Article

pubs.acs.org/IECR

Novel Sorption-Enhanced Methanation with Simultaneous CO2

Removal for the Production of Synthetic Natural Gas
Soo Ik Im and Ki Bong Lee*
Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 136-713, Republic of Korea
ABSTRACT: With increasing consumption of natural gas as a
clean energy source and demand for ecient use of cheap and
abundant coal, the production of synthetic natural gas from
coal has been receiving considerable interest. In this study, the
methanation reaction of coal-derived syngas for the production
of synthetic natural gas was investigated using numerical
simulations. In particular, the concept of a sorption-enhanced
reaction, in which CO2 removal by sorption is carried out simultaneously with the reaction, was newly applied to the methanation
reaction. Eects of the operating parameters such as the fraction of catalyst and sorbent, temperature, pressure, and feed ratio
(H2/CO, H2O/CO, and CO2/CO) on CO conversion and purity, selectivity, and productivity of CH4 were evaluated by
computational studies. It was found that the performance of the sorption-enhanced methanation reaction is controlled by both
thermodynamic equilibrium and reaction kinetics. Therefore, the reaction would require an optimal catalyst fraction,
temperature, and pressure conditions for maximum eciency. Optimal H2/CO and H2O/CO ratios exist considering reaction
performance, and any CO2 content in the feed reduces CH4 productivity. Compared to the conventional methanation reaction,
the sorption-enhanced methanation reaction produces CH4 in high purity (>95%), which can be directly used for synthetic
natural gas without further separation processes.

1. INTRODUCTION
Since the past few years, the demand for energy has been
increasing incredibly due to the rapid development of energyintensive industries and increasing human activities. Currently,
about 80% of the global energy is produced from conventional
fossil fuels. This massive usage of fossil fuels is primarily
responsible for serious environmental problems such as
pollution and global warming.1 With increasing awareness of
these issues, the global consumption of natural gas has been
increasing because it is considered to be a clean energy source;
burning of natural gas is a highly ecient combustion process
with lower emissions of CO2 and pollutants than any other
fossil fuel.2,3 In contrast, coal has long been known as the major
factor contributing to environmental issues. However, coal is
cheap and abundant, and therefore, numerous eorts have been
made to develop clean coal technologies to reduce the
environmental impacts of the usage of coal energy.4 One of
the promising clean coal technologies is to produce synthetic
natural gas (SNG) from coal-derived synthesis gas. Unlike
direct coal combustion, coal-to-SNG can reduce and eciently
control the emissions of CO2 and pollutants caused by coal
usage.4 Also, established infrastructures such as pipelines and
distribution networks for natural gas can be used for the
transportation of SNG.57 In the production of SNG from coal,
the raw material is initially converted to gases such as methane,
carbon monoxide, hydrogen, carbon dioxide, and water vapor at
high temperatures (>1000 C). Additionally, the carbon
monoxide and carbon dioxide in the rened synthesis gas are
converted to methane, the main component of SNG, based on
a catalytic methanation reaction. Before the reaction, sulfur
compounds are removed by commercial processes based on
2016 American Chemical Society

absorption using solvent (e.g., Selexol) and adsorption using

ZnO.
SNG production processes have been developed since the
1960s, and since then, most of the research eorts have been
directed toward the design of ecient reactors and improvement in reaction eciency.8 Since the reactions involved in
SNG production are exothermic, it is preferable to carry out the
reactions at lower temperatures, but then, the kinetics of the
catalytic reaction would be unfavorable at very low temperatures. In addition to methanation reactions, the separation of
the remaining CO in the feed and byproduct components such
as CO2 and H2O is important for the production of high-purity
methane.8 New reaction schemes also have been studied to
improve the conventional methanation reaction. Lim et al.
invented a new SNG production process in which the
methanation reaction is carried out in two steps with the
water gas shift (WGS) reaction sandwiched between them. This
method can control the heat generation from the exothermic
methanation reaction and extend catalyst lifetimes.9 Duyar et al.
proposed a new methanation reaction process in which a dualfunctional material is used to capture CO2 from a ue gas at
320 C, and the captured gas is directly used for a CO2
methanation reaction at the same temperature. The new
process can save thermal energy required for the reaction.10
Recently, a new sorption-enhanced reaction (SER) concept was
applied to methanation reactions to enhance conversion and to
Received:
Revised:
Accepted:
Published:
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DOI: 10.1021/acs.iecr.6b01681
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simultaneously remove the byproducts.2,1113 This simultaneous byproduct removal by sorption, which occurs in the same
reactor, enhances the reaction eciency based on Le Chateliers
principle. The SER process circumvents the thermodynamic
limitation in the reaction: The conversion of reactants to
products can be enhanced through the byproduct sorption for
the same equilibrium constant, compared to the catalyst-alone
case. It enables direct production of high-purity product
without further purication process via a compact reaction
process.14,15 The SER process has been mainly applied to the
WGS and steam methane reforming reactions for high-purity
hydrogen production.1620
In this study, the methanation reaction, the WGS reaction,
and CO2 sorption were integrated together to develop a novel
sorption-enhanced methanation (SE-methanation) process
(Figure 1). In this process, CO2 sorption is introduced for

