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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Combined steam and CO2 reforming of methane using catalytic nickel

membrane for gas to liquid (GTL) process
Shin-Kun Ryi a,b, , Sung-Wook Lee a , Jin-Woo Park a , Duck-Kyu Oh a ,
Jong-Soo Park a , Sung Su Kim b
a
Energy Materials and Convergence Research Department, Korea Institute of Energy Research (KIER), 102 Gajeong-ro, Yuseong-Gu,
Daejeon 305-343, South Korea
b
Department of Chemical and Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, BC, Canada V6T 1Z3

a r t i c l e

i n f o

Article history:
Received 29 July 2013
Received in revised form 14 October 2013
Accepted 1 November 2013
Available online xxx
Keywords:
Methane
Synthesis gas
Catalytic nickel membrane
Steam and CO2 reforming of methane
Gas to liquid (GTL)

a b s t r a c t
In this study, test on the combined steam and dry reforming of methane were carried out over a catalytic nickel membrane within a very short residence time of 120 ms under different process conditions
(CO2 /H2 O feed ratio and temperature). The effect of the molar ratio of CO2 /H2 O in the reactants on the
H2 /CO ratio in the products was investigated at 9231023 K. In the reaction of the combined steam and dry
reforming of methane, CH4 conversion was strongly inuenced by the CO2 /H2 O feed ratio and decreased
with the increase in the CO2 /H2 O feed ratio at 923 K, while the inuence of the CO2 /H2 O feed ratio on CH4
conversion was not signicant at temperatures 973 K. Unlikely CH4 conversion, the conversion of CO2
increased with the increase in the CO2 /H2 O feed ratio over the temperature range of 9231023 K. The
conversion of CH4 and that of CO2 both increased with increasing temperature because the corresponding
reactions are endothermic and remained nearly constant at temperatures 973 K. The H2 /CO molar ratio
could be adjusted by the CO2 /H2 O feed ratio for downstream applications. No carbon deposition on the
catalytic nickel membrane was observed after the combined steam and dry reforming of methane tests
under all process conditions.
2013 Elsevier B.V. All rights reserved.

1. Introduction
With the depletion of liquid petroleum, natural gas has increasingly been considered one of the main resources for chemicals and
energy. Natural gas contains primarily methane and can be converted to useful products by two different routes, i.e., direct and
indirect routes [15]. The direct routes include the oxidative coupling of methane, in which methane is reacted with oxygen to give
the desired product, and non-oxidative coupling of methane, in
which methane is converted directly to the desired product. Meanwhile, the indirect route involves two-step processes whereby
methane is rst converted to synthesis gas (a mixture of H2 and
CO) by steam reforming [5], CO2 reforming [6] or a combination of
these two reactions [68] and partial oxidation [6,7,9]; then, the
components of the synthesis gas react with each other to produce
the desired products.
Synthesis gas is converted to synthetic fuels by the Fischer
Tropsch (FT) process with a H2 /CO ratio of 2 [10]. Although, the
partial oxidation of methane produces a suitable H2 /CO ratio for FT

Corresponding author. Tel.: +82 42 860 3155; fax: +82 42 860 3134.
E-mail address: h2membrane@kier.re.kr (S.-K. Ryi).

synthesis, it is difcult to control the operating temperature and

risk of explosion [11,12]. With the growing concerns about global
warming, the dry reforming of methane for the utilization of CO2
is garnering increasing attention. However, the dry reforming of
methane is a highly endothermic reaction and requires very high
operating temperatures (8001000 C) to reach a high conversion
of methane. These very high operating temperatures result in
catalyst deactivation by coke deposition, mainly due to the deep
cracking of methane, which is thermodynamically favored at
high temperature [13,14]. The steam reforming of methane is the
dominant process to produce synthesis gas but is not suitable for
FischerTropsch synthesis because of the very high H2 /CO ratio
(>3) associated with the process [15,16]. These problems of steam
and dry reforming of methane can be overcome combining these
two reactions. This combination has two main advantages in the
GTL process: (i) carbon formation is reduced due to the oxidation
of the carbon precursor species and (ii) a desirable H2 /CO ratio
can be obtained via the adjustment of the CH4 /H2 O/CO2 ratio in
the feed stream [68]. Environmentally, the combination of the
steam and dry reforming of methane utilizes greenhouse gases,
i.e., methane and carbon dioxide, and produces useful chemical
products. Koo et al. investigated the combination of the steam
and dry reforming of methane for the GTL process [17,18]. They

