaction [26]. In
addition, measuring the extent of side reaction helps to maximize
the yield of target product. From this study, preferable reaction
conditions which can maximize conversions and yields in parallel
with satisfying prerequisite were determined.
In the present work, thermodynamic analysis of the CSCRM reac-
tion with different (CO2 + H2O)/CH4 ratios, CO2:H2O ratios,
temperatures, and pressures were studied. The results of the CSCRM
reaction obtained from thermodynamic analysis were compared
with those of side reactions to understand the reaction pathway
of CSCRM. Coke yield was analyzed to determine the coke-formed
and coke-free regions. The H2/CO ratio of synthesis gas was
investigated for downstream application. The preferable reaction
conditions for the production of synthesis gas with the H2/CO ratio
ð4Þ of 2.0 and coke yield of 0% were determined. The wide range of
(CO2 + H2O)/CH4 ratio was studied to offer practical guidelines
which enables the estimation of suitable reaction conditions for
ð5Þ considering the amount of excess steam. The simulated conditions
are applied to the CSCRM reaction and the experimental data are
compared with the thermodynamic equilibrium results.
2. Methodology
2.1. Thermodynamic equilibrium analysis
The spontaneity of a chemical reaction is determined by the
Gibbs free energy. The system is thermodynamically favorable
when the value of the total Gibbs free energy is at a minimum

Table 1
Summary of thermodynamic equilibrium analysis and experimental conditions.

Description CH4 CO2 H2O N2 (CO2 + H2O)/ CO2: P

CH4 H2O (atm)
Molar Flow rate Molar Flow rate Molar Flow rate Molar Flow rate
ratio (mL/min) ratio (mL/min) ratio (mL/min) ratio (mL/min)
The effect of 1.00 20.05 0.29 5.81 0.62 12.43 3.08 61.70 0.9 1.0:2.1 1.0
(CO2 + H2O)/CH4 1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 1.0
ratio 1.00 20.05 0.44 8.82 0.93 18.65 2.62 52.48 1.4 1.0:2.1 1.0
1.00 20.05 0.63 12.63 1.37 27.47 1.99 39.85 2.0 1.0:2.1 1.0
1.00 20.05 0.91 18.25 1.95 39.10 1.13 22.61 2.9 1.0:2.1 1.0
The effect of CO2:H2O 1.00 20.05 0.89 17.90 0.30 5.98 2.80 56.09 1.2 3.0:1.0 1.0
ratio 1.00 20.05 0.81 16.24 0.38 7.62 2.80 56.09 1.2 2.1:1.0 1.0
1.00 20.05 0.60 11.93 0.60 11.93 2.80 56.09 1.2 1.0:1.0 1.0
1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 1.0
1.00 20.05 0.30 5.98 0.89 17.90 2.80 56.09 1.2 1.0:3.0 1.0
The effect of pressure 1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 1.0
1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 3.0
1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 5.0
1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 10.0
1.00 20.05 0.38 7.62 0.81 16.24 2.80 56.09 1.2 1.0:2.1 20.0

The bold text indicates the changing variables.