CO2 methanation reaction

H298K = 165 kJ/mol

CO2 + 4H 2 CH4 + 2H 2O

(3)

2.1. Methanation and WGS Reactions. The empirical

expressions by Xu and Froment (1989) were used for
evaluating the reaction rates as follows:22
CO methanation reaction
R1 =

k1
pH

2.5

(pCH pH O pH 3 pCO K1)

4

1
DEN2

(4)

WGS reaction
R2 =

k2
pH

pH pCO 1

2
2

pCO pH O
2
K
DEN2

(5)

CO2 methanation reaction

pH 4 pCO K1 1
k3
2
2
2

p p
R3 =

DEN2
K2
pH 3.5 CH4 H2O

DEN = 1 + K COpCO + K H2pH + K CH4pCH

2

+ K H2OpH O /pH
2

Figure 1. Scheme of sorption-enhanced methanation process.

* (P , T ) =
nads

2. NUMERICAL MODELING
SNG production normally involves multiple catalytic reactions.
Methanation reactions are used to produce CH4, the main
component of SNG, from CO and CO2 in the feed stream,
while the WGS reaction simultaneously proceeds in the reactor
as a side reaction in the presence of Ni-based catalysts.21 CO2
methanation reaction is a linear combination of CO
methanation and WGS reactions and therefore the CO2
methanation reaction rate is dependent on the rates of CO
methanation and WGS reactions.
CO methanation reaction

mK C[1 + (a + 1)KR P a]
1 + K CP + K CKRP a + 1

(1)

q
K C = K C0 exp c
RT

(2)

KR = KR0 exp
RT

H298K = 206 kJ/mol

H298K = 41 kJ/mol

(7)

(8)

where nads
* denotes the specic amount of CO2 sorbed on the
sorbent at an equilibrium state as a function of pressure, P, and
temperature, T. m is the maximum sorption capacity of CO2
and a is the stoichiometric ratio of the reaction between
gaseous CO2 and chemisorbed CO2. KC and KR are the
equilibrium constants for the chemisorption and the additional
reaction between gaseous CO2 and chemisorbed CO2,
respectively. These equilibrium constants are dependent on
the temperature as follows:

WGS reaction
CO + H 2O CO2 + H 2

where ki and Ki are the rate and equilibrium constants,

respectively, of reaction i. These values are given as a function
of temperature. pj is the partial pressure of component j. DEN
represents the denominator and is a term consisting of KCO,
KH2, KCH4, and KH2O, which are the surface adsorption
parameters at equilibrium.22
2.2. CO2 Sorption on K2CO3-Promoted Hydrotalcite.
K2CO3-promoted hydrotalcite was used as a CO2 sorbent in
this study because of its high sorption stability at the operating
temperature (300350 C) of the methanation reaction.23,24
Lee et al. developed a CO2 sorption model for K2CO3promoted hydrotalcite as a function of temperature.23 The
model assumes a two-step CO2 sorption mechanism: (i)
reversible chemisorption of CO2 on the sorbent and (ii)
reversible chemical reaction between gaseous CO2 and
chemisorbed CO2 to produce a chemical complex.

promoting the WGS reaction to produce more H2, which can

then be used for the CO methanation reaction, consequently
leading to more CH4 production. The SE-methanation process
was investigated using numerical simulations and the eects of
operating parameters such as the catalyst fraction, temperature,
pressure, and feed composition on reaction performance were
examined. The performance of the SE-methanation process was
compared with that of the conventional methanation reaction.
From numerical simulation results, suitable operational
conditions were obtained for an ecient SE-methanation
process. The feasibility of this process was studied to ensure
that the product composition could meet the natural gas grid
specication for direct use of the product as SNG.

CO + 3H 2 CH4 + H 2O

(6)

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(9)

(10)
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where K0C and K0R are constants, qc is the molar isosteric heat of
sorption and HR is the reaction enthalpy of chemical complex
formation. All the parameters related to CO2 sorption are
summarized in Table 1. Other sorbent materials that can sorb
high-temperature CO2 also can be applied in this process.

Energy balance
b Vstagec ps

dT
= N inAc pg(T in T )
dt

b Vstage[ fcat iR i +

(1 fcat )Hads, jR ads, j]

Table 1. Model Parameters for CO2 Sorption and Reaction

parameter

value

m (mol/kg)
A
K0C (1/atm)
K0R (1/atm)
qc (kJ/mol)
HR (kJ/mol)
b (g/cm3)
Lc (cm)

dc (cm)
no. of stages

0.25
0.285 exp(12.2/RT)
0.878
0.00134
21.0
42.2
0.824
50
0.75
1.2
1.73
30

+ dcLstageU0(Tw T )