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Fig. 1. Gas ow passage and membrane effect in catalytic nickel membrane.

determined that a H2 /CO ratio of 2 could be attained by a feed ratio

of CH4 :H2 O:CO2 = 1:0.8:0.4. Even though they could reduce the
rate of coke formation by ceria promotion on a Ni/Al2 O3 catalyst,
coke formation was not avoidable [17].
In previous studies, we developed a novel catalytic nickel membrane and examined the steam reforming of methane and the
methanation reaction for synthesis gas production [15,19]. The gas
ow passage and membrane effect in the catalytic nickel membrane is shown in Fig. 1. The reforming reactions take place on the
porous wall of the catalytic nickel membrane which has sub-micron
sized pores. H2 passed the catalytic nickel membrane faster than
other gases because of viscous and Knudsen ow. The membrane
effect was described in previous study in detail [15]. The objective of this study was to examine the performance of the combined
steam and dry reforming of methane over a catalytic nickel membrane for the GTL process. To obtain a desirable H2 /CO ratio, the
activity and stability of the combined process over a catalytic nickel
membrane were investigated at various reaction temperatures and
CH2 :H2 O:CO2 ratios.

controlled by a K-type thermocouple placed on the outside of the

assembly and the temperature at the bottom of the catalytic nickel
membrane was monitored to determine the reaction temperature.
CH4 and CO2 were supplied by mass ow controller (MFC, Brooks
5850 series) and liquid water was supplied by a micro liquid pump
(NS, MINICHEMI PUMP). The combined steam and dry reforming
test was carried out at a (H2 O + CO2 )/CH4 molar ratio of 3. The
CO2 /H2 O moral ratio was varied from 0 to 1.0 to adjust the H2 /CO
molar ratio to create a system designed for GTL processing. The
effect of the feed molar ratio on the H2 /CO ratio was probed over the
temperature range of 9231023 K. The residence time was 120 ms.
The product gases were analyzed by a gas chromatograph (Agilent
6890N) equipped with HP-MOLSIV and HAYESEP D columns and
thermal conductivity detectors (TCD). Water in the products was
separated by a cold trap before analyzing the product gases. The
experimental conditions and the results are summarized in Table 1.

2. Experimental

2.3. Characterization of catalytic nickel membrane

2.1. Catalytic nickel membrane

Pore size, pore volume and porosity of catalytic nickel

membrane were investigated using mercury porosimeter (Micromeritics, AutoPore IV 9520) and color confocal microscope
(Lazertec, Optics H1200). X-ray photoelectron spectroscopy (XPS)
analysis was conducted to investigate the oxidation state of Ni on
membrane surface. When testing was completed at each temperature, the catalytic nickel membrane was cooled under nitrogen and
characterized by SEM/EDX to verify coke formation.

A catalytic nickel membrane was created by the sintered metal

method. Ten grams of alumina-modied nickel powder was compressed without a binder in a cylindrical metal mold with a
diameter of 51 mm under a pressure of 70 MPa using a homemade pressure device described in a previous study [20]. The
compressed powder was then sintered at 900 C under hydrogen
for 2 h. Nickel powder with an average particle size of 3 m from
Inco Co. was pre-treated with an alumina coating by the incipient
wetness impregnation method, as described in previous studies, to
increase its thermal stability [21]. After heat treatment, the diameter and thickness of the catalytic nickel membrane were 50.8 and
0.8 mm, respectively. The prepared catalytic nickel membrane was
mounted on a plate-type metal module and tightened by eight
metal bolts and nuts. A metal O-ring was used for gas tightness.
The prepared catalytic nickel membrane and assembly are shown
in Fig. 2.
2.2. Combined steam and dry reforming test
A schematic of the combined steam and dry reforming test
is shown in Fig. 3. The gas tightened assembly shown in Fig. 2
was heated in an electric furnace equipped with a programmable
temperature controller. The temperature of the furnace was

Fig. 2. Photograph of catalytic nickel membrane and assembly.