82 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91
and its differential becomes zero for a given set of operating condi-
tion [27]. Thus, Gibbs free energy minimization is a common
method to predict the equilibrium composition of a particular sys-
tem [20]. Prior to this calculation, it is necessary to determine the
phases and components of a system. The major components of the
CSCRM reaction are gas phase species such as CH4, CO2, H2O, CO, H2
and N2. A solid species should also be introduced as a component
due to the formation of coke [22]. The total Gibbs free energy is
expressed by Eq. (8). The detailed procedure to derive the equation
was described in supporting information.
! !
XN ^iP
yi / X and was vaporized at 180 °C upstream of the reactor. Effluent gases
Gt ¼ ni G0;g
f ;i þ RT ln þ kk aik þ nC DG0;s
f ;C ¼ 0
P0
i¼1 k
Here, Gt is the total Gibbs free energy, N is the number of compo-
nents, ni is the number of moles of component ‘i’, G0f ;i is the Gibbs
free energy of formation of component ‘i’, R is the universal gas con-
stant, T is the temperature of the system, yi is the molar faction of
component ‘i’, / ^ i is the fugacity coefficient of component ‘i’, P is
the pressure of the system, kk is the Lagrange multiplier, aik is the
number of atoms of the kth element in each molecular species,
and DG0;s
f ;C is the standard Gibbs free energy of coke formation. The
thermodynamic equilibrium analysis with the Gibbs free energy
minimization method was conducted using HSC chemistry (Version
3.0, Outokumpu Research Oy, Finland).
The detailed conditions for the simulation are summarized in
Table 1. First, (CO2 + H2O)/CH4 ratio was varied from 0.9 to 2.9 at
fixed CO2:H2O ratio of 1.0:2.1 to identify the effect of total amount
of oxidizing agent, shown in Section 3.1. Second, CO2:H2O ratio was
changed from 3.0:1.0 to 1.0:3.0 at fixed (CO2 + H2O)/CH4 ratio of
1.2 to check the effect of the type of oxidizing agent, shown in Sec-
tion 3.2. Third, pressure was varied from 1.0 to 20 atm at fixed
(CO2 + H2O)/CH4 ratio of 1.2 and CO2:H2O ratio of 1.0:2.1 to check
the applicability of reaction condition at elevated pressure.
The conversion and yield are defined as follows [23,28]:
½CH4 in  ½CH4 out
CH4 conversion ¼  100
½CH4 in
½CO2 in  ½CO2 out
CO2 conversion ¼  100
½CO2 in
2  ½H2 out
H2 yield ¼  100
4  ½CH4 in þ 2  ½H2 Oin
½COout
CO yield ¼  100
½CH4 in þ ½CO2 in
½Cout
Coke yield ¼  100
½CH4 in þ ½CO2 in
2.2. Experimental procedure
A Ni–MgO–Ce0.8Zr0.2O2 catalyst was prepared by a one step
co-precipitation method [11,29,30]. The Ni and metal oxide loadings
were fixed at 15 and 10 wt.%, respectively. Stoichiometric quantities
of Ni(NO3)26H2O (97%, Junsei), Mg(NO3)26H2O (99%, Aldrich),
Ce(NO3)36H2O (99%, Aldrich), and zirconyl nitrate solution
(20 wt.% ZrO2 basis, MEL Chemicals) were combined in distilled
water. To this solution, a 15% KOH solution was added drop-wise
at 80 °C under constant stirring to attain a pH of 10.5. After digestion
for 3 days, the catalyst was thoroughly washed with distilled water
several times to remove K impurities. It was then air-dried for 24 h
and dried at 110 °C for 6 h. The catalyst was calcined at 800 °C for
6 h in air. The BET surface area of the Ni–MgO–Ce0.8Zr0.2O2 catalyst
was ca. 80 m2/g and the detailed characterization of the catalyst
have been reported previously [11,29,30].
The CDR reaction was carried out in a fixed-bed micro-tubular
quartz reactor with an inner diameter of 4 mm at atmospheric
pressure. The prepared catalyst charge was 0.3 g. The reaction tem-
perature was measured and controlled by a K-type thermocouple
which was inserted directly into the middle bed of the catalyst.
Before each measurement, the catalyst was reduced in 5% H2/N2
at 850 °C for 3 h. The catalytic reaction was conducted at a GHSV
of 20,000 h1. The reactant feed was composed of gaseous mixture
of CH4:CO2:H2O:N2. N2 was employed as a reference to maintain
the total volume of the reactant feed. The detailed flow rates are
summarized in Table 1. The steam was fed using a syringe pump
ð8Þ
from the reactor were analyzed on-line using a micro gas chro-
matograph (Agilent 3000). Quantitative analysis of the amount of
coke on the used catalyst was measured with a thermogravimetry
analyzer (TGA, TA instruments SDT 2960). The used catalysts were
collected after a long-term stability test for 500 h. A 15 mg sample
was heated from 30 to 800 °C at a heating rate of 10 °C/min in oxy-
gen to oxidize the coke on the used catalysts.
3. Thermodynamic equilibrium analysis
3.1. Effect of the (CO2 + H2O)/CH4 ratio
Fig. 1(a)–(f) exhibit the effects of (CO2 + H2O)/CH4 ratio and
temperature on CH4 conversion, CO2 conversion, H2 yield, CO yield,
coke yield, and H2/CO ratio in the CSCRM reaction at a fixed CO2:
H2O ratio of 1:2.1.
As shown in Fig. 1(a), CH4 conversion increased with increasing
the temperature for all (CO2 + H2O)/CH4 ratios because of the
endothermic nature of the SRM (Eq. (1)) and CDR (Eq. (3)). The
lower (CO2 + H2O)/CH4 ratios (0.9, 1.2, and 1.4) showed higher
CH4 conversion than the higher (CO2 + H2O)/CH4 ratios (2.0 and
2.9) at temperatures below 650 °C. When the temperature was
above 650 °C, the CH4 conversion of the higher (CO2 + H2O)/CH4
ratios (2.0 and 2.9) exceeded that of the lower (CO2 + H2O)/CH4
ratios (0.9, 1.2, and 1.4). Almost 100% CH4 conversion was achieved
ð9Þ
above 850 °C, with the exception of the lowest (CO2 + H2O)/CH4
ratio (0.9). This result indicates that the insufficient amount of oxi-
ð10Þ dizing agent leads to a low CH4 conversion because the oxidizing
agent is considered to be a limiting reactant.
ð11Þ Fig. 1(b) shows two trends of CO2 conversion as a function of
temperature for all (CO2 + H2O)/CH4 ratios. Initially, CO2 conver-
ð12Þ sion slightly decreased with the temperature range from 500 to
550 °C. This is due to the fact that the WGS (Eq. (4)) is favorable
at lower temperatures compared to CDR (Eq. (3)). The produced
ð13Þ
CO and H2O are converted into CO2 and H2 by WGS (Eq. (4)). As
a result, the increased amount of CO2 caused a decrease in CO2 con-
version. Alternatively, it can be seen that CO2 conversion for the
higher (CO2 + H2O)/CH4 ratios (2.0 and 2.9) has a negative value
between 500 and 600 °C. This indicates that the amount of CO2
produced by WGS is larger than the amount of CO2 consumed by
CDR. These results are in good agreement with those of Özkara-
Aydinoǧlu and Nikoo [22,24]. An increasing trend in CO2 conver-
sion was observed above 550 °C. This reflects that CDR is dominant
at high temperatures, due to its highly endothermic nature and
stable CO2.
Fig. 1(c) exhibits H2 yield as a function of temperature with var-
ious (CO2 + H2O)/CH4 ratios. H2 yield for the lower (CO2 + H2O)/CH4
ratios (0.9, 1.2, and 1.4) increased with rising temperatures. This
indicates that H2 was produced by SRM (Eq. (1)), CDR (Eq. (3)),
and WGS (Eq. (4)). Likewise, H2 yield for the higher (CO2 + H2O)/
CH4 ratios (2.0 and 2.9) also increased at the temperature up to
750 °C. However, H2 yield started to decrease slightly at 800 °C.
This could be caused by the occurrence of RWGS (Eq. (5)). To iden-
 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91 83