(15)

where N is the total molar ux, A is the cross-sectional area of

the reactor, b is the bulk density of solid consisting of catalyst
and sorbent, and fcat is the fraction of the catalyst in the solid. yj
is the mole fraction of component j and Ri is the rate of reaction
i. is a factor accounting for the heat capacity of the heatexchanger tube and body while nt is the total number of moles
of gaseous components. cps and cpg are the heat capacities of the
solid and gas phases, respectively. In the energy balance (eq
15), heat transfer between inside reactor and wall was
considered, assuming a constant wall temperature (Tw). The
parameters used in the numerical simulations are shown in
Table 1. The equations were solved by Matlab software using
ODE15s function, which is a solver for sti dierential
equations with a variable order method.
2.4. Evaluation of Reaction Performance. To evaluate
the performance of the SE-methanation process, CO and H2O
conversions were used and they are dened as follows:

2.3. Mathematical Model. The well-known model of

continuous stirred tank reactors (CSTRs) in series was adopted
for our numerical simulations. For a same total reactor volume,
a plug ow reactor can be described simply by CSTRs in a
series model with a large number of CSTRs.25 The main
assumptions for the mathematical model were (i) ideal gas
behavior, (ii) instantaneous thermal equilibrium between the
gas and solid inside the reactor, and (iii) no axial dispersion and
pressure drop. The widely used linear driving force model was
chosen for the mass transfer of CO2 sorption.2528 From
material and energy balances, the following governing
equations were derived.

tR

CO conversion (%) =

in
N inyCO
t R N outyCO dt
0
in
N inyCO
tR

(16)

H 2O conversion (%)
tR

N inyHin O t R N outyH O dt
0
2

N inyHin O t R

100
(17)

Ideal gas law

nt =

where Nin and Nout are the total molar uxes of feed and
product streams, respectively, and tR is the time on stream of
the reaction. Since Nout and yH2O change with time, integration
is needed to calculate the cumulative outlet concentration of
each component. H2O conversion is used only when H2O
exists in the feed stream. CH4 purity, CH4 selectivity, and CH4
productivity are also dened to assess the performance of the
SE-methanation process.

PVstage
(11)

RT

Molar balance in the solid phase (linear driving force model)

R ads, j =

dnads, j
dt

* j nads, j)
= kads, j(nads,

(12)

Overall molar balance in the gas phase

N A = N A b Vstage[ fcat R i , j+
out

in

CH4 purity (%) =

dn
(1 fcat )R ads, j] t
dt
j

dt

0 R N outyCH4 dt

CH4 selectivity (%) =

(18)

0 R N outyCH4 dt
t

0 R N out(yCH4 + yCO2 ) dt

100

CH4 productivity =

+ (1 fcat )R ads, j} yj b Vstage{ fcat R i , j

(1 fcat )R ads, j}]

100

(19)

1 in in
[N A(yj yj ) + b Vstage{ fcat R i , j
nt
i

0 R N out dt
t

(13)

Component molar balance in the gas phase

dyj

100

0 R N outyCH4 dt
b Lc

(20)

CH4 selectivity is calculated based on the CH4 fraction of the

total amount of carbon compounds in the product stream. CH4
productivity is dened as the rate of CH4 production based on
the total amount of solid in the reactor.

(14)

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Figure 2. Change of mole fraction prole in the SE-methanation process: (a) output gas stream and (b) CO2 gas inside the reactor. T = 350 C, P =
10 atm, H2/CO = 1, CO2/CO = 0.2.

Figure 3. Eect of catalyst and sorbent ratio on the performance of SE-methanation process: (a) CO conversion, (b) CH4 purity, (c) CH4 selectivity,
and (d) CH4 productivity. T = 350 C, P = 10 atm, H2/CO = 1, CO2/CO = 0.2.

3. RESULTS AND DISCUSSION

To systematically investigate the eects of the parameters on
the SE-methanation process, a base condition (as given below)
was chosen and a single parameter was changed while
maintaining other parameters constant. The reaction temperature was set at 350 C because the reaction for bulk
production of methane is usually carried out at 300350 C.8 A
feed gas ratio was selected at CO2/H2/CO = 0.2/1/1 based on
the syngas composition of the coal gasication process (CO2,
2.115.1 mol%; H2, 28.533.5 mol%; and CO, 34.457.2 mol
%).4 The gas composition is over stoichiometric in terms of the
methanation process. The total feed ow rate was xed at 0.8
mmol/cm2/min, corresponding to weight hourly space velocity
(WHSV) of 700 1/h.
T = 350 C,