3. Results and discussion

3.1. Catalytic nickel membrane
Heterogeneous catalysis using porous material is generally
controlled by the following factors: external diffusion, internal diffusion, surface reaction, internal diffusion and external diffusion.
Among these factors, internal diffusion resistance is closely related
to the pore structure and size. The effect of internal diffusion resistance on the porous material can be assessed based on the pore
shape and diameter of the material. Since the tortuosity of the pore
is difcult to measure, the effect of internal diffusion was examined
by measuring the average pore diameter or porosity. The surface
pore area of the catalytic nickel membrane which was investigated by color confocal microscope is shown in Fig. 4. Dark spots
and yellow spots are nickel grains and surface pores, respectively.

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Fig. 3. Schematic of experimental set-up for the combined steam and dry reforming of methane.

Table 1
The effect of temperature and feed ratios on activity and productivity.
Production rate of Syn. gas (H2 + CO) [N m3 h1 ]

Temp. [K]

Feed [CH4 :H2 O:CO2 ]

XCH4 [%]

923

1.0:3.0:0
1.0:2.7:0.3
1.0:2.25:0.75
1.0:1.5:1.5

84.2
80.6
75.8
69.3

11.0
7.5
4.6
2.3

4.57 102
4.45 102
4.27 102
4.02 102

973

1.0:3.0:0
1.0:2.7:0.3
1.0:2.25:0.75
1.0:1.5:1.5

95.8
94.1
93.4
92.7

8.1
5.7
3.7
2

5.43 102
5.39 102
5.46 102
5.42 102

1023

1.0:3.0:0
1.0:2.7:0.3
1.0:2.25:0.75
1.0:1.5:1.5

96.0
94.5
93.6
92.9

7.5
5.3
3.4
1.8

5.52 102
5.56 102
5.67 102
5.68 102

Table 2
Pore properties of the catalytic nickel membrane measured by mercury porosimeter.
Average pore diameter (nm)
Total pore area (m2 g1 )
Total pore volume (cm3 g1 )
Porosity (%)

390
0.83
0.08
39.90

The average surface pore area of the catalytic nickel membrane

was 5 m2 . The porosity calculated by the pore area was 40.2%.
This value is similar with the one (39.9%) analyzed by mercury
porosimeter shown in Table 2. As shown in Table 2, the catalytic
nickel membrane has average pore diameter of 390 nm, total pore
area of 0.83 m2 g1 and total pore volume of 0.08 cm3 g1 .
The average pore diameter is considerably high compared with
a powder catalyst. Generally, the catalyst that has relatively small
sized pore is more affected by internal diffusion than the one which
has large sized pores. Therefore, the catalytic membrane which has

H2 /CO ratio

lager pore size has an advantage in mass transfer when considering

the internal diffusion resistance. However, it should be noted that
catalytic membrane may lose the function of membrane if pore
size is getting higher and higher to decrease the internal diffusion
resistance. Therefore, it is very important to control the porosity
and pore size for ensuring the performance of catalytic membrane.
The average pore size and porosity can be controlled by the powder
size [22], fabrication conditions such as molding pressure [20] and
amount of the loaded alumina on the nickel powder [21].
3.2. Activity of combined steam and dry reforming
The combined steam and dry reforming of methane was carried
out by introducing a mixture of CH4 , H2 O and CO2 over the catalytic nickel membrane at different CO2 /H2 O ratios (01.0), while
maintaining a (H2 O + CO2 )/CH4 ratio of 3.0 in the feed stream over
a temperature range of 9231023 K and a residence time of 120 ms.

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Fig. 4. Surface color confocal microscope image of catalytic nickel membrane: dark
spots are nickel grains and yellow spots are pores. (For interpretation of the references to color in gure legend, the reader is referred to the web version of the
article.)

The conversion of methane into synthesis gas is usually carried out

by the steam reforming of methane according to Eq. (1), which is
generally accompanied by the water-gas shift reaction (WGS, Eq.
(2)). Synthesis gas can be produced by the dry reforming of methane
according to Eq. (3).
CH4 + H2 O CO + 3H2
CO + H2 O CO2 + H2
CH4 + CO2 2CO + 2H2

H = 206 kJ mol1
H = 41 kJ mol1
H = 247 kJ mol1

(1)
(2)
(3)

Fig. 5(a) shows the conversion of CH4 as a function of the reaction temperature over a catalytic nickel membrane. As expected,
the conversion of CH4 increased with increasing temperature and
remained nearly constant at temperatures 973 K. The conversion
of CH4 reached 96% at 1023 K when CO2 was not included in the
reactants. The addition of CO2 to the steam led to a decrease in the
CH4 conversion. This result indicates that the catalytic nickel membrane is more active for steam reforming than for dry reforming. At