(a) (b)
CO2: H2O = 1.0 : 2.1 CO2: H2O = 1.0 : 2.1
100 100

80
80

CO2 conversion (%)

CH4 conversion (%)

60
60
40

40 20
(CO2+H2O)/CH4 = 0.9 (CO2+H2O)/CH4 = 0.9
(CO2+H2O)/CH4 = 1.2 (CO2+H2O)/CH4 = 1.2
0
20 (CO2+H2O)/CH4 = 1.4 (CO2+H2O)/CH4 = 1.4
(CO2+H2O)/CH4 = 2.0 (CO2+H2O)/CH4 = 2.0
(CO2+H2O)/CH4 = 2.9 -20 (CO2+H2O)/CH4 = 2.9
0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

(c) (d)
CO2: H2O = 1.0 : 2.1 CO2: H2O = 1.0 : 2.1
100 100

80 80
CO yield (%)
H2 yield (%)

60 60

40 40
(CO2+H2O)/CH4 = 0.9 (CO2+H2O)/CH4 = 0.9
(CO2+H2O)/CH4 = 1.2 (CO2+H2O)/CH4 = 1.2
20 (CO2+H2O)/CH4 = 1.4 20 (CO2+H2O)/CH4 = 1.4
(CO2+H2O)/CH4 = 2.0 (CO2+H2O)/CH4 = 2.0
(CO2+H2O)/CH4 = 2.9 (CO2+H2O)/CH4 = 2.9
0 0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

(e)
CO2: H2O = 1.0 : 2.1
100
(CO2+H2O)/CH4 = 0.9
(CO2+H2O)/CH4 = 1.2
80
(CO2+H2O)/CH4 = 1.4
(CO2+H2O)/CH4 = 2.0
Coke yield (%)
(f)
CO2: H2O = 1.0 : 2.1
16 (CO2+H2O)/CH4 = 0.9 (CO2+H2O)/CH4 = 1.2
(CO2+H2O)/CH4 = 1.4 (CO2+H2O)/CH4 = 2.0
14
(CO2+H2O)/CH4 = 2.9
12

(CO2+H2O)/CH4 = 2.9 3
H2/CO ratio

60 10

8
40 2
6

20 4 1
600 800 1000
2
0
0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

Fig. 1. Effect of (CO2 + H2O)/CH4 ratio as a function of temperature at a fixed CO2:H2O ratio of 1.0:2.1: (a) CH4 conversion, (b) CO2 conversion, (c) H2 yield, (d) CO yield, and
(e) Coke yield, and (f) H2/CO ratio.