P = 10 atm,

CO2 /CO = 0.2,

Figure 2a, it can be seen that the product gases start to come
out of the reactor column at 20 min after the reaction begins.
It is noteworthy that high-purity CH4 can be produced between
20 min and 60 min. During this period, CH4 is produced
from the CO methanation reaction (eq 1) and the byproduct
H2O further reacts with CO to produce CO2 and H2 via the
WGS reaction (eq 2). The H2 produced from the WGS
reaction can also be used for the CO methanation reaction. In
the SE-methanation process, CO2 produced from the WGS
reaction or initially contained in the feed stream can be
removed in the reactor, facilitating the WGS reaction with more
H2 production. Eventually, high-purity CH4 production can be
increased. The sorption-enhanced reaction continues until the
sorbent in the reactor is saturated with CO2. After the sorbent
is saturated with CO2 (60 min in Figure 2a), CO2 and CO
breakthroughs come out from the reactor, and the concentration of CH4 reduces. Finally, the euent composition
becomes the same as the equilibrium composition in the
presence of the catalyst only (CH4, 41.1 mol%; CO2, 57.2 mol
%; and CO, 1.1 mol%; H2, 0.2 mol%; H2O, 0.4 mol%).
Therefore, to obtain high-purity CH4, the SE-methanation

H 2 /CO = 1,

fcat = 0.7

3.1. Sorption-Enhanced Methanation Process. Figure 2

shows the change in the mole fraction prole during the SEmethanation process operated in the base condition. From
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Figure 4. Eect of temperature on the performance of SE-methanation process and conventional methanation reaction: (a) CO conversion, (b) CH4
purity, (c) CH4 selectivity, and (d) CH4 productivity. P = 10 atm, H2/CO = 1, CO2/CO = 0.2.

catalyst, there is no noticeable change in performance with

increasing the catalyst fraction any further. It is noteworthy that
CH4 productivity rst increases with increasing fcat, reaches a
maximum, and then decreases when fcat is larger than 0.7. In the
presence of a large catalyst fraction, CO2 sorption is reduced
due to the small amount of sorbent present in the system,
resulting in diminished eects of the sorption-enhanced
reaction and lower CH4 productivity. From the two conicting
eects of catalyst and sorbent amounts, there is an optimal fcat
(0.7) for maximum CH4 productivity in this condition.
3.3. Eect of Temperature. Since reaction rate is strongly
dependent on temperature, it is one of the important
operational parameters for the SE-methanation process. Figure
4 depicts the eect of temperature on the SE-methanation
process and conventional methanation reaction. At low reaction
temperatures of 275300 C, a very low CO conversion
(<20%) is obtained (Figure 4a), resulting from a slow reaction
rate for both the methanation and WGS reactions. The CO
conversion increases signicantly at temperatures above 300 C
and a similar trend was reported in previous studies.3032 Over
350 C, in the conventional methanation reaction without CO2
sorption, CO conversion decreases with increasing temperature
because the reaction is exothermic, and therefore, is unfavorable
at high temperatures. However, in the SE-methanation process,
a high CO conversion is seen (>95%) at 350600 C due to
the eect of the sorption-enhanced reaction which compensates
for the reduction of reaction performance at high temperatures:
byproduct (CO2) removal can increase the conversion of CO
to products based on the Le Chateliers principle. Since the
reactor temperature can rise up to 600 C during the
methanation reaction,8,33 maintaining a high CO conversion
over a wide temperature range is benecial. Compared to the
methanation and WGS reactions, the exothermic eect of CO2
sorption is not signicant.
Figure 4b shows that a low CH4 purity (<30%) is obtained at
low temperatures (275325 C) because the methanation

process should be continued until CO2 and CO breakthroughs

come out. The CO2-saturated reactor column is then
regenerated by using a thermal swing or pressure swing
operation for recycling. Lee et al. developed a scheme called the
thermal swing sorption enhanced reaction (TSSER) process in
which CO2-saturated sorbent is regenerated by heating the
column to desorb CO2 from the sorbent after the SER is
nished.29 Since natural gas normally contains 3% CO2,2 the
SE-methanation process in this study is carried out until
cumulative CO2 in the product stream reaches 3%.
Figure 2b exhibits the changes in the CO2 gas mole fraction
inside the reactor column with time. The position in the reactor
is normalized by the total column length. Initially, the CO2 in
the feed stream is removed quickly by sorption. Subsequently,
the CO2 concentration in the gas phase increases due to the
production of CO2 by the WGS reaction. The byproduct CO2
is captured by sorption until the sorbent is saturated with CO2.
As the operating time increases, a CO2 frontal wave develops
and proceeds toward the end of the reactor column.
3.2. Eect of Catalyst and Sorbent Ratio. The packing
ratio of the catalyst and the sorbent in the reactor aects the
performance of the SE-methanation process because of their
dierent roles in the reaction while the available amount of
solid materials in the reactor is limited. A high sorbent ratio
causes high CO2 sorption, which promotes the sorptionenhanced reaction, but the reduced amount of catalyst can limit
the reaction rate, and thereby lead to low CO conversion and
CH4 productivity. The eects of the catalyst fraction in the
solid phase (fcat) on the performance of the SE-methanation
process can be seen in Figure 3. CO conversion, CH4 purity,
and CH4 selectivity increase with increasing fcat when its value is
less than 0.4, and then remain at maximum values when fcat is
larger than 0.4. When the catalyst fraction is small, the reaction
rate is lower and therefore, the catalyst fraction plays an
important role in overall reaction performance. Once the
reaction rate is fast enough with adequate amounts of the
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Figure 5. Eect of pressure on the performance of the SE-methanation process and conventional methanation reaction: (a) CO conversion, (b) CH4
purity, (c) CH4 selectivity, and (d) CH4 productivity. T = 350 C, H2/CO = 1, CO2/CO = 0.2.

