Fuel Processing Technology 119 (2014) 151–157

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Fuel Processing Technology

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Syngas production via combined steam and carbon dioxide reforming

of methane over Ni–Ce/MgAl2O4 catalysts with enhanced coke resistance
Kee Young Koo a, Sung-hun Lee a,b, Un Ho Jung a, Hyun-Seog Roh c,⁎, Wang Lai Yoon a,⁎⁎
a
Hydrogen and Fuel Cell Department, Korea Institute of Energy Research, 71-2, Jang-dong, Yuseong, Daejeon 305-343, Republic of Korea
b
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seoul 120-749, Republic of Korea
c
Department of Environmental Engineering, Yonsei University, 1 Yonseidae-gil, Wonju, Gwangwon 220-710, Republic of Korea

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

Article history: A Ni–Ce/MgAl2O4 catalyst was prepared by the co-impregnation method by adjusting the Ce/Ni ratio in a range of
Received 14 June 2013 0.0–1.0 for the combined steam and carbon dioxide reforming of methane (CSCRM). The characterization as to
Received in revised form 30 September 2013 surface area, metal dispersion, NiO crystallite size as well as reduction temperature and basicity of prepared
Accepted 3 November 2013
catalysts was analyzed by BET, H2-chemisroption, XRD, TPR and CO2-TPD. The used catalysts were collected to
Available online 28 November 2013
investigate the coke formation and surface characteristics through SEM, TGA, XPS and Raman analysis. The Ce
Keywords:
addition to Ni/MgAl2O4 catalyst has significant effects on the NiO crystallite size, metal dispersion and reduction
Synthesis gas degree. The Ni–Ce/MgAl2O4 catalyst with the Ce/Ni ratio of 0.25 showed the smallest NiO crystallite size of
Combined steam and carbon dioxide reforming 8.3 nm and the highest metal dispersion of 4.91%. Meanwhile, in the Ni/MgAl2O4 (Ce/Ni = 0) catalyst, the
Coke resistance NiO crystallite size was found to be as large as 11.0 nm and showed a low metal dispersion of 3.49%. The
Ni–Ce/MgAl2O4 Ni–Ce/MgAl2O4 (Ce/Ni = 0.25) catalyst shows the highest activity and coke resistance in CSCRM due to
the improvement of metal dispersion, excellent reducibility as well as effective surface oxygen transfer
as evidenced by XPS results.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
The high oil prices resulting from the imbalance in crude oil demand
and supply, environmental contamination, and climate change have
contributed to a rise in the interest in alternative energy development
and energy source diversification. In particular, natural gas has come
to the fore as primary alternative energy sources, thank to the develop-
ment of unconventional gas sources like shale gas with abundant
reserves [1]. The natural gas is converted to synthetic gas (syngas) com-
posed mainly of H2 and CO through a reforming process. This syngas is
being used as a main raw material in the production of clean synthetic
fuels, such as methanol, syncrude, and DME (Dimethyl ether). In
addition, the required H2/CO ratio depends on the applications [2,3].
In this study, the combined steam and carbon dioxide reforming of
methane (CSCRM) was introduced to produce synthetic gas with
various H2/CO ratios. In general, conventional reforming processes
such as steam reforming of methane (SRM) and CO2 reforming of
methane (CRM) require an additional process to adjust the H2/CO
ratio. Besides, partial oxidation of methane (POM) and autothermal
reforming (ATR) have some problems such as the requirement of
expensive air separation unit and formation of the hot spot. On the
other hand, the most important advantage of CSCRM is that the
⁎ Corresponding author. Fax: +82 33 760 2571.
⁎⁎ Corresponding author. Fax: +82 42 860 3739.
E-mail addresses: hsroh@yonsei.ac.kr (H.-S. Roh), wlyoon@kier.re.kr (W.L. Yoon).
produced H2/CO ratio is easily achieved by directly adjusting the feed
ratio of H2O and CO2 [4–6]. In addition, this process has the merits
of producing the required syngas by using CH4 and CO2, which are
greenhouse gases. It is also capable of utilizing the gas field in Southeast
Asia where the CO2 ratio in natural gases is high [7–9].
Generally, Ni-based catalysts which are cheap but excellent in
performance as compared to precious metal catalysts are being used
in commercial processes although they engender problems of coke
formation and sintering which can result in the abrupt deactivation
of Ni catalysts. Since low S/C-ratio is applied in CSCRM to adjust the
H2/CO ratio, Ni catalysts are easily deactivated by carbon deposition
[10]. To resolve this deactivation of catalysts by carbon formation,
researchers have continuously investigated two potential causes. They
controlled the particle size in active metals (at nanosizes), or improved
the reaction characteristics of catalysts by adding promoters such as Ca,
Mg, Ce and La [11,12]. CeO2, in particular, is widely used as a promoter
since CeO2, with its redox property (Ce4 +/Ce3 +), easily gasifies the
deposited coke on the catalysts surface by storing and delivering active
oxygen and increases Ni dispersion. Daza et al. [13] have reported that
the catalytic activity of Ni–Ce/mineral clay catalyst was enhanced and
coke formation was restricted in the dry reforming of methane due
to the improvement of Ni dispersion and CO 2 adsorption. Potdar
et al. [14] have reported that the Ni–Ce–ZrO2 nanocatalyst prepared
via co-precipitation method showed a stable reaction activity and
coke resistance due to its high surface area and high oxygen mobility
in the carbon dioxide reforming process. Also, Roh et al. [15] have