tify the equilibrium for the WGS reaction (Eq. (4)), the equilibrium
mole fractions of CO, H2O, H2, and CO2 are shown in Fig. 2. The
mole fractions of CO and H2O exceeded those of H2 and CO2 at tem-
peratures above 800 °C. This indicates that RWGS (Eq. (5)) is more
favored than WGS in the high temperature region. Thus, it can be
expected that the consumption of H2 by RWGS (Eq. (5)) leads to
a decrease of H2 yield at temperatures above 800 °C. Alternatively,
the maximum value of H2 yield decreased as the (CO2 + H2O)/CH4
ratio increased. This is due to the fact that CH4 is the limiting
reactant and the excess oxidizing agent is considered to be denom-
inators of the H2 yield equation.
Fig. 1(d) depicts CO yield as a function of temperature with
various (CO2 + H2O)/CH4 ratios. CO yield monotonically increased
with increasing the temperature as a result of the favorable nature
84
50
Water gas shift: CO + H 2O <-> CO2 + H2
Reactant: CO (50%) + H 2O (50%)
40
Concentration (%)
30
20
10
0
500 600 700
Temperature ( C)
Fig. 2. Equilibrium mole fraction for the water gas shift reaction as a function of
temperature (CO = 50% and H2O = 50%).
of the reforming reactions at high temperatures. Below 650 °C, the
increasing trend of CO yield as a function of temperature was sim-
ilar in all (CO2 + H2O)/CH4 ratios. However, from 650 °C, CO yield
for the lower (CO2 + H2O)/CH4 ratios (0.9, 1.2, and 1.4) has
increased sharply, while the CO yield for the higher (CO2 + H2O)/
CH4 ratios (2.0 and 2.9) has increased gradually. When the temper-
ature was above 750 °C, the CO yield of the lower (CO2 + H2O)/CH4
ratios (0.9, 1.2, and 1.4) exceeded those of the higher (CO2 + H2O)/
CH4 ratios (2.0 and 2.9). The reason for this result will be discussed
at next section.
Fig. 1(e) shows coke yield as a function of temperature with var-
ious (CO2 + H2O)/CH4 ratios. Coke yield decreased with increasing
the temperature. In addition, coke yield dramatically decreased
with increasing the (CO2 + H2O)/CH4 ratio. This result indicates
that high temperatures and high (CO2 + H2O)/CH4 ratio suppress
the formation of coke. In the case of the higher (CO2 + H2O)/CH4
ratios (2.0 and 2.9), coke formation can be avoided at temperatures
above 650 °C. When the temperature increased up to 750 °C, nearly
0% of coke yield could be achieved for the lower (CO2 + H2O)/CH4
ratios (1.2 and 1.4). Conversely, a considerable amount of coke
yield was observed for the lowest (CO2 + H2O)/CH4 ratio (0.9) even
at high temperatures due to the insufficient oxidizing agent.
It should be pointed out that the formation of coke originates
from the CH4 decomposition (Eq. (6)) and the Boudouard reaction
(Eq. (7)). This demonstrates that coke yield is closely related with
CH4 conversion and CO yield. In general, the excess oxidizing agent
can be expected to achieve a high CH4 conversion via the reforming
reaction [31]. However, CH4 conversion value for the lower
(CO2 + H2O)/CH4 ratios is higher than CH4 conversion for the higher
(CO2 + H2O)/CH4 ratios in the temperature range from 500 to
650 °C. In addition, the lower (CO2 + H2O)/CH4 ratios showed lower
CO yield than the higher (CO2 + H2O)/CH4 ratios in this tempera-
ture range. These results are possibly due to the consumption of
CH4 and CO by the CH4 decomposition (Eq. (6)) and Boudouard
reaction (Eq. (7)). However, these trends have changed at temper-
atures above 650 °C. To identify the dependence of coke formation
on temperature, the carbon containing products in the presence of
only CH4 or CO are shown in Fig. 3(a) and (b), respectively. The CH4
decomposition (Eq. (6)) is favored at high temperatures, but a sig-
nificant amount of coke formation was observed at low tempera-
tures (Fig. 1(e)). The Boudouard reaction (Eq. (7)) was favored at
low temperatures and did not occur above 900 °C. This indicates
that the formation of coke is due to both the CH4 decomposition
(Eq. (6)) and Boudouard reaction (Eq. (7)), but it is mainly affected
W.-J. Jang et al. / Applied Energy 173 (2016) 80–91
by the Boudouard reaction (Eq. (7)) in the low temperature region.
Thus, it can be explained that the high CH4 conversion and low CO
yield for the lower (CO2 + H2O)/CH4 ratios are originated from coke
formation by the CH4 decomposition (Eq. (6)) and Boudouard reac-
tion (Eq. (7)).
It should be noted that coke yield strongly depends on the type
of oxidizing agent, even when the ratio between oxidizing agent
and CH4 is same. To identify the effect of the type of oxidizing
agent on the product, the carbon containing product was simulated
and shown in Fig. 3(c) and (d). In the presence of H2O, the domi-
nant residue was CH4. Conversely, the main product was coke in
CH4 CO the presence of CO2. This indicates that H2O can more effectively
CO2 H2 prevent the formation of coke than CO2. On the contrary, CO2 helps
H2O C to accelerate the conversion of CH4, resulting in increased coke for-
mation. According to Figs. 1(e), 3(c), and (d), an important similar-
800 900 1000 ity is that the formation of coke cannot be avoided in the low
o temperature region, even though there is excess oxidizing agent
(irrespective of the type of oxidizing agent). However, these figures
also showed that the oxidizing agent can suppress the formation of
coke in the high temperature region. This indicates that the key
factors which affect coke formation are the type and amount of
the oxidizing agent, and temperature. Coke formation in the low
temperature region clearly depends on these aforementioned fac-
tors, but coke formation in the high temperature region is only
affected by the (CO2 + H2O)/CH4 ratio. Thus, these factors should
be taken into account to determine the appropriate reaction
conditions.
Fig. 1(f) depicts H2/CO ratio as a function of temperature with
various (CO2 + H2O)/CH4 ratios. In the low temperature region,
high H2/CO ratios were obtained. This is due to the production of
H2 by the CH4 decomposition (Eq. (6)) and the consumption of
CO by the Boudouard reaction (Eq. (7)) and WGS (Eq. (4)). H2/CO
ratio approached a fixed value with increasing temperature. For
an (CO2 + H2O)/CH4 ratio of 0.9, H2/CO ratio converged to ca. 2.2.
This result suggests that the entire oxidizing agent reacted with
CH4 via the reforming reaction and the remaining CH4 formed coke
and H2 without producing CO. In the case of (CO2 + H2O)/CH4 ratios
of 1.2 and 1.4, H2/CO ratio gradually approached 2.0 at tempera-
tures above 850 °C. For the higher (CO2 + H2O)/CH4 ratios (2.0
and 2.9), as a result of the dominant SRM reaction (Eq. (1)), H2/
CO ratio was higher than 2.0 between 750 and 800 °C. Conversely,
H2/CO ratio decreased to below 2.0 above 900 °C. In case of higher
(CO2 + H2O)/CH4 ratios (2.0 and 2.9), there are two possible reasons
to explain this result; (i) the CDR reaction is favorable than the
SRM reaction at high temperatures even at the same reaction con-
dition, or (ii) the RWGS reaction occurs at high temperature.
3.2. Effect of the CO2:H2O ratio
To demonstrate the reaction pathway of CSCRM, the CO2:H2O
ratio was varied at a fixed (CO2 + H2O)/CH4 ratio of 1.2.
Fig. 4(a)–(f) show the effects of the CO2:H2O ratio and temperature
on CH4 conversion, CO2 conversion, H2 yield, CO yield, coke
yield, and H2/CO ratio in the CSCRM reaction. The results at other
(CO2 + H2O)/CH4 ratios are illustrated in supporting information
(Figs. S1–S4(a)–(f)).
As shown in Fig. 4(a), CH4 conversion monotonically increased
with increasing temperature for all CO2:H2O ratios. When the
portion of CO2 was larger than that of H2O in the oxidizing agent,
a large amount of CH4 was converted at temperatures below
750 °C. However, all CO2:H2O ratios showed a similar value of
CH4 conversion above 750 °C. Moreover, the maximum CH4
conversion was achieved at temperatures above 850 °C, without
regard to the CO2:H2O ratio. This indicates that the temperature
that can achieve the maximum CH4 conversion depends not on
the CO2:H2O ratio but on the (CO2 + H2O)/CH4 ratio.
 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91 85

(a) CH4 (b) CO

100 100

Carbon containing product (%)

Carbon containing product (%)

C
80 80
C

60 60

40 40
CH4
CO2
20 20

CO
0 0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

(c) CH4 + H2O (d) CH4 + CO2

100 100
Carbon containing product (%)

Carbon containing product (%)

C

80 80
C
CO2

60 CO 60

40 40
CH4 CO2

20 20
CO
CH4
0 0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

Fig. 3. Carbon containing product for the various reactions: (a) CH4 decomposition (CH4 = 100%), (b) Boudouard reaction (CO = 100%), (c) Reforming of CH4 with H2O
(CH4 = 50% and H2O = 50%), and (d) Reforming of CH4 with CO2 (CH4 = 50% and CO2 = 50%).

