Journal of Industrial and Engineering Chemistry 28 (2015) 229–235

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Synthesis gas production process for natural gas conversion

over Ni–La2O3 catalyst
Wonjun Cho a,*, Hyejin Yu a,b, Wha-Seung Ahn b, Seung-Soo Kim c,**
a
DME Technology Research Center, KOGAS, 973 Dongchung-dong, Yeonsu-gu, Incheon 406-130, Republic of Korea
b
Department of Chemical Engineering, Inha University, 100 Inha-ro, Nam-gu, Incheon 402-751, Republic of Korea
c
Department of Chemical Engineering, Kangwon National University, 346 Joongang-ro, 245-711 Samcheok, Gangwon-do, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: The synthesis gas (syngas) is a mixture of hydrogen and carbon monoxide, which is suitable as a feed gas
Received 22 September 2014 to produce clean liquid synthetic fuel in natural gas conversion reactor. In order to achieve the efficiency
Received in revised form 23 January 2015 reactor, the syngas composition should match the usage ratio of the reactors. In this work, we investigate
Accepted 20 February 2015
the development of synthesis gas production process in the steam-CO2 reforming (SCR) over Ni–La2O3
Available online 25 February 2015
catalyst supported Ce–ZrO2/Al2O3. And, we developed the kinetics model for SCR used by the profiles of
concentration and temperature in the SCR reactor.
Keywords:
ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Syngas
reserved.
Steam-CO2 reforming (SCR)
Synthetic fuel reactor
Catalyst
Kinetics

Introduction conversion in industry typically involves an indirect route through

In 21st century, there is a clear trend towards cleaner burning of
methane as an energy source. Fortunately, natural gas is an
extremely abundant resource throughout the world. Also, use of
these gas reserves is a natural step in the progression of moving
from oil-based fuels to hydrogen and renewable.
There are approximately 5000 trillion cubic feet (TCF) of
natural gas reserves in the world. However, a significant fraction
of this is considered ‘‘stranded’’ that is, not accessible using
traditional gas processing technologies (e.g., LNG or pipeline) due
to contamination and/or geography. Approximately 15 TCF of gas
in associated wells is vented, flared or re-injected each year. Given
the environmental impact of venting and flaring and the huge
amount of resources left untapped, there is great incentive to
develop technologies that will allow these stranded wells to be
used [1].
One way to use these wells is to convert the gas into an easily
transportable liquid product. Unfortunately, the direct conversion
of methane into a liquid is severely limited by thermodynamics.
Therefore, much of the developing effort devoted to methane
* Corresponding author. Tel.: +82 32 810 0321; fax: +82 32 810 0321.
** Corresponding author. Tel.: +82 33 570 6544; fax: +82 33 570 6535.
E-mail addresses: williamcho86@gmail.com (W. Cho),
sskim2008@kangwon.ac.kr, ks7070@dreamwiz.com (S.-S. Kim).
a ‘‘syngas’’ intermediate. In general, ‘‘synthetic fuel’’ refers to fuels
manufactured via Fischer–Tropsch (FT) conversion, methanol to
gasoline and/or oxygenate conversion or direct liquefaction.
Conversion technologies in the commercial processes could be
either direct conversion to liquid fuels or indirect conversion of the
source substance initially to ‘‘syngas’’ which then goes through
additional conversion process to make a liquid fuel. The growing
attention to the production of syngas (H2/CO) is attributed to the
conversion of synthetic fuel from natural gas, biomass, coal and/or
coal base gas.
Syngas is manufactured industrially from hydrocarbon fuels
either by steam reforming (SRM), catalytic partial oxidation (CPO),
carbon dioxide reforming (CDR), autothermal reforming (ATR) or
tri-reforming (TRM) [2–6].
Korea Gas Corporation (KOGAS) is one of the major energy
companies to pursue development and commercialization of
dimethyl-ether (DME) and FT-oil production from gas-to-liquid
(GTL) process. KOGAS’ research effort in the past decade has
produced novel technologies such as the tri-reformer reactor that
produces syngas with a good control of H2/CO ratio, a key operating
variable in DME production and with a minimum coke formation
[7–9]; and one-step synthesis of DME reactor [10]. Also, KOGAS has
developed a complete GTL process incorporating these technolo-
gies and has successfully been operating 1 bbl per day pilot plant
since 2010. In KOGAS GTL process, nickel-based catalysts are used