0378-3820/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.11.005
152 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157

investigated the effect of Ce/Zr-ratio on the catalyst activity of Ni– in a quartz reactor was pre-treated with He gas at 700 °C for 1 h and
CexZr1 − xO2 and on its carbon deposition in the CSCRM. The cubic then reduced with 5%H2/He gas at 700 °C for 1 h. After reduction, the
Ni–Ce0.8Zr0.2O2 catalyst showed the highest catalytic performance sample was cooled down. CO2 was adsorbed at 50 °C for 1 h and weakly
which results from highly dispersed NiO and high oxygen storage adsorbed CO2 was removed by purging with He. The sample was heated
capacity. Recently, we have reported on the important effect from 50 to 700 °C at a heating rate of 10 °C/min in He flow and the
that both Ce contents and the Ni–Ce loading method have an desorbed amount of CO2 was detected with a thermal conductivity
influence on the efficient active oxygen transfer between Ni and detector (TCD). Scanning Electron Microscopy (SEM, Philips XL30SREG)
Ce as preliminary researches to improve coke resistance of the was carried out to observe the morphology of used catalysts and
12wt.%Ni/α-Al 2 O 3 catalyst in the CSCRM [16,17]. However, the coke formation. The coke amount was quantitatively determined
characteristics of supports are also important factors affecting by a thermogravimetry analyzer (TGA, Netzsch TG209F3). The sam-
carbon deposition [18]. In particular, α-Al 2 O 3 support causes the ple of 5–7 mg was heated from 30 to 800 °C with a heating rate of
carbon deposition due to rather acidic property [19]. Besides, active 5 °C/min in the air. The electron state of used catalysts was measured
Ni metal and Al2 O 3 supports interact with each other to form an with an X-ray photoelectron spectroscope (XPS, MultiLab 2000,
inactive NiAl2O4, thereby deactivating the catalyst [11]. According Thermo) using Al Kα source with 200 W X-ray power and the bind-
to the previous works, Baek et al. [20] have reported that the Ni– ing energy (BE) was calibrated by using the C 1s peak at 284.6 eV as a
Ce/MgAl 2 O 4 (MgO/Al 2 O 3 = 3/7) showed better catalytic stability reference. The peak was deconvoluted using the program of Thermo
and higher coke resistance than Ni–Ce/θ-Al2 O3 in CSCRM. Eltejaei Avantage v4.45 (Thermo Fisher Scientific Co.). The Gaussian–Lorentzian
et al. [21] have also reported that Ni/Ce 0.75 Zr0.25 O 2 –MgAl 2 O 4 peak shape with 30% Lorentzian contribution was applied to fit the exper-
exhibited higher coke resistance than Ni/γ-Al 2 O 4 in methane dry imental data after subtraction of the smart-type background. The Raman
reforming. These previous reports demonstrated that the basic spectra were obtained with a LabRam HR spectrometer (Horiba Jobin
property of MgAl2O4 and Ce or CeZrO2 promotion has an important Yvon) using a 514 nm excitation source. A 100 μm pinhole was used
effect on the catalytic performance and coke removal on the catalyst with the spectral resolution grating, yielding about 1.0 cm−1 resolution.
surface.
This study intends to investigate the effect of Ce/Ni ratio on the
2.3. Catalytic test
catalyst activity and coke resistance in CSCRM by introducing
hydrotalcite-like structured MgAl 2 O 4 as a support with basic
5 mg of catalyst and 0.1 g of diluent MgAl2O4 were sorted into
property and large surface area, along with optimizing the Ce/Ni
60–100 mesh and mixed evenly. The mixture was filled into a 1/4″ quartz
ratio.
tube and a thermocouple was positioned in the middle of a catalyst bed
to measure the temperature of the catalyst layer. Before reaction, the
2. Experimental
catalyst was reduced at 700 °C under a 10%H2/N2 atmosphere for 1 h.
The gas mixture of CH4:H2O:CO2:N2 = 1:0.8:0.4:1 was fed into the reac-
2.1. Catalyst preparation
tor with a space velocity of 530,000 ml/h-gcat. A catalyst performance test
was carried out at different temperatures by decreasing the temperature
Hydrotalcite-like MgO–Al2O3-mixed oxide (MgO = 30%, SASOL)
in increments of 50 °C from 700 °C to 550 °C over 20 h. The effluent was
was employed as a precursor of support and pre-calcined at 1100 °C
connected to microGC (Agilent) to analyze its composition. To examine
for 6 h. Nickel(II) nitrate hexahydrate (97%, Jnsei) and Cerium(III)
coke formation behavior according to promoted Ce contents, only
nitrate hexahydrate (99%, Aldrich) were used as precursors of Ni and
15 mg of catalyst without diluent was filled into a reactor and
Ce, respectively. The Ce-promoted Ni/MgAl2O4 catalysts were prepared
tested under the same reaction condition as CSCRM at a low reaction
through a co-impregnation method and then calcined at 800 °C for 6 h.
temperature of 600 °C, which is favorable for the coke formation for 16 h.
Ni content was fixed at 10 wt.% and Ce/Ni ratio was regulated at a range
of 0.0–1.0.
3. Results and discussion
2.2. Characterization
3.1. Catalyst characterization
X-ray diffraction analysis (XRD, Rigaku D/Max-III C, CuKα radiation)
was performed to identify the composition and crystal structure of the Fig. 1 shows the XRD results of the Ni–Ce/MgAl2O4 catalysts
prepared catalyst. NiO crystallite size was calculated by using the prepared with different Ce/Ni ratios. From the Ni/MgAl2O4 catalyst
Scherrer equation. The reduction temperature and reducibility were
confirmed by temperature programmed reduction analysis (TPR, BEL
CAT B, BEL Japan, Inc.). The sample of 0.1 g in a quartz reactor was
pre-treated with He gas at 250 °C for 1 h and then cooled down to
50 °C before being re-heated in the electrical furnace at a heating rate
of 10 °C/min from 50 to 1000 °C under 10% H2/Ar gas. The surface
area of catalysts was measured by BET (Belsorp max, BEL Japan, Inc.)
after the nitrogen adsorption at − 196 °C for the sample of 0.2 g that
was pretreated at 300 °C in vacuum. H2-chemisorption was performed
by using a pulse technique to identify the metallic dispersion and
metal surface area in a BEL-METAL-3(BEL Japan, Inc.). The sample of
50 mg was reduced in H2 flow at 700 °C for 1 h. The sample was purged
at 700 °C for 1 h in He flow and cooled to 50 °C. A H2 pulse (20%H2/Ar)
was injected into the catalyst. The adsorbed H2 amount was used
to estimate Ni dispersion and surface area by assuming the adsorption
stoichiometry of one hydrogen atom per nickel atom on the
surface (H/Nisurface = 1). CO2-temperature programmed desorption
(CO2 -TPD, BEL-METAL-3) was performed to identify the strength Fig. 1. XRD patterns of Ni–Ce/MgAl2O4 catalysts prepared with Ce/Ni ratios of (a) 0.0,
and distribution of basic sites in the catalyst. The sample of 50 mg (b) 0.25, (c) 0.50, (d) 1.00.
 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157 153