Fig. 4(b) depicts CO2 conversion as a function of temperature
with various CO2:H2O ratios. As discussed in the previous section,
CO2 conversion showed two trends as a function of temperature.
CO2 conversion slightly decreased from 500 to 550 °C, but started
to increase at temperatures above 550 °C. One interesting observa-
tion is that CO2 conversion showed a similar increasing rate irre-
spective of the CO2:H2O ratio.
Fig. 4(c) and (d) exhibit H2 yield and CO yield as a function of
temperature with various CO2:H2O ratios, respectively. H2 yield
and CO yield increased with rising temperatures as a result of
the reforming and secondary reactions. The differences in H2 and
CO yields with various CO2:H2O ratios are negligible. This indicates
that similar portions of reactants can be converted into H2 and CO,
even at a different CO2:H2O ratio. This result is in good agreement
with CO2 conversion (Fig. 4(b)), which showed a similar increasing
rate, even at a different CO2:H2O ratio. On the contrary, H2O and
CO2 competitively react with CH4 at the higher (CO2 + H2O)/CH4
ratios, as shown in Fig. 1(a)–(d). Thus, it can be concluded that
the yield of the synthesis gas depends not on the CO2:H2O but on
the (CO2 + H2O)/CH4 ratio.
Fig. 4(e) shows coke yield as a function of temperature with var-
ious CO2:H2O ratios. Coke yield decreased with rising temperature
and coke formation can be avoided at temperatures above 800 °C.
When the portion of CO2 was larger than that of H2O, coke forma-
tion was significant in the low temperature region. This is consis-
tent with the interpretation in the previous section (Fig. 3(a)–(d)).
Fig. 4(f) depicts H2/CO ratio as a function of temperature with
various CO2:H2O ratios. In contrast with the results in Fig. 1(f),
the H2/CO ratio of the product gas converged to different values
at different CO2:H2O ratios. When the portion of CO2 was larger
than that of H2O, synthesis gas with a low H2/CO ratio was pro-
duced via CDR. H2/CO ratio increased with the increase of H2O
amount due to the occurrence of SRM. Thus, it can be concluded
that H2/CO ratio of synthesis gas can be controlled by changing
the CO2:H2O ratio at a fixed (CO2 + H2O)/CH4 ratio. In addition, in
order to produce synthesis gas with an H2/CO ratio of 2.0, the por-
tion of H2O should be twice greater than that of CO2.
To confirm the validity of derived results, the effect of the CO2:
H2O ratio as a function of temperature at a fixed (CO2 + H2O)/CH4
ratio of 0.9, 1.4, 2.0, and 2.9 are shown in supporting information
(Figs. S1, S2, S3, and S4). When (CO2 + H2O)/CH4 ratio increased,
the maximum CH4 conversion can be achieved at low temperature
(Figs. S1–S4(a)). However, there was no relationship between the
CO2:H2O ratio and the temperature in this temperature region.
When the (CO2 + H2O)/CH4 ratio was fixed, H2 and CO yields
(Figs. S1–S4(c) and (d)) showed the same trend even at a different
CO2:H2O ratio. On the contrary, the H2/CO ratio (Figs. S1–S4(f)) has
converged to different values at different CO2:H2O ratios. When the
portion of H2O is twice higher than that of CO2 in the oxidizing
agent, H2/CO ratio of 2.0 can be achieved at 850 °C irrespective of
the (CO2 + H2O)/CH4 ratio. This indicates that CO2:H2O ratio of
1:2.1 is the only way to produce synthesis gas with the H2/CO ratio
86 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91

(a) (b)
(CO2+H2O)/CH4 = 1.2 (CO2+H2O)/CH4 = 1.2
100 100

80 80
CH4 conversion (%)

CO2 conversion (%)

60
60

40
40
CO2 : H2O = 3.0 : 1.0 CO2 : H2O = 3.0 : 1.0
CO2 : H2O = 2.1 : 1.0 20 CO2 : H2O = 2.1 : 1.0
20 CO2 : H2O = 1.0 : 1.0 CO2 : H2O = 1.0 : 1.0
CO2 : H2O = 1.0 : 2.1 CO2 : H2O = 1.0 : 2.1
0
CO2 : H2O = 1.0 : 3.0 CO2 : H2O = 1.0 : 3.0
0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

(c) (d)
(CO2+H2O)/CH4 = 1.2 (CO2+H2O)/CH4 = 1.2
100 100

80 CO yield (%) 80
H2 yield (%)

60 60

40 40
CO2 : H2O = 3.0 : 1.0 CO2 : H2O = 3.0 : 1.0
CO2 : H2O = 2.1 : 1.0 CO2 : H2O = 2.1 : 1.0
20 CO2 : H2O = 1.0 : 1.0 20 CO2 : H2O = 1.0 : 1.0
CO2 : H2O = 1.0 : 2.1 CO2 : H2O = 1.0 : 2.1
CO2 : H2O = 1.0 : 3.0 CO2 : H2O = 1.0 : 3.0
0 0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