http://dx.doi.org/10.1016/j.jiec.2015.02.019
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
230 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235

for methane steam and CO2 reforming in order to produce a proper

syngas ratio (H2/CO = 2.0), which can produce a FT synthetic fuel.
KOGAS plans to bring its research and demonstration effort into
establishing technology license [11]. Future development by
KOGAS includes designing a DME/GTL plant on a mobile platform
such as on a floating production and storage and off-loading (FPSO)
unit.
In our previous result, the Ni/Ce–ZrO2/Al2O3 catalyst with the
additives (MgO, La2O3) catalyst seemed to play an important role
to prevent the formation of carbon deposition over the catalysts
because the binary support might have improved the oxygen
storage capacity and thermal stability [12]. The objective of this
work is to investigate the catalytic performance of Ni–La2O3
catalyst supported Ce–ZrO2/Al2O3 developed by KOGAS for SCR
reforming process. It is important to develop the kinetic study of
hydrogen rich syngas for optimization of SCR reactor design and
GTL process.

Experimental

Catalyst preparation

The Ni–La2O3/Ce–ZrO2/Al2O3 catalyst was prepared by co- Fig. 1. The schematic diagram of reactor.
impregnation method. The Ni loading amount was fixed to 7 wt%.
The lanthanum was loaded with various contents from 0 to 20 wt%.
reforming reactions were performed under different conditions in
The La2O3-promoted on Ni was prepared using an aqueous solution
the temperature range 973–1173 K and by maintaining the
of nickel (III) nitrate hexahydrate and lanthanum nitrate hexahy-
pressure of reactant at 20 bar [17]. For each run, 7.0 g catalyst
drate. These solutions were dissolved in distilled water with
was loaded into a reactor [18]. The ratio of CH4:H2O:CO2 in the feed
stirring 500 rpm. The Ce–ZrO2/Al2O3 support was prepared by
gas was kept to 1.0:1.6:0.9 in order to produce a proper ratio of H2/
impregnation method. Cerium (III) acetate hydrate and zirconium
CO to make reactants for Fischer–Tropsch reaction, and the space
nitrate were dissolved in the same as the above method. This
velocity conditions were changed 2500 h1 into 4000 h1.
mixed solution was impregnated on a-Al2O3 followed by drying in
The effluents from the reactor were analyzed on-line with a gas
microwave oven and then calcined at 1173 K for 6 h in air. The
chromatograph (GC, Younglin, Autochro 2000) using a packed
supported Ni solution was onto Ce–ZrO2/Al2O3 by impregnation
column (Porapak N) equipped with a thermal conductivity
and calcined at 1023 K for 6 h in air [13].
detector (TCD) and flame ionization detector (FID).
The conversion of CH4 and CO2, the yield of H2, CO and H2/CO
Analysis of prepared catalyst
ratio was calculated on the basis of the feed flow rates and the dry
exit gas composition as obtained by gas chromatography using the
The BET surface area, total pore volume and average pore
following formulas [19]. In Eq. (3), 2 moles of methane needed due
diameter of the catalysts were measured by nitrogen adsorption at
to methane that is sourced from 2 feed streams namely CO2/CH4
77 K using a BET instrument (Micromeritics, ASAP 2020). About
and H2O/CH4.
0.5 g of catalyst was used, respectively. The samples were pre-
treated in high vacuum at 123 K to remove moisture and other ½CH4 in  ½CH4 out
adsorbed gases from the catalyst surface. X-ray diffraction (XRD, CH4 conversion ð%Þ ¼  100 (1)
½CH4 in
Bruker, D2 Phase) patterns were recorded to investigate the crystal
structure and compositional homogeneity of the prepared ½CO2 in  ½CO2 out
catalysts. The crystallite size was estimated by using the Scherrer CO2 conversion ð%Þ ¼  100 (2)
½CO2 in
equation [14]. The morphologies of fresh catalysts and deposited
coke were examined by scanning microscopy (SEM, Hitachi, SU- ½H2 out
8010). The electron state of used catalysts was measured with an H2 yield ¼  100 (3)
½CH4 in  2 þ ½H2 Oin
X-ray photoelectron spectroscope (XPS, K-alpha) using the binding
energy (BE) was calibrated by using the C 1s peak at 284.6 eV and ½COout
Ni 2p peak at 855.5 eV as a reference [15]. Fourier transform CO yield ¼  100 (4)
½CH4 in þ ½CO2 in
infrared spectra (FT-IR) were obtained in the range of 4000–
400 cm1 by diluting the samples with KBr powder and measured
using a spectrometer instrument (Bruker, Vertex.80V) [16]. Table 1
Characteristic of the catalysts.
Catalytic reaction
La2O3 (wt%) Surface Ni crystallite Pore volume Average pore
area (m2/g)a size (nm)b (cc/g) diameter (nm)
The methane reforming performances of the catalysts were
0 5.2 25.8 0.03 21.0
investigated using a high pressure fixed-bed reactor system. The
3 7.3 10.5 0.02 42.8
reactor with an inner diameter of 8 mm was heated in an electric 7 8.5 37.2 0.01 63.2
furnace a shown Fig. 1. 10 8.9 39.2 0.01 64.5
The study of the effect of contact time (W=FCH4 , g cat/ 20 14.2 41.0 0.02 48.6
g methane/h, feed ratio), feed ratio of CO2/CH4 on conversion a
Estimated from N2 adsorption at 196 8C.
and product yield were done under integral conditions. The SCR b
Estimated from XRD.
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235 231