without Ce addition, only peaks of MgAl2O4 catalyst with spinel struc-

ture and NiO were observed. In the case of Ce-promoted Ni/MgAl2O4
catalysts, characteristic peaks of CeO2 corresponding to a cubic phase
were co-present, and with increases in added Ce, NiO peak intensity
was decreased [16]. The crystallite size of NiO was calculated from
the XRD diffraction peak that appeared at 2θ with a value of 62.9°.
The calculation result is arranged in Table 1. The NiO crystallite size of
Ni–Ce/MgAl2O4 catalysts with the Ce addition was smaller than that of
the Ni/MgAl2O4 catalyst. The smallest NiO crystallite size of 8.3 nm
was found from the catalyst prepared with Ce/Ni = 0.25. The metal
dispersion of Ni/MgAl2O4 catalyst without Ce addition was 3.49%, but
the Ni metal dispersion of Ni–Ce/MgAl2O4 catalysts was 3.95–4.91%. It
was confirmed that the Ce addition was beneficial for the improvement
of metal dispersion in the Ni/MgAl2O4 catalyst. The Ni–Ce/MgAl2O4
catalyst had the highest dispersion of 4.9% when the Ce/Ni ratio was
0.25. This result is in agreement with results in preceding research
that Ce promotion improved Ni dispersion over a support surface [9]. Fig. 2. TPR patterns of Ni–Ce/MgAl2O4 catalysts prepared with Ce/Ni ratios of (a) 0.0,
The 10Ni–2.5Ce/MgAl2O4 catalyst (Ce/Ni = 0.25) having the smallest (b) 0.25, (c) 0.50, (d) 1.00.