(e)
(CO2+H2O)/CH4 = 1.2
100
CO2 : H2O = 3.0 : 1.0
CO2 : H2O = 2.1 : 1.0
80
CO2 : H2O = 1.0 : 1.0
CO2 : H2O = 1.0 : 2.1
Coke yield (%)
(f)
(CO2+H2O)/CH4 = 1.2
16 CO2 : H2O = 3.0 : 1.0 CO2 : H2O = 2.1 : 1.0
CO2 : H2O = 1.0 : 1.0 CO2 : H2O = 1.0 : 2.1
14
CO2 : H2O = 1.0 : 3.0
12

CO2 : H2O = 1.0 : 3.0 3.0

H2/CO ratio

60
10
2.5
8
40 2.0
6
1.5

20 4 1.0
600 800 1000
2
0
0
500 600 700 800 900 1000 500 600 700 800 900 1000
o o
Temperature ( C) Temperature ( C)

Fig. 4. Effect of CO2:H2O ratio as a function of temperature at a fixed (CO2 + H2O)/CH4 ratio of 1.2: (a) CH4 conversion, (b) CO2 conversion, (c) H2 yield, (d) CO yield, and (e)
Coke yield, and (f) H2/CO ratio.

of 2.0. These results are consistent with the results shown in Fig. 4
(a)–(f). It is interesting to note that the value of H2/CO ratio is
below 1.0 at a (CO2 + H2O)/CH4 ratio of 2.9 and a CO2:H2O ratio
of 3.0:1.0. The H2/CO ratio of synthesis gas produced by the CDR
reaction is 1.0. Thus, this indicates that the decrease of H2/CO ratio
at high temperature is mainly due to the RWGS reaction.
3.3. The effect of pressure
Performing the reforming process at elevated pressures can
reduce the compression steps for downstream applications, which
are typically performed at pressures above 10 atm [32,33]. Ther-
modynamic simulations with various pressures (1, 3, 5, 10, and

100
Boudouard : 2CO -> C(s) + CO 2
Gas molecule : 2 -> 1
Tendency : Favourable at high P
80
Concentration (%)
60
40
20
0
500 600 700
Temperature ( C)
Fig. 5. Equilibrium mole fraction for the Boudouard reaction as a function of
temperature with different pressure (Pressure = 1 and 20 atm).
100
CH4 decomposition : CH4 -> C(s) + 2H2
Gas molecule : 1 -> 2
Tendency : Favourable at low P
80
Concentration (%)
60
40
20
0
500 600 700
Temperature ( C)
Fig. 6. Equilibrium mole fraction for the CH4 decomposition reaction as a function
of temperature with different pressure (Pressure = 1 and 20 atm).
20 atm) were investigated to study the effect of pressure on
CSCRM. Fig. S5(a)–(f) show the effect of pressure and temperature
on CH4 conversion, CO2 conversion, H2 yield, CO yield, coke yield,
and H2/CO ratio at a fixed reaction condition ((CO2 + H2O)/
CH4 = 1.2 and CO2:H2O = 1:2.1). Since the total number of moles
of the product is larger than that of the reactant, the reforming
reactions are not favorable at high pressures. As a result, conver-
sions and yields are significantly suppressed by increasing the
pressure, as shown in Fig. S5(a)–(d). However, the tendency of coke
formation is affected by the temperature region. To identify the
dependence on pressure in the aspect of coke formation, the equi-
librium mole fractions for the CH4 decomposition (Eq. (6)) and the
Boudouard reaction (Eq. (7)) are shown in Figs. 5 and 6, respec-
tively. The CH4 decomposition (Eq. (6)) was preferable at low pres-
sures, while the Boudouard reaction (Eq. (7)) was favorable at high
pressures. In the case of the Boudouard reaction (Eq. (7)), the reac-
tant (2 mol of CO) has larger moles of gas than the product (1 mol
of CO2). When pressure increased, the equilibrium shifted to the
forward reaction with fewer moles of gas. On the contrary, the
reactant (1 mol of CH4) has less moles of gas than the product
(2 mol of H2) for the CH4 decomposition (Eq. (6)) reaction. When
pressure increased, the equilibrium shifted to the reverse reaction
with larger moles of gas. The CH4 decomposition (Eq. (6)) and the
W.-J. Jang et al. / Applied Energy 173 (2016) 80–91 87
Boudouard reaction (Eq. (7)) showed the opposite tendency with
increasing pressure. To estimate the total amount of coke forma-
tion with increasing the pressure, the equilibrium mole fractions
for the coke formation reactions are shown in Fig. S6. The total
amount of coke formation increased with increasing the pressure
Pressure increase
(1 atm -> 20 atm)
even though tendency of two reactions are opposite. Thus, this
pressure dependence caused an increase of the minimum temper-
ature, where coke formation can be avoided. In details, 0% coke
CO yield can be achieved above 750 °C for all (CO2 + H2O)/CH4 ratios
CO2 at 1 atm in Fig. 1(e), with the exception of the lowest
C (CO2 + H2O)/CH4 ratio (0.9). However, the minimum temperature
increased up to 850 °C with increasing pressure from 1 to
Pressure increase
(1 atm -> 20 atm)
20 atm, as shown in Fig. S5(e). H2/CO ratio converged to fixed value
at 850 °C irrespective of the pressure, as shown in Fig. 1(f) and
Fig. S5(f). These results indicate that, at temperatures above
800 900 1000 850 °C, the reforming reaction occurs dominantly.
o
4. Experimental results and discussion
4.1. Maximum yield of useful synthesis gas
First, the main purpose of CSCRM is to produce synthesis gas for
CH4 the Fischer–Tropsch synthesis. Thus, the H2/CO ratio of the pro-
H2 duced synthesis gas should be preferentially taken into account
C to determine the reaction conditions. In addition, the suppression
of coke formation is also an important factor for stable operation
of the process. Excess oxidizing agents effectively inhibit coke
formation, but extra operating costs are required to supply excess
oxidizing agents. Thus, finding methods which do not increase the
Pressure increase
operating costs, and simultaneously maintaining the yields of
(1 atm -> 20 atm) product are important for the CSCRM reaction.
To check the availability of the synthesis gas, thermodynamic
equilibriums of H2/CO ratio and coke yield are compared, as shown
in Figs. 7 and 8. The (CO2 + H2O)/CH4 ratio of 0.9 is not suitable for
CSCRM due to the high H2/CO ratio and coke yield. In the
(CO2 + H2O)/CH4 ratio range from 1.2 to 2.9, a temperature of at least
800 900 1000 850 °C is required to produce the synthesis gas with an H2/CO ratio
o of ca. 2.0. In addition, a temperature of at least 850 °C is needed to
avoid coke formation at high pressures. Among the various CO2:
H2O ratios, 1:2.1 is the only possible option that can produce syn-
thesis gas with an H2/CO ratio of 2.0. Therefore, it can be concluded
that the (CO2 + H2O)/CH4 ratios of above 1.2, the CO2:H2O ratio of
1:2.1, and temperature of at least 850 °C are preferable reaction
conditions to prepare the synthesis gas in the GTL technology.
4.2. Application for the CSCRM reaction
To verify the applicability of these results, the thermodynamic
equilibrium results should corroborate with the experimental
reaction results. The Ni–MgO–CeO2–ZrO2 catalyst has been
reported to exhibit excellent catalytic performance in the reform-
ing reaction [11,29,30]. Table S2 provides a comparison of reported
data for the reforming reaction using Ni–CeO2 based catalysts [34–
39]. Thus, this catalyst is suitable to obtain experimental data
under equilibrium thermodynamic conditions. The CSCRM reaction
was carried out over the Ni–MgO–CeO2–ZrO2 catalyst at a GHSV of
20,000 h1 and a reaction temperature of 850 °C.
The comparison results between the thermodynamic equilib-
rium and experimental data are displayed in Fig. 9(a) and (b). Con-
versions and yields from the experimental data match those from
the thermodynamic equilibrium. However, 100% CO2 conversion
was achieved at an (CO2 + H2O)/CH4 ratio of 0.9, indicating that
the entire CO2 and H2O were converted into the product even
though the value is higher than the value obtained via thermody-
namic equilibrium. This indicates that reforming and side reactions
88 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91