923 K, the results showed a strong inuence of the CO2 /H2 O feed
ratio on the CH4 conversion, while the inuence of the CO2 /H2 O
feed ratio on the CH4 conversion was not signicant at temperatures 973 K. These phenomena are illustrated in Fig. 5(b), which
shows the conversion of CH4 as a function of the CO2 /H2 O feed
ratio at different temperatures. These effects are due to the lower
endothermic nature of steam reforming compared with that of
dry reforming meaning that the activation energy for both the dry
reforming and steam reforming of methane is sufcient at temperatures 973 K, while the activation energy for the dry reforming is
not high enough to attain a sufciently high conversion of methane
at 923 K. Above 973 K, very high CH4 conversion (92.796%) is
attained over the range of all CO2 /H2 O feed ratios (01.0) because
CH4 becomes the limiting reactant and is consumed in both steam
and dry reforming. Similar results were reported in thermodynamic and experimental studies of the combined dry and steam
reforming of methane over different types of catalysts [8,23,24]. It
was reported that the addition of extra steam to the feed stream
of a 50CH4 + 50CO2 mixture increased the conversion of methane
considerably, especially at temperatures below 1073 K. Choudhary
et al. reported the opposite results when they carried out the combined steam and dry reforming of methane at 1123 K [7,25]. They
concluded that the increase in CH4 conversion with the increase in
the CO2 /H2 O feed ratio is due to the higher activity of their catalyst
for dry reforming compared to that for steam reforming.
The conversion of CO2 as a function of the reaction temperature and CO2 /H2 O feed ratio is shown in Fig. 6(a) and (b). At low
temperature, CO2 does not seem to be a reagent, but a product
because of negative value of CO2 conversion. There are many side
reactions in the combined steam and dry reforming of methane
reaction such as steam reforming (Eq. (1)), dry reforming (Eq. (3)),
methane dehydrogenation (CH4 2H2 C), Boudouard reaction
(2CO C CO2 ), carbon gasication (C 2H2 O CO2 2H2 ), WGS
(Eq. (2)) and reverse-WGS. Among them, CO2 is a reactant in dry
reforming, CO generation (reverse-Boudourd) and reverse-WGS
reactions, and a product in WGS and carbon gasication. If WGS
reaction and carbon gasication are faster than the reactions where
CO2 is reactant, the conversion of CO2 indicates the negative value.
In the inverse case, denitely, the conversion of CO2 should be the
positive value. The magnitude of CO2 participation as a reactant in
each reaction is heavily dependent on the reaction conditions, such
as temperature and partial pressure of reactants and products. As
the temperature increased, the conversion of CO2 increased due to
the dominating dry reforming reaction. Because both CO2 and H2 O
acted as co-oxidants in the combined steam and dry reforming of
methane, CH4 reacted with H2 O instead of CO2 at low temperature

Fig. 5. Conversion of CH4 as a function of the reaction temperature (a) and the CO2 /H2 O feed ratio (b) for catalytic nickel membrane.

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Fig. 6. Conversion of CO2 as a function of the reaction temperature (a) and the CO2 /H2 O feed ratio (b) for catalytic nickel membrane.

due to the higher stability of CO2 . Like the conversion of CH4 , the
conversion of CO2 is nearly constant at temperatures 973 K due to
the limitation of CH4 as reactant. As shown in Fig. 6(b), the conversion of CO2 increased with the increase in the CO2 /H2 O feed ratio.
The negative values of the conversion of CO2 at low CO2 /H2 O feed
ratios indicate that the dry reforming of methane is suppressed by
the water-gas shift reaction. The increase of CO2 content caused
a considerable increase in the conversion of CO2 by dry reforming, instead of the water-gas shift reaction related to the steam
reforming of methane.
The H2 /CO molar ratios for this catalytic nickel membrane as
a function of reaction temperature are displayed in Fig. 7(a). The
H2 /CO molar ratios decrease with increasing temperature, especially at low CO2 /H2 O molar ratios in the feed stream. This result
is explained by the fact that the effect of the water-gas shift reaction increases at low temperature, while the H2 /CO ratio is affected
by the highly endothermic steam and dry reforming of methane
at elevated temperature because the water-gas shift reaction is
thermodynamically unfavorable at elevated temperature [26]. On
the contrary, the effect of temperature on the H2 /CO molar ratio is
not signicantly at high CO2 /H2 O molar ratios in the feed stream
because the effect of the water-gas shift reaction under these conditions is reduced.
The effect of the CO2 /H2 O molar ratio on the combined steam
and dry reforming is shown in Fig. 7(b). The gure shows that with
the increase in the CO2 /H2 O feed ratio, the H2 /CO molar ratio in the
product stream decreased appreciably. As shown in Table 1, the

Table 3
H2 /gases selectivities of the catalytic nickel membrane.