NiO crystallite size and the highest metal dispersion also shows the
largest BET surface area of 26.4 m2/g. However, if non-porous Ce is
added in excess of a Ce/Ni ratio of 0.50, specific surface area is decreased
and the interaction between supports and Ni metal becomes weak. This
results in decreased dispersion due to Ni agglomeration. Here, it should
be noted that there exists an optimum Ce/Ni ratio that increases Ni
metal dispersion and provides a favorable preparation condition for
catalysts having a large BET surface area.
The TPR analysis performed to examine reduction temperature
and reduction characteristics is presented in Fig. 2. In the Ni/MgAl2O4
catalyst without Ce addition, a reduction peak of free NiO appeared at
350 °C and a reduction peak caused by the interaction between Ni and
support appeared at 780 °C [10]. The reduction of Ni–Ce/MgAl2O4
catalysts started from a temperature of 200 °C, which was lower than
the initial reduction temperature for the Ni/MgAl2O4 catalyst. It can be
expected that catalytic activity improves at low temperatures due to
enhanced reducibility by adding Ce. With increases in added Ce, the
intensity of the reduction peak of surface-capping oxygen that used to
appear at lower than 350 °C increased and the reduction peak intensity
of Ni2+ species interacting with CeO2 also increased at near 550 °C. This
tendency for increased reducibility at lower temperature by adding Ce
was in conformity with the reduction degree results in Table 1. The
reduction peak appearing at 780 °C is attributed to the reduction of
complex NiO species that strongly interact with MgAl2O4 support
[9,22–24]. With Ce/Ni ratio increased, the reduction peak moves
towards a higher temperature to some extent, which suggests that
strong metal to support interaction (SMSI) between highly dispersed
Ni and support is enhanced due to the Ce addition [16]. This tendency
matches the results of the decreases in NiO crystallite size by adding
Ce and the consequent increases in metal dispersion.
To investigate the effect of Ce addition on the strength and distribu-
tion of basic site in prepared catalysts, CO2-TPD analysis was performed
after reduction at 700 °C for 1 h under 5%H2 in He gas. Fig. 3 shows the
Ni/MgAl2O4 catalyst shows the weak basic site at between 100 °C and
159 °C, the basic site of middle strength at 270 °C as well as the strong
site at 420 °C. As the Ce/Ni ratio increases, TPD peaks shift to the high
temperature and the peak intensity increases. This result indicates
that the Ce addition enhances the strength of basic site of catalysts.
In addition, it was confirmed that Ce enhanced the thermal stability
of the basic sites of the catalyst from the TPD-CO2 results of the Ce-
promoted Ni/Mg–Al mixed oxides according to the previous report
by Daza et al. [2]. The total amount of desorbed CO2 was estimated
from the integration of CO2-TPD peak area. The total amount of desorbed
CO2 increased with the increase of Ce/Ni ratio in the following order:
Ce/Ni = 1.0 (70.4 mmol/g) N Ce/Ni = 0.5 (50.3 mmol/g) N Ce/Ni =
0.25 (45.4 mmol/g) N Ce/Ni = 0 (42.9 mmol/g). The desorbed amount
of CO2 in Ce-promoted Ni/MgAl2O4 catalysts was larger than that of the
Ni/MgAl2O4 catalyst. It should be noted that Ce addition promoted the
CO2 adsorption on the catalyst surface due to the increase of total basicity
of catalysts. The adsorbed CO2 provides more oxygen species on the
catalysts surface which results in the removal of the deposited coke by
gasification [11,21]. In other words, the dissociation of adsorbed CO2 gen-
erates the active oxygen species and the oxygen transfer between Ce2O3
and CeO2 induces the coke gasification which converts deposited coke
into CO and CO2. From these results, it is expected that the Ce promoted
catalysts show good catalytic activity and high coke resistance in
CSCRM due to the increase of adsorbed CO2, oxygen transfer and Ni
metal dispersion.
CO2 desorption (a.u.)