process, considering both equilibrium factors and reaction

kinetics.
3.4. Eect of Pressure. From a thermodynamic standpoint, the methanation reaction can be facilitated with
increasing pressure because the direction of reaction is toward
decreasing number of moles of components. However,
increasing the pressure can also decrease the reaction rates,
which makes it necessary to select an appropriate operating
pressure. Figure 5a shows that the CO conversion gradually
increases with increasing pressure in both the SE-methanation
process and conventional methanation reaction. This results
from a shift in equilibrium toward the forward reaction. The
CO conversion of the SE-methanation process is higher than
that of conventional methanation reaction except at a very high
pressure of 30 atm. At high pressures, the methanation reaction
becomes slow, and then the amount of the catalyst present
plays a dominant role. At a xed solid packing density,
compared to the conventional methanation reaction, the SEmethanation process contains a smaller amount of the catalyst
and is limited by the reaction rate at high operation pressure
conditions.
CH4 purity and selectivity exhibit a similar trend as shown in
Figure 5b,c. CH4 purity and selectivity of more than 95% are
obtained in the SE-methanation process, suggesting that a
considerable amount of CO2 is removed by sorption during the
reaction. In the conventional methanation reaction, CH4
selectivity and purity close to 50% are hardly achieved because
a large amount of CO2 is produced and remains with CH4 at a
H2/CO feed ratio of 1.
A higher operating pressure leads to lower CH4 productivity
in both the SE-methanation process and conventional
methanation reaction (Figure 5d). Although a high pressure
provides the advantage of a thermodynamic shift in the
equilibrium position of the methanation reaction and increases
CO2 sorption uptake for the SE-methanation process, the

reaction is slow under these conditions and only a small

amount of CH4 is produced while large amounts of CO remain
in the system. At 350 C, CH4 purity reaches 95% in the SEmethanation process compared to 40% in the conventional
methanation reaction. In the SE-methanation process, CO2
produced from the WGS reaction is removed by sorption. The
byproducts H2O and H2 are used for WGS and methanation
reactions, respectively, resulting in a very high CH4 fraction in
the product. Therefore, the product of the SE-methanation
process can be directly used for SNG without the need for
further separation processes. Above 350 C, in both the SEmethanation process and conventional methanation reaction,
CH4 purity decreases with increasing temperature because the
reaction is exothermic. With increasing temperature, CH4
selectivity rst increases and then is maintained at 95% and
40% in the SE-methanation process and conventional
methanation reaction, respectively, at temperatures higher
than 350 C (Figure 4(c)).
A comparison of CH4 productivities between the SEmethanation process and the conventional methanation
reaction shows that the productivity of SE-methanation process
is lower than that of the conventional methanation reaction in
the temperature range from 275 to 325 C (Figure 4d). This is
because the methanation reaction is limited by the reaction
kinetics at low temperatures while the conventional methanation reaction, which uses more catalyst than the SEmethanation process, can exhibit an improved reaction
performance.19,34 Above 350 C, the reaction rate becomes
fast enough not to be limited by the amount of catalyst, and the
eect of the sorption-enhanced reaction can be clearly seen
with improved CH4 productivity. However, at high temperatures over 350 C, CH4 productivity slightly decreases
(practically constant) with increasing temperature due to the
exothermicity of the methanation reaction and reduced CO2
sorption capacity. From these results, 350 C is thought to be
an optimal operating temperature for the SE-methanation
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Figure 6. Eect of H2/CO ratio on the performance of SE-methanation process and conventional methanation reaction: (a) CO conversion, (b)
CH4 purity and mole fraction of H2O in the product stream of SE-methanation process, (c) CH4 selectivity, and (d) CH4 productivity. T = 350 C, P
= 10 atm, CO2/CO = 0.2.

Figure 7. Eect of H2O/CO ratio on the performance of SE-methanation process and conventional methanation reaction: (a) CO conversion and
H2O conversion, (b) CH4 purity, (c) CH4 selectivity, and (d) CH4 productivity. T = 350 C, P = 10 atm, H2/CO = 1, CO2/CO = 0.2.

signicantly with increasing H2/CO ratio in the feed for both

the SE-methanation process and conventional methanation
reaction until the ratio reaches 1. When the H2 content in the
feed is low, the overall CO conversion is limited by decient
H2. At the H2/CO ratio of 1, CO conversion reaches 99%,
suggesting that a considerable amount of CO reacts with H2O
via the WGS reaction to produce H2. This H2 from the WGS
reaction further undergoes the methanation reaction with CO

reduction in reaction rates under these conditions has a

dominant eect, resulting in a lower CH4 productivity.
3.5. Eect of H2/CO Ratio in the Feed. The H2/CO ratio
in syngas produced from the coal gasication process is
normally 0.51,35 which is much lower than the stoichiometric
ratio of the methanation reaction (H2/CO = 3). To promote
the methanation reaction, additional H2 can be supplied to the
feed. Figure 6a shows that CO conversion increases
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Figure 8. Eect of H2O/CO ratio on the performance of SE-methanation process and conventional methanation reaction at low H2/CO ratio: (a)
CO conversion, (b) CH4 purity, (c) CH4 selectivity, and (d) CH4 productivity. T = 350 C, P = 10 atm, H2/CO = 0.5, CO2/CO = 0.2.