Results and discussion

Catalyst characterization

Table 1 summarizes the characteristics of the catalysts with

various La2O3 contents. It shows the BET surface area, pore volume
and the Ni crystallite size. The surface area of Ni/Ce–ZrO2/Al2O3
without La2O3 is 5.2 m2/g, shown the lowest BET surface area. As
La2O3 content increase 3–20 wt%, BET surface area and Ni
crystallite size show the tendency to increase. The Ni crystallite
size of Ni–La2O3/Ce–ZrO2/Al2O3 with 20 wt% La2O3 is 41.0 nm,
indicating that the NiO crystallite size of this catalyst is larger than
the other catalysts.
The XRD patterns of La2O3-promoted Ni/Ce–ZrO2/Al2O3 cata-
lysts with various La2O3 contents are given in Fig. 2. The main
phase of nickel in these catalysts was NiO that exhibited three
major peaks at 2u values of 35.08, 49.78 and 62.58 [20].
Fig. 2. XRD data of the catalysts prepared.
As the lanthanum content increases, the intensity of NiO peak
decreases. It is likely that the reduced NiO peaks as the active site
H2 ½H2 out for this reaction exhibiting different catalytic activity and coking
ratio ¼  100 (5) tolerance. For the La2O3-promoted catalyst, the characteristic
CO ½COout

Fig. 3. SEM images of fresh catalysts with various contents as support.

232 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235

Table 2 CO2 are improved with the La2O3 loadings increasing from 3 wt% to
The comparison of reaction results over Ni–La2O3/Ce–ZrO2/Al2O3 in SCR.
7 wt%. In case of 7 wt% La2O3, it showed higher activity and
La2O3 (wt%) CH4 CO2 H2/CO H2 CO stability than the other catalysts for SCR process for 24 h. It is well
conversion (%) conversion (%) yield (%) yield (%) established that selection of additives content is important for
0 90.9 64.5 1.85 56.0 57.4 enhancement in catalytic activity and stability in the SCR process.
3 90.0 69.3 1.81 56.3 58.9
7 91.5 73.7 1.84 57.5 59.4 Kinetic study
10 88.0 67.5 1.98 57.5 55.0
20 77.9 42.7 2.51 54.4 42.4
Several relevant efforts for steam and carbon dioxide reforming
of methane model can be found in literature [23]. Some are based
reflections of LaNiO3 were present at 32.78 and 47.08. In the case of on effective rate equations and others are based on detailed
20 wt% lanthanum, La2O3 peak was formed [21]. descriptions of transport to the catalyst surface and reactions at the
The morphologies of the fresh catalysts were observed by SEM surface. The SCR process combines the endothermic steam
analysis, as shown in Fig. 3. The fresh Ni/Ce–ZrO2/Al2O3 catalyst reforming reaction:
showed relatively uniform angular particles, whereas the fresh Ni–
CH4 þ H2 O $ CO þ 3H2 (6)
La2O3/Ce–ZrO2/Al2O3 catalysts with various contents showed
particles to spread of allocation of different particle sizes and
CH4 þ 2H2 O $ CO2 þ 4H2 (7)
shapes [22].
The accompanying water–gas shift:
Performance test of catalyst
CO þ H2 O $ CO2 þ H2 (8)