CO2-TPD patterns of Ce-promoted Ni/MgAl2O4 catalysts. It is identified

that three types of basic site are present. The CO 2 -TPD profile of

Table 1
Characteristics of Ni–Ce/MgAl2O4 catalysts. (d)
Ce/Ni NiO crystallite BET surface area Metal dispersion Reduction (c)
ratio size (nm) (m2/g)a (%)b degree (%)c
(b)
0.0 11.0 25.6 3.49 28.4
0.25 8.3 26.4 4.91 51.1 (a)
0.50 9.4 25.7 4.12 59.5 100 200 300 400 500 600 700
1.00 10.5 24.7 3.95 85.2
Temperature (oC)
a
Estimated from N2 adsorption at −196 °C.
b
Estimated from H2-chemisorption at 50 °C. Fig. 3. CO2-TPD patterns of Ni–Ce/MgAl2O4 catalysts prepared with Ce/Ni ratios of (a) 0.0,
c
Calculated from reduction of the catalyst at 700 °C for 1 h. (b) 0.25, (c) 0.50, (d) 1.00.
154 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157

Table 2
CSCRM results over Ni–Ce/MgAl2O4 catalysts at 700 °C.

Ce/Ni ratio CH4 conversion (%) CO2 conversion (%) H2/CO ratio

0.0 77.5 62.5 2.2

0.25 81.3 65.9 2.1
0.50 80.1 67.1 2.1
1.00 74.9 52.3 2.2

3.2. Catalytic test in CSCRM

Table 2 shows the CSCRM results over Ni–Ce/MgAl2O4 catalysts

prepared with a different Ce/Ni ratio at a reaction temperature of
700 °C for 5 h. The catalysts in which Ce was added showed high CH4
conversion as well as high CO2 conversion except in the catalyst
prepared with Ce/Ni = 1.00. The low catalytic activity in Ce/Ni = 1.00
is due to decrease in Ni metal dispersion by excessive Ce addition.
It has been found from the examination of the H2/CO ratio in the
syngas that a ratio in proximity of 2 was generated, which is required
for Fischer–Tropsch synthesis. The CH4 and CO2 conversions as well as
H2/CO ratio of prepared catalysts according to reaction temperature
changes at 650 °C and at 600 °C in CSCRM were presented in Fig. 4.
As reaction temperature decreased, the effect of the Ce addition was
apparent as Ni/MgAl2O4 catalyst without a Ce addition showed greatly
reduced CH4 and CO2 conversions as compared with that of catalysts
with a Ce addition. One explanation for this could be that catalytic
activity and stability were improved due to the enhancement of
reducibility at low temperature and high Ni dispersion by adding Ce
[9]. CO2 conversion also showed similar trends with CH4 conversion.

3.3. Coke study

To investigate the effect of Ce addition on the coke formation,

CSCRM was carried out at a low temperature of 600 °C for 16 h, which
is a favorable condition for coke formation. SEM analysis was performed
with the used catalysts (Fig. 5). It was confirmed that a large amount
of whisker shaped coke was formed on the surface of all the prepared
catalysts except the 10Ni–2.5Ce/MgAl2O4 catalyst because of the
Boudouard reaction (2CO → CO2 + C) where CO dissociation occurs
mainly at low temperature [18,25]. In accordance with the Guo et al.'s
report, Boudouard reaction (CO disproportionation) is exothermic;
thus the equilibrium constant increases with decreasing temperature
[26]. On the contrary, CH4 decomposition reaction is favorable at high
temperature of 750 °C owing to the endothermic reaction. There-
fore, in our study, it can be explained that the coke formation is
attributed to the Boudouard reaction. In addition, it is evident that
10Ni–2.5Ce/MgAl2O4 catalyst has resistance to the coke deposition
due to the high Ni dispersion. The results of reforming test and
SEM analysis demonstrated that the catalytic performance and
coke deposition are related to the Ce content.
To measure the amount of deposited coke precisely, the TGA analysis
was carried out with the used catalyst after reforming reaction at 600 °C Fig. 4. (a) CH4 conversion, (b) CO2 conversion and (c) H2/CO ratio of prepared Ni–Ce/
MgAl2O4 catalysts at 650 °C and at 600 °C in CSCRM (reaction conditions: CH4: H2O:
for 16 h. The TGA results obtained by conducting quantitative analysis
CO2: N2 = 1: 0.8: 0.4: 1, GHSV = 530,000 ml/h gcat).
for the deposited coke on the catalyst surface were arranged in Fig. 6
and Table 3. It is identified that the TGA profiles showed the different
behaviors of weight loss. Tsyganok et al. [27] explained the different work concerning the TG data of used 5%Ni/MgAl2O4 spinel catalyst in
behaviors of TGA profiles by temperature variation as follows. The initial CRM [28]. Carbon deposition by Ce contents, as in Table 3, shows that
weight reduction that appears in the TGA profile before temperatures the least amount of coke (8.0%) was formed when Ce/Ni = 0.25,
reached 300 °C, as is shown in Fig. 6, is caused by the thermal desorp- whereas the largest amount of coke (25.5%) was formed from the
tion of H2O and CO2 and the removal of carbonaceous species which 10Ni/MgAl2O4 catalyst without Ce addition. It is evident that the Ce
are easily oxidizable amorphous coke. The weight reduction at temper- addition has a significant effect on the prevention of coke formation.
ature higher than 500 °C is due to the gasification of whisker coke As mentioned above, amorphous carbonaceous species are oxidized at
where CO and CO2 (COx) are generated through the oxidation of coke. low temperature of 250–300 °C, while the oxidation of graphitic carbon
In used catalysts, it is noted that the weight gain due to the oxidation occurs at high temperature over 500 °C. At the temperature where
of the metallic Ni particles on the surface is not observed between 400 weight reduction occurs, the amount of amorphous carbon and graphit-
and 450 °C. These results accord closely with the Guo et al.'s previous ic carbon was estimated by dividing by the sample weight for TGA
 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157 155