and particularly the CH4 purity, an H2/CO ratio 1 in the feed

is thought to be optimal.
3.6. Eect of H2O in the Feed. To investigate the eect of
H2O on the methanation reaction performance, it was added to
the feed stream without changing the ow rates of other
components. Figure 7a shows the change in CO and H2O
conversion with increasing amounts of H2O in the feed. Here,
H2O conversion is introduced to demonstrate how much H2O
in the feed reacts with CO. For both the SE-methanation
process and conventional methanation reaction, there is no
noticeable change in CO conversion with the addition of H2O
because a high CO conversion is already obtained in the base
condition without H2O. CH4 purity decreases with increasing
H2O/CO ratio (Figure 7b) because the unreacted H2O remains
in the product. In addition, CH4 selectivity and productivity are
not aected by the presence of H2O (Figure 7c,d).
To further study the eect of H2O under the conditions of
decient H2 in the feed, the H2/CO ratio is decreased from 1 to
0.5. When the H2/CO ratio is 0.5, CO conversion increases
from 50% to 99% as the H2O/CO ratio is increased from 0 to
0.5 for both SE-methanation process and conventional
methanation reaction (Figure 8a). This indicates that additional
H2O promotes the WGS reaction between CO and H2O to
produce H2. The H2O conversion of the SE-methanation
process is higher than that of conventional methanation
reaction because the WGS reaction is enhanced by CO2
removal in the SE-methanation process. At H2O/CO ratios
over 0.2, an excess of H2O remains in the reactor and therefore
H2O conversion decreases.
As can be seen in Figure 8b, CH4 purity increases with
increasing H2O supply until the H2O/CO ratio reaches 0.25.
The change in CH4 purity is more prominent in the SEmethanation process, while the CH4 purity is kept low in the
conventional methanation reaction due to the unreacted H2O
and byproduct CO2 from the WGS reaction. At a H2O/CO

resulting in an increase in CO conversion. When the H2/CO

ratio is larger than 1, a very high CO conversion (more than
99%) is achieved with almost no change in conversion but the
dominant reaction for CO consumption can be varied with
increasing H2/CO ratio. For the conventional methanation
reaction, there is a slight improvement in CH4 purity with
increasing H2/CO ratio as can be seen in Figure 6b. For the SEmethanation process, CH4 purity signicantly increases with
the H2/CO ratio until the ratio reaches 1, and then CH4 purity
is reduced from 95% to less than 50% with the increasing H2/
CO ratio. The reason for the CH4 purity change with H2/CO
ratio in the SE-methanation process can be explained by the
mole fraction of H2O in the product stream as can be seen in
Figure 6b. In the H2/CO ratio between 0.5 and 1, H2O is
undetected because most of the H2O produced by the
methanation reaction is removed by the WGS reaction. With
an increase in the H2/CO ratio to more than 1, the WGS
reaction is suppressed and the H2O produced by the
methanation reaction remains in the reactor resulting in a
reduction in CH4 purity.
Figure 6c shows that the CH4 selectivity does not change
much with dierent H2/CO ratios. A high CH4 selectivity of
more than 90% can be obtained for a wide range of H2/CO
ratios in the SE-methanation process. In the conventional
methanation reaction, CH4 selectivity increases almost proportionally with the H2/CO ratio, implying that the methanation
reaction is preferred over the WGS reaction under conditions
of increasing H2 content in the feed.
CH4 productivity increases with increasing H2/CO ratio in
both the SE-methanation process and conventional methanation reaction (Figure 6d). In the conventional methanation
reaction, the higher is the H2 content, the better is the overall
reaction performance. However, the cost of H2 will limit the
increase of additional H2 amount in the feed. In the SEmethanation process, considering overall reaction performance
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Figure 9. Eect of CO2/CO ratio on the performance of SE-methanation process and conventional methanation reaction: (a) CO conversion, (b)
CH4 purity, (c) CH4 selectivity, and (d) CH4 productivity. T = 350 C, P = 10 atm, H2/CO = 1.