Selectivity

H2 /CO

H2 /CO2

H2 /CH4

2.78

2.75

1.85

H2 /CO molar ratio could be adjusted by the ratio of CH4 :H2 O:CO2
in the feed stream. At 973 K, the H2 /CO molar ratios were 8.1, 5.7,
3.7 and 2.0 for CO2 /H2 O ratios of 0, 0.11, 0.33 and 1.0, respectively.
A similar trend was observed at 1023 K, where the H2 /CO molar
ratios were 7.5, 5.3, 3.4 and 1.8 for CO2 /H2 O ratios of 0, 0.11, 0.33
and 1.0, respectively. The stoichiometric steam reforming reaction
produces a H2 /CO molar ratio of 3. However, a very high H2 /CO ratio
(>7) in the steam reforming alone, i.e., for a CO2 /H2 O feed ratio of 0,
is observed. Gas permeation tests were carried using pure H2 , CO,
CO2 and CH4 at 373 K and pressure difference of 100 kPa. Table 3
shows that the selectivities of H2 /CO, H2 /CO2 and H2 /CH4 were 2.78,
2.75 and 1.85 respectively. It means that H2 passed the catalytic
nickel membrane faster than other gases. The very high value of
H2 /CO ratio in the steam reforming alone is due to the H2 selective
behavior of the catalytic nickel membrane [15]. It is not surprising
that the CO2 /H2 O feed ratio strongly affects the H2 /CO molar ratios
in the product stream because the stoichiometric dry reforming
reaction produces a H2 /CO molar ratio of 1, while the steam reforming reaction produces a H2 /CO molar ratio of 3. It is expected that
intermediate H2 /CO ratios would be produced upon combining the

Fig. 7. H2 /CO molar ratios for the catalytic nickel membrane as a function of reaction temperature (a) and the CO2 /H2 O feed ratio (b).

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dry reforming and steam reforming of methane. These intermediate values indicate that more CO and less H2 are formed by the dry
reforming of methane upon increasing CO2 /H2 O ratio as shown in
Fig. 8, which depicts the composition of the products as a function
of the CO2 /H2 O ratio at 1023 K. It can be concluded that it is possible to modify the H2 /CO ratio by varying the CO2 /H2 O ratio in
the feed stream and temperature, depending on the downstream
application [10,27].
Fig. 9(a) and (b) shows the total ow rate (H2 , CO, CO2 , and
CH4 ) of the production stream and the syngas gas ow rate (H2
and CO) in the products after steam removal by cold trap, respectively. The results show the effect of the CO2 /H2 O ratio on the dried
total ow rate of the production stream. With the increase in the
CO2 /H2 O ratio, the dried total ow rate of the production stream is
increased at all temperatures of 923, 973 and 1023 K. For the GTL
process, the syngas (H2 and CO) production rate is more important
than the total product ow rate because H2 and CO are converted
to synthetic fuels by the FischerTropsch (FT) synthesis. Except at

Fig. 8. Composition of products as a function of CO2 /H2 O ratio at 1023 K.

Fig. 9. Total ow rate (H2 , CO, CO2 , and CH4 ) of production stream (a) and the syngas gas ow rate (H2 and CO) (b) in the products after steam removal.

Fig. 10. Surface (ac) and cross-sectional (df) SEM images of catalytic nickel membrane after the combined steam and dry reforming of methane as a function of the CO2 /H2 O
ratio: (a) and (d) are at 923 K, (b) and (e) 973 K (c) and (f) 1023 K.