Fig. 5. SEM images of used Ni–Ce/MgAl2O4 catalysts prepared with Ce/Ni ratios of (a) 0.0, (b) 0.25, (c) 0.50, (d) 1.00.

analysis, respectively. According to the previous reports, the graphitic-
like carbon is less reactive with oxygen or steam than the amorphous
carbon [28,29]. It is identified that a great deal of graphitic carbon
was formed in the 10Ni/MgAl2O4 catalyst without Ce addition. This
illustrates that Ce induced the absorption and dissociation of reaction
gases H2O and CO2 by its Ce4+/Ce3+ redox property, enabling itself to
supply active oxygen to the surface of the catalyst in order to remove
deposited coke more easily [24].
Fig. 7 shows the Raman spectra of used Ni–Ce/MgAl2O4 catalysts
with various Ce/Ni ratios in the range 1200–1800 cm−1. There are two
peaks in the vicinity of 1350 cm−1 (D band) and 1600 cm−1 (G band),
100
10Ni-2.5Ce/MgAl2O4
Sample weight (%)
respectively. The D band indicates the spectrum of polycrystalline
and imperfect graphite, while the G band provides the information
concerning the electronic properties of the filamentous carbons [26]. It
was confirmed that the Ce-promoted Ni/MgAl2O4 catalysts exhibited
the decrease of peak intensity due to the less coke formation on the
catalyst surface as compared with Ni/MgAl2O4 catalyst without Ce
addition. When the Ce/Ni ratio was 0.25, Ni–Ce/MgAl2O4 catalyst
showed the lowest intensity of peak which was attributed to the
prevention of coke formation by adding Ce. These results correspond
with the TGA results. On the other hand, the formation of amorphous
carbon and graphite carbon was indubitably observed in the Raman
spectra of Ni/MgAl2O4 catalyst. In particular, Ni/MgAl2O4 catalyst
showed that the peak intensity of amorphous coke in D band was
noticeably higher as compared with Ce-promoted catalysts. It proves
that the deposited amorphous coke is not easily removed on the surface
of Ni/MgAl2O4 catalyst, whereas the Ce-promoted Ni/MgAl2O4 catalysts
are favorable to remove the amorphous coke on the surface due to

90 the redox property of CeO2. Besides, a large amount of graphitic carbon

10Ni-5.0Ce/MgAl2O4 was formed on the surface of used Ni/MgAl2O4 catalyst. As a consequence
of coke deposition, the active site was blocked and the Ni/MgAl2O4

80 Table 3
10Ni-10Ce/MgAl2O4 Quantitative data of carbon deposited on used Ni–Ce/MgAl2O4 catalysts.

Ce/Ni ratio Amorphous carbon Graphitic carbon Total amount of

10Ni/MgAl2O4 (gC/gcat) (gC/gcat) coke (%)a

0.0 0.0068 0.2484 25.5

70
100 200 300 400 500 600 700 800 0.25 0.0068 0.0733 8.0
0.50 0.0130 0.0799 9.3
Temperature (oC)
1.00 0.0097 0.1987 20.8
a
Fig. 6. TG profiles of used Ni–Ce/MgAl2O4 catalysts under air. Coke deposition was quantified by thermogravimetry.
156 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157

noted is that in the case of the used Ni/MgAl2O4 catalyst, the BE of NiO
(Ni2p3/2) has been shifted towards the lower side by 1.12. This is
G band because Ni having low metal dispersion interacted weakly with support,
which caused the agglomeration of Ni particles during reaction. On the
Intensity (a.u.)