Table 2. Comparison of Product Composition and Performance of SE-Methanation Process and Conventional Methanation
Reaction at the Base Condition

SE-methanation
methanation

yCO

y H2

yCH4

yH2O

yCO2

CO conversion
(%)

CH4 purity
(%)

CH4 selectivity
(%)

CH4 productivity
(mol/kg/h)

0.0014
0.0105

0.0007
0.0017

0.9676
0.4111

0.0004
0.0044

0.03
0.5723

99.9
98.8

96.8
41.1

97.0
41.8

0.270
0.248

reaction, with increasing CO2/CO ratio, the CO conversion,

CH4 purity, and selectivity decrease because the additional CO2
in the feed remains in the product stream. If the CO2
methanation reaction (eq 3) occurs, the additional CO2 in
the feed would improve the methanation reaction performance.
However, it appears that CO2 methanation is limited by the
condition of insucient H2. It has been reported previously
that the CO2 methanation reaction can be ignored in the
presence of CO in the feed stream.36,37 CH4 productivity
decreases with increasing CO2/CO ratio in both the SEmethanation process and conventional methanation reaction.
This is because the CO2 in the feed hinders the WGS reaction
so that additional H2 supply to the methanation reaction is
limited. Additionally, in the SE-methanation process, CO2 in
the feed stream accelerates the saturation of sorbent, and the
eect of sorption-enhanced reaction ends earlier.
3.8. Comparison of the SE-Methanation Process and
Conventional Methanation Reaction. According to the
Groningen gas grid specication, the impurity composition
levels of SNG are dened as CO2 < 3%, H2 < 0.5%, and CO <
0.5%.2 Table 2 compares the product compositions of the SEmethanation process and conventional methanation reaction at
the base condition. The product stream of conventional
methanation reaction contains 1.05% CO and a large amount
of CO2 (57.2%), therefore additional purication is required to
remove the CO and CO2. In the product of the SEmethanation process, mole fractions of CO and H2 signicantly
drop to 0.136% and 0.065%, respectively, while the mole
fraction of CO2 remains at 3%. This clearly indicates that the

ratio greater than 0.25, CH4 purity reduces with increasing

content of H2O because the amount of superuous H2O
increases as shown in Figure 8a.
In Figure 8c, CH4 selectivity is kept almost constant in both
the SE-methanation process and conventional methanation
reaction, showing that the addition of H2O to the feed does not
noticeably aect the CH4 selectivity. CH4 productivity increases
with increasing the H2O/CO ratio from 0 to 0.35 and then
remains constant at ratios above 0.35, particularly in the case of
the SE-methanation process (Figure 8d). From the above
results, it is inferred that an adequate supplement of H2O to the
feed stream can enhance the methanation reaction performance
by promoting the WGS reaction to eventually provide H2 under
conditions of insucient H2 content, which can be seen in
syngas obtained from coal gasication.
3.7. Eect of CO2 in the Feed. The syngas obtained from
coal gasication can contain some amount of CO2 but its
composition varies (CO2/CO = 00.44) with the operation
conditions and the type of gasication process used.4,35
Therefore, the study of the eect of CO2 in the feed on the
SE-methanation process is important. Figure 9 shows the
change in the performance of the SE-methanation process and
conventional methanation reaction with variation of CO2/CO
ratio in the feed stream. In the SE-methanation process, there is
no noticeable change in CO conversion, CH4 purity, and CH4
selectivity with increasing CO2/CO ratio. The removal of CO2
by sorption in the SE-methanation process can dampen the
change in CO conversion, CH4 purity, and CH4 selectivity
caused by CO2 in the feed. In the conventional methanation
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low reaction rates. However, very high temperatures can reduce

the CH4 productivity because the methanation and WGS
reactions are exothermic and CO2 sorption is favorable at low
temperatures. The methanation reaction performance is
relatively insensitive to operating pressure though a high
pressure value is preferred from a thermodynamic viewpoint.
However, very high pressures slow down the reaction
considerably leading to decreased CH4 productivity.
With increasing H2/CO ratio, CO conversion and CH4
productivity increase due to a facile methanation reaction.
However, when the H2/CO ratio is larger than 1, the CH4
purity in the SE-methanation process reduces due to the
production of H2O during the reaction. The H2/CO ratio of 1
appears suitable for the SE-methanation process using the
syngas obtained from coal gasication, since under these
conditions there would be no need for expensive H2 addition.
The addition of H2O to the feed is benecial for the reaction
because it can promote the WGS reaction, resulting in the
additional production of H2. However, an excess H2O supply
decreases the CH4 purity due to the unreacted H2O and
additionally produced CO2. The content of CO2 in the feed
does not noticeably change the CO conversion, CH4 purity,
and CH4 selectivity during the SE-methanation process because
CO2 sorption can minimize the eect of CO2 in the feed.
However, the CO2 in the feed saturates the sorbent quicker
resulting in reduced CH4 productivity. The comparison of
product composition and reaction performance between the
SE-methanation process and conventional methanation reaction shows that the product of the SE-methanation process can
be directly used for SNG without additional separation
processes to remove CO, CO2, and H2O. From these results,
the SE-methanation process is expected as a promising process
to eciently convert synthesis gas into SNG. Future work
would be focused on verifying the new process by experiments.