4 4
o o
700 C 700 C
o o
750 C 750 C
o o
800 C 800 C
o o
850 C 850 C
o o
900 C 900 C
H2 /CO ratio 3 3

2 2

1 1
0.9 1.2 1.4 2.0 2.9 3.0: 1.0 2.1: 1.0 1.0:1.0 1.0: 2.1 1.0: 3.0
Oxidant content CO2 : H2O ratio

Fig. 7. Thermodynamic equilibrium comparison of H2/CO ratio with different (CO2 + H2O)/CH4 ratios and CO2:H2O ratios.

0.5 0.5
o o
700 C 700 C
o o
750 C 750 C
o o
0.4 800 C 0.4 800 C
o o
850 C 850 C
o o
900 C 900 C
0.3 0.3
Coke yield (%)

0.2 0.2

0.1 0.1

0.0 0.0

0.9 1.2 1.4 2.0 2.9 3.0: 1.0 2.1: 1.0 1.0:1.0 1.0: 2.1 1.0: 3.0
Oxidant content CO2 : H2O ratio

Fig. 8. Thermodynamic equilibrium comparison of coke yield with different (CO2 + H2O)/CH4 ratios and CO2:H2O ratios.

under conditions with insufficient oxidizing agent were mainly
ruled by kinetics as a result of incorrect material balance between
reactants. Thus, all of limiting reactants (oxidizing agents CO2 and
H2O) were converted into synthesis gas by the reforming reactions
and remaining CH4 was converted into C and H2 by the CH4 decom-
position reaction. It was also observed that CO2 conversion and CO
yield in the experimental data became slightly higher than those of
the equilibrium data, when the (CO2 + H2O)/CH4 ratio increased
above 2.0. On the contrary, H2 yield and H2/CO ratio were slightly
lower than the thermodynamic equilibrium. As discussed in the
previous section (Fig. 1(f)), this is mainly due to the RWGS reaction.
This result indicates that the RWGS reaction is kinetically fast in
the real chemical reaction with excess oxidizing agent at the tem-
perature of 850 °C.
To check the effect of temperature on the difference between
the thermodynamic equilibrium and experimental data, conver-
sions, yields, and H2/CO ratio as a function of temperature are
shown in Fig. 10(a). The thermodynamic equilibrium and experi-
mental data showed the same trend, but the differences between
two values were observed at 800 °C. CO2 conversion and CO yield
in the experimental data were slightly higher than the thermody-
namic equilibrium, while H2 yield and H2/CO ratio were slightly
lower than the thermodynamic equilibrium. The gap of thermody-
namic equilibrium and experimental data became larger with
increasing temperature from 800 to 850 °C. This indicates that
the RWGS reaction occurs at temperature above 800 °C. This result
is consistent with the results shown in previous paragraph and
Fig. 2.
Fig. 10(b) shows conversions, yields, and H2/CO ratio as a function
of time on stream at an (CO2 + H2O)/CH4 ratio of 1.2, a CO2:H2O ratio
of 1:2.1, and a temperature of 850 °C for 500 h. Although the equilib-
rium simulation suggested a coke yield of 0% at (CO2 + H2O)/CH4
ratios above 1.2, a long-term stability test was conducted to check
for the stable operation under the studied conditions in the CSCRM
 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91 89