D band (a) other hand, it was observed that the catalyst prepared with a Ce/Ni ratio
of 0.25 did not have its BE of Ni2p peak changed due to the strong inter-
action between highly dispersed Ni and its support. This result is consis-
tent with the metal dispersion and TPR analysis results. Ce3d5/2 and
Ce3d3/2 peaks are marked as a solid line in a spectrum of CeO2 and
(b) Ce2O3 as in Fig. 8. In the CeO2 spectrum, v, v″, and v‴ as well as u, u″,
(d) and u‴ represent the peak intensity of Ce3d5/2 and Ce3d3/2, while v′
and u′ represent the peak intensities of Ce3d5/2 and Ce3d3/2 in the
(c)
Ce2O3 spectrum [30]. Electron conditions at the surface of the used
Ni–Ce/MgAl2O4 catalyst with Ce/Ni = 0.25 was confirmed as a co-
1200 1300 1400 1500 1600 1700 1800 existent form of Ce3+ and Ce4+. According to previous research by Xu
Raman Shift (cm-1) et al. [31], the presence of CeO2 and Ce2O3 in a catalyst will improve
the inhibition of the surface carbon formation. The added Ce in CSCRM
Fig. 7. Raman spectra of the cokes over used Ni–Ce/MgAl2O4 catalysts with Ce/Ni ratios of
(a) 0.0, (b) 0.25, (c) 0.50, (d) 1.00.
receives active oxygen through the dissociation of H2O and CO2 by a
low-valence state Ce3 + and transfers the active oxygen to Ni, thus
removing deposited coke on the surface of the catalyst as CO, CO2, and
catalyst showed lower catalytic activity than Ce-promoted catalysts in H2 through the gasification reaction. The C 1s spectrum showed that
CSCRM. hydrocarbon and an adventitious carbon peak were observed at
Fig. 8 shows the result of the XPS analysis performed to examine the 285 eV in fresh catalyst, but the carbon peak was shifted to 284 eV in
electron states of Ni, Ce, and carbon on the catalyst surface. In the used catalysts after the reaction was completed [7]. Horváth et al. [32]
spectrum of Ni2p + Ce3d, main peaks from Ni2p3/2 and Ni2p1/2 demonstrated that the C 1s peak was broadened and shifted to lower
appeared at 855.2 eV and 872.9 eV, respectively, while satellite peaks BE after CO2 + CH4 reaction at 660 °C. He explained that this peak
appeared at 861.1 eV and 879.9 eV [7,31]. It was, therefore, confirmed shift was caused by an increased conductivity of sample due to the
that supported Ni existed in the form of Ni2+ corresponding to mainly carbonaceous layer. In other words, the XPS peak shift to lower BE
NiO and Ni(OH)2 on the surface of a catalyst. A particular thing to be is caused by the coke formation on the surface of used catalysts.
Interestingly, this result matches with the SEM and TGA analysis results
wherein a large amount of whisker coke formation was observed in
used catalysts. The C 1s peak was deconvoluted to identify the carbon
species on the surface of catalyst from the XPS results in Table 4.
According to the previous reports, the peak of graphitic-like carbon
and carbide is present at 284.6 eV and 282.8 eV, respectively. The
peak at 288.9 eV is attributed to oxidized carbon (\C_O) [7,29]. As
compared with the used Ni–Ce/MgAl2O4 catalyst, the total C 1s peak
area of used Ni/MgAl2O4 catalyst increases due to the coke formation.
It is noteworthy that a considerable amount of carbide was only present
on the surface of used Ni/MgAl2O4 catalyst. As mentioned above, the
XPS results demonstrate the chemical states of carbon species on the
catalyst surface within the compass of 10 nm. Meanwhile, the TGA
analysis measures the overall amount of coke in the used catalysts.
From these results, amorphous carbon like carbide was mainly deposit-
ed on the surface of Ni/MgAl2O4 catalyst, whereas the graphitic carbon
was formed at the whole of catalyst particles. In addition, it was
confirmed that the Ni–Ce/MgAl2O4 catalyst had higher coke resistance
than Ni/MgAl2O4 catalyst. These results explain why the 10Ni–2.5Ce/
MgAl2O4 catalyst displays stable catalytic activity and excellent coke
resistance with a synergetic effect between Ni and CeO2. First, CeO2,
which was in intimate contact with Ni, transferred active oxygen
through the dissociative absorption of H2O and CO2. As a result, coke
was easily removed by gasification during which deposited coke was
converted into CO, CO2 and H2. Also, due to the improved SMSI through
the Ce addition, coke formation on the catalyst surface was suppressed.
To investigate coke deposition characteristics by reaction tempera-
tures, the catalyst prepared with Ce/Ni = 0.25 was tested at 700 °C,
650 °C, 600 °C, and 550 °C and then TGA analysis of used catalysts
was performed. The results are arranged in Table 5. While deposition
of amorphous carbon was not changed much by reaction temperature,
graphitic carbon showed increases in carbon deposit with a decrease
in reaction temperature. A close examination revealed that there was
no graphitic carbon deposition at all in the catalyst reacting at 700 °C.
Fig. 8. XPS spectra of (a) fresh 10Ni/MgAl2O4 catalyst, (b) used 10Ni/MgAl2O4 catalyst after
Furthermore, the deposited amount of carbon sharply increased to
coke test, (c) fresh 10Ni–2.5Ce/MgAl2O4 catalyst, and (d) 10Ni–2.5Ce/MgAl2O4 catalyst 0.0017gC/gcat, 0.0186gC/gcat, and 0.0641gC/gcat when reaction tempera-
after coke test. tures were decreased to 650 °C, 600 °C, and 550 °C respectively. As has
 K.Y. Koo et al. / Fuel Processing Technology 119 (2014) 151–157 157