methanation reaction is facilitated by a sorption-enhanced

reaction and the byproduct CO2 is eciently removed during
the reaction. Therefore, the product from the SE-methanation
process can be directly used for SNG without further separation
processes, which can considerably save operating costs to
produce SNG that satises the required specications.
In the SE-methanation process, CO conversion and CH4
productivity are improved compared to the conventional
methanation reaction (Table 2), which is attributed to
overcoming the limit of reaction equilibrium. CH4 purity and
CH4 selectivity increase 2-fold in the SE-methanation process,
which indicates that simultaneous CO2 removal with
methanation reaction crucially enhances the reaction performance for the syngas feed obtained from coal gasication without
providing any additional H2.
Figure 10 shows the rate of reactions and CO2 sorption in
the column for the SE-methanation process at 20 min after the

Figure 10. Rate of reactions (CO methanation, CO2 methanation, and

WGS) and CO2 sorption as a function of normalized reactor column
at 20 min after the reactions start for the SE-methanation process (T =
350 C, P = 10 atm, H2/CO = 1, CO2/CO = 0.2).

AUTHOR INFORMATION

Corresponding Author

*Tel: +82-2-3290-4851. Fax: +82-2-926-6102. E-mail:

[email protected].

reactions start. The operating condition is the same as the base

condition. At rst, CO methanation proceeds to produce CH4
and H2O. When enough H2O is produced, the WGS reaction
begins simultaneously with CO2 sorption to produce H2 that is
one of the reactants for CO methanation. It can be found that
the reaction rate of CO2 methanation is very slow and the CO2
methanation is negligible in this system.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was supported by grants from Human Resources
Development Program (20134010200600) of the Korea
Institute of Energy Technology Evaluation and Planning
(KETEP) funded by Korea Government Ministry of Trade,
Industry & Energy.

4. CONCLUSIONS
The eects of the operating parameters such as catalyst fraction,
temperature, pressure, and feed ratios (H2/CO, H2O/CO, and
CO2/CO) on the performance (CO conversion, CH4 purity,
CH4 selectivity, and CH4 productivity) of a novel SEmethanation process were studied by numerical simulation,
and the results were compared with a conventional
methanation reaction. In the SE-methanation process, methanation, WGS reaction, and CO2 sorption were carried out
simultaneously in a single reactor. The performance of the SEmethanation process is limited by the reaction kinetics when
the catalyst fraction in the solid phase is small, and hence, there
exists an optimal catalyst fraction for maximum CH 4
productivity. The methanation reaction is sensitive to temperature with a high temperature of at least 350 C required to
operate the SE-methanation process without the limitation of

9253

NOMENCLATURE
A = cross-sectional area of the reactor (cm2)
a = stoichiometric ratio of the reaction between CO2 and
chemisorbed CO2
cpg = heat capacity of gas phase (J/mmol/K)
cps = heat capacity of solid phase (J/g/K)
dc = reactor inner diameter (cm)
DEN = denominator in eqs 46
fcat = fraction of catalyst in solids
Ki = equilibrium constant of reaction i (i = 1 and 3, 1/atm2; i
= 2, dimensionless)
Kj = parameters of surface adsorption in equilibrium of
component j (1/atm)
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Kc = equilibrium constant for the surface chemisorption (1/

atm)
K0C = constant in eq 9 (1/atm)
KR = equilibrium constant for the additional reaction in
sorbent surface (1/atma)
K0R = constant in eq 10 (1/atma)
kads,j = linear driving force mass transfer coecient of
component j (1/min)
ki = kinetic constant of reaction i (i = 1 and 3, mmolatm1/2/
g/min; i = 2, mmol/g/min/atm)
Lc = length of the reactor (cm)
Lstage = length of CSTR stage (cm)
m = maximum adsorption capacity of CO2 (mol/kg)
Nin = total molar ux of feed stream (mmol/cm2/min)
Nout = total molar ux of product stream (mmol/cm2/min)
* = the amount of CO2 sorbed on the sorbent at
nads
equilibrium state (mol/kg)
nads,j = the amount of component j sorbed on the sorbent
(mol/kg)
nads,j
* = the amount of component j sorbed on the sorbent at
equilibrium state (mol/kg)
nt = moles of all components (mol)
P = total pressure (atm)
pj = partial pressure of component j (atm)
qc = molar isosteric heat of CO2 sorption (kJ/mol)
R = universal gas constant (atmcm3/mmol/K)
Rads,j = sorption rate of component j (mmol/min)
Ri = reaction rate of reaction i (mmol/g/min)
Ri,j = reaction rate of reaction i for component j (mmol/g/
min)
Tin = inlet temperature (K)
T = temperature (K)
Tw = outside tube wall temperature (K)
t = time (min)
tR = reaction time (min)
U0 = overall heat transfer coecient (J/cm2/K/min)
Vstage = volume of CSTR stage (cm3)
yj = mole fraction of component j
yjin = mole fraction of component j in feed stream
Greek Letters

Hads,j = enthalpy of sorption for component j

Hi = reaction enthalpy of reaction i (kJ/mol)
HR = reaction enthalpy of producing complex (kJ/mol)
= void fraction of methanation catalyst
= factor for heat capacity of heat-exchanger tube and body
= circular constant
b = bulk solid density (g/cm3)

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