(a) (Lines)Thermodynamic eqilibrium (b) (Lines)Thermodynamic eqilibrium

(Symbols) Experimental result (Symbols) Experimental result

100 100
Conversion (%)

Conversion (%)
80 80

60 60
XCH4 XCH4
40 XCO2 40 XCO2

100 100

90 90

Yield (%)
Yield (%)

80 80
YH2 YH2
YCO YCO
70 70

3.0 2.5
H2/CO ratio
2.5
H2 /CO ratio

H2/CO ratio
2.0
2.0
1.5
1.5
H2/CO ratio
1.0 1.0
0.9 1.2 1.4 2.0 2.9 3.0:1.0 2.1:1.0 1.0:1.0 1.0:2.1 1.0:3.0
Oxidant content CO2 : H2O ratio

Fig. 9. Comparison between thermodynamic equilibrium (lines) and experimental result (symbols): (a) (CO2 + H2O)/CH4 ratio and (b) CO2:H2O ratio.

(a) (Lines)Thermodynamic eqilibrium (b) (Lines)Thermodynamic eqilibrium

(Symbols) Experimental result (Symbols) Experimental result
100 100
Conversion (%)

Conversion (%)

80 80

60 60
XCH4 XCH4
40 XCO2 40 XCO2
100 100

80 80
Yield (%)

Yield (%)

60 60
YH2 YH2
YCO YCO
40 40

3.0 3.0
H2 /CO ratio

H2 /CO ratio

2.5 2.5

2.0 2.0

1.5 H2/CO ratio 1.5 H2/CO ratio

650 700 750 800 850 0 100 200 300 400 500
o
Temperature ( C) Time on stream (h)

Fig. 10. Conversions, yields, and H2/CO ratio at an (CO2 + H2O)/CH4 ratio of 1.2 and a CO2:H2O ratio of 1:2.1: (a) as a function of temperature and (b) as a function of time on
stream at a temperature of 850 °C for 500 h.

reaction. All of the conversions and yields were extremely stable and used catalyst after the reaction was also investigated by TGA/DTG
maintained their equilibrium values for 500 h without any detect- in an oxidative atmosphere; these results are shown in Fig. 11. Up
able deactivation. Quantitative analysis of coke formation over the to 230 °C, the initial weight loss is caused by the thermal desorption
90 W.-J. Jang et al. / Applied Energy 173 (2016) 80–91
Reactantads↑ Ni → NiO
0
C → CO and CO2
105
Sample weight (%)
100
Used Ni-MgO-CeO2-ZrO2
95
200 400 600
o
Temperature ( C)
Fig. 11. TGA profile of used catalyst after the CSCRM reaction (Reaction condition:
T = 850 °C, TOS = 500 h).
of H2O [29,40,41]. In the temperature range from 230 to 420 °C, the
increase in the weight is due to the oxidation of metallic Ni
[29,40,41]. In general, the weight loss above 420 °C is ascribed to
the oxidation of coke to CO and CO2 [29,40,41]. However, this weight
loss was not observed in the TGA result of the used catalyst, indicat-
ing that coke formation was not detectable for 500 h. As a result, this
application of the CSCRM reaction in real condition demonstrated
that the thermodynamic equilibrium was in good agreement with
the experimental data and that stable operation was also achieved
in the tested conditions.
5. Conclusions
The (CO2 + H2O)/CH4 ratio, CO2:H2O ratio, pressure, and temper-
ature have a significant influence on conversions, yields, coke yield,
and H2/CO ratio in the combined H2O and CO2 reforming of
methane reaction. In particular, the (CO2 + H2O)/CH4 ratio strongly
affects the temperature, which can achieve the maximum conver-
sion of CH4 and CO2. The formation of coke cannot be avoided at
the low temperature region even with excess oxidizing agent,
but coke formation in the high temperature region can be sup-
pressed by increasing the (CO2 + H2O)/CH4 ratio. An (CO2 + H2O)/
CH4 ratio of at least 1.2 is required to avoid coke formation. We
also found that H2/CO ratio of the synthesis gas can be controlled
by changing CO2:H2O ratio. When the portion of H2O is twice
higher than that of CO2 in the oxidizing agent, the synthesis gas
with an H2/CO ratio of 2.0 can be obtained above 850 °C. Thus, it
has been concluded that a (CO2 + H2O)/CH4 ratio above 1.2, a
CO2:H2O ratio of 1:2.1, and a temperature of at least 850 °C are
preferable reaction conditions for synthesis gas preparation in
the GTL technology. The CSCRM reaction is carried out to verify
the applicability of the simulation results. The thermodynamic
equilibrium data is consistent with the experimental data, but
the H2/CO ratio of the experimental data is slightly lower than
those of the simulation values at high temperatures due to the
RWGS reaction. The long-term stability test carried out under sim-
ulated condition ((CO2 + H2O)/CH4 ratio of 1.2, the CO2:H2O ratio of
1:2.1, and the temperature of 850 °C) shows that the equilibrium
conversion was maintained for 500 h and that coke formation on
the used catalyst was not observed.
Acknowledgements
The authors gratefully acknowledge financial support from the
Samsung Advanced Institute of Technology (SAIT), Samsung
Electronics Co. Ltd. This research was supported by Basic Science
Research Program through the National Research Foundation of
Korea (NRF) funded by the Ministry of Science, ICT and Future
Planning (2013R1A1A1A05007370).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apenergy.2016.
04.006.
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