Table 4
Estimation of the carbon species on the surface of catalysts from C 1s peak of XPS.

Carbon species 10Ni/MgAl2O4 (fresh) 10Ni/MgAl2O4 (used) 10Ni–2.5Ce/MgAl2O4 (fresh) 10Ni–2.5Ce/MgAl2O4 (used)

Carbide – 20.1% – –
Graphitic carbon 78.4% 63.9% 79.5% 83.3%
\C_O 21.6% 16.0% 20.5% 16.7%

Table 5 and Planning (KETEP) grant funded by the Korea Government Ministry
Quantitative data of carbon deposited on 10Ni–2.5Ce/MgAl2O4 catalyst (Ce/Ni = 0.25) of Knowledge Economy (20122010200040).
tested at different reaction temperatures.

Temperature Amorphous carbon Graphitic carbon Total amount References

(°C) (gC/gcat) (gC/gcat) of coke (%)a
700 0.0125 0 1.3
650 0.0168 0.0017 1.9
600 0.0095 0.0186 2.8
550 0.0110 0.0641 7.5
a
Coke deposition was quantified by thermogravimetry.
been explained previously, whisker shaped graphite carbon deposition
at low temperatures is induced by a Boudouard reaction. Total amount
of coke was the smallest at 1.3% under a high reaction temperature of
700 °C, while carbon deposition was increased by around 6 times
their previous value up to 7.5% decreasing in the reaction temperature
to 550 °C. This coke deposition behavior by reaction temperature can
be explained by the reaction mechanism and the reaction rate [33,34].
In the low temperature reaction at 550 °C, carbonaceous intermediates
which are generated by the dissociative adsorption of methane reacts
slowly with H2O and CO2 reactants, making the coke removal process
via gasification of coke on the catalyst surface slower, ultimately leading
to coke deposition. As a result, accumulated coke on the catalyst surface
is dissolved as Ni metal to form a nickel carbide, which further grows
into whisker carbon.
4. Conclusions
The Ce-promoted Ni/MgAl2O4 catalysts have been prepared via
co-impregnation method by controlling the Ce/Ni-ratio for CSCRM.
When compared with the Ni/MgAl2O4 catalyst without Ce addition,
Ni–Ce/MgAl2 O 4 catalysts exhibited higher metal dispersion and
excellent reducibility at low temperatures of 550 °C. In particular,
Ni–Ce/MgAl2O4 catalyst with a Ce/Ni ratio of 0.25 showed the highest
catalytic activity and coke resistance at low temperatures in CSCRM. It is
mainly due to the enhancement of strong metal-support interaction
and the effective active oxygen transfer through intimate contact with
Ni–Ce. Hence, the Ce-promoted Ni/MgAl2O4 catalyst is expected to be a
promising catalyst with excellent coke resistance in CSCRM for the syngas
production.
Acknowledgment
This work was conducted under the framework of Research and
Development Program of the Korea Institute of Energy Research
(KIER) (B3-2413). This work was supported by the Energy Efficiency
& Resources of the Korea Institute of Energy Technology Evaluation
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