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is main species. This result implies the surface of catalytic membrane can be changed reversibly, and thus the membrane can have
a function participated in reforming reaction. XPS is surface analysis and reforming reaction in this paper is also surface reaction.
It is hard to insist that bulk valence of the membrane is reversible
when considering the analysis limitation (only surface), mechanical strength of membrane and unique characteristics of catalysis.
However, from the XPS result, it is obvious that a change in valence
state on surface can function in the reforming reaction as a catalyst
and such sites are reversible.
4. Conclusions
The following results were obtained from the combined steam
and dry reforming tests using a catalytic nickel membrane made of
nickel powder with different CO2 /H2 O ratios as the oxidant:

Fig. 11. XPS spectrum of catalytic nickel membrane.

923 K, as the CO2 /H2 O ratio increased, an increasing trend for the
syngas production rate is observed over the CO2 /H2 O ratio range
of 00.33. The syngas production rate is almost at and reaches
5.68 102 N m3 h1 at 1023 K at a CO2 /H2 O ratio of 1.0. A decrease
in the syngas production rate was observed at 923 K. While both
the dry reforming and steam reforming reactions are endothermic
reaction and are favored at high temperature, the WGS is favored
at low temperature because it is an exothermic reaction.
3.3. SEM/EDX analysis
After the combined steam and dry reforming of methane tests
at each temperature, the catalytic nickel membrane were removed
from the membrane assembly and characterized by SEM/EDX.
Fig. 10 shows surface (ac) and cross-sectional (df) SEM images
after the combined steam and dry reforming of methane with a
CO2 /H2 O ratio of 1.0 at 923 (a and d), 973 (b and e) and 1023 K (c
and f), respectively. As shown in Figs. 10, the nickel powder was
spherical but possessed an undulating shape with an average powder size of 3 m. The SEM and EDX analysis of the tested catalytic
nickel membrane showed no sign of any carbon deposition after the
combined steam and dry reforming of methane tests. From Eqs. (1)
and (3), 2 mol of CH4 needs 2 mol of oxidants (CO2 H2 O) for combined steam and dry reforming of methane reaction. In general, the
ratio of oxidants/CH4 in the reforming reactions is kept 1 to avoid
carbon deposition. In this study, we used a (H2 O CO2 )/CH4 molar
ratio of 3 to prevent carbon deposition. The reforming tests were
continued 50 h at each temperature. There was no indication of
deactivation during the test period. The SEM analysis shows that
there is no deformation of the catalytic nickel membrane.
3.4. XPS analysis
XPS analysis was conducted to investigate the oxidation state
of Ni on membrane surface. 856 and 853.3 eV is assigned to Ni2+
and Ni0 , respectively [28]. As shown in Fig. 11, the XPS spectrum
of catalytic membrane after combined steam and dry reforming of
methane test reveals that Ni2+ species are dominant on the surface, while the spectrum after the pretreatment shows metallic Ni

The conversion of CH4 was increased with increasing temperature and reached 96% at 1023 K when the CO2 was not included
in the reactants.
The increase in the CO2 /H2 O ratio leads to a decrease in the CH4
conversion because the catalytic nickel membrane is more active
for steam reforming than for dry reforming.
A strong inuence of the CO2 /H2 O feed ratio on the CH4 conversion was observed at 923 K, while the inuence of the CO2 /H2 O
feed ratio on the CH4 conversion was not signicant at temperatures 973 K.
The conversion of CO2 was increased with increasing temperature due to the dominating dry reforming reaction at high
temperature and was nearly constant at temperatures 973 K
due to the limitation of CH4 as the reactant.
It is possible to modify the H2 /CO ratio by varying the CO2 /H2 O
ratio in the feed stream and the temperature. The H2 /CO molar
ratios were 8.1, 5.7, 3.7 and 2.0 at 973 K and 7.5, 5.3, 3.4 and 1.8
at 1023 K for CO2 /H2 O ratios of 0, 0.11, 0.33, 1.0 and respectively.
A syngas production rate of 5.68 102 N m3 h1 at a H2 /CO
molar ratio of 1.8 was obtained at 1023 K at a CO2 /H2 O ratio of
1.0 and a residence time of 120 ms.
No carbon formation on the catalytic nickel membranes was
observed by the SEM and EDX analysis after the combined steam
and dry reforming of methane tests.
Acknowledgement
This work was conducted under the framework of Research and
Development Program of the Korea Institute of Energy Research
(KIER) (B3-2461-6).
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Please cite this article in press as: S.-K. Ryi, et al., Combined steam and CO2 reforming of methane using catalytic nickel membrane for gas to
liquid (GTL) process, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.11.001