Table 2 summarizes the reaction results over these catalysts. and the CO2 reforming reaction:
The SCR reaction was carried out for 24 h under same condition as
CH4 þ CO2 $ 2CO þ 2H2 (9)
catalytic reaction. CH4 conversion and CO2 conversion increased
with the rise of La2O3 loading up to 7 wt%, and above this content it To achieve a syngas with the desired composition, care has to be
decreased. In the case of 7 wt% La2O3, it exhibited the highest CH4 taken to avoid carbon decomposition according to the Boudouard
conversion and CO2 conversion as 91.5% and 73.7%, respectively. reaction:
From the data in Fig. 4, the result showed CH4 and CO2
2CO $ C þ CO2 (10)
conversion over the catalysts during the reaction for 24 h at the
same condition as above-mentioned. The conversions of CH4 and and to methane cracking:
CH4 $ C þ 2H2 (11)

Fig. 4. Reaction results during 24 h reaction time with various La2O3 contents Fig. 5. Effect of W=FCH4 ;0 and W=FCO2 (CH4:H2O:CO2 = 1.0:1.6:0.9) on CH4 and CO2
in SCR. conversion at different at different temperature.
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235
The H2/CO ratio of the process gas can be adjusted by
controlling the CO2/CH4 and H2O/CH4 ratio of the feed. The kinetic
study was based on the power rate law as shown in Eq. (12).
!
Eiapp
r i ¼ Aexp ðPCO2 Þa;i ðP H2 O Þb;i (12)
RT
where i is CH4 or CO2, ri the CH4 or CO2 conversion rate, A is the pre-
exponential factor, (a, i), (b, i) the reaction orders, and Eiapp is the
apparent activation energy with respect to CH4 or CO2 conversion.
Catalytic performance test was investigated at different tempera-
tures ranging from 973 to 1173 K with CH4:H2O:CO2 = 1.0:1.6:0.9.
The effect of contact time (W=FCH4 and W=FCO2 ) on CH4 and CO2
conversion at different temperature is shown in Fig. 5. CH4 and CO2
conversion increased with increasing reaction temperature and W/
Fi.
Song and Pan [8] proposed a kinetic mechanism based on
power-law rate equations based on their experimental measure-
ments. We have applied some of these techniques to study the
kinetics over Ni/Ce–ZrO2/Al2O3 catalyst.
Fig. 6 shows the plots of ln[r(CH4)] or ln[r(CO2)] versus lnðPCO2 Þ
or lnðPH2 O Þ and Fig. 7 shows the plots of ln[r(CH4)] or ln[r(CO2)]
versus 1/T over Ni/Ce–ZrO2/Al2O3 added 7 wt% La2O3. The partial
pressure of CO2 and H2O was controlled by back pressure regulator
in the experimental apparatus. Especially, the vapor pressure of
H2O was controlled considering steam table. CH4:H2O:CO2 was
fixed value. The kinetic data show the interaction relation of CH4
conversion by CO2 in the presence of H2O and CO2. The CH4 and CO2
conversion rates show a slight increase over catalyst with the rise
in a reaction temperature.
Fig. 6. CO2 and H2O partial pressure effect on CH4 and CO2 conversion rate (mol/s g-
cat) and H2/CO ratio at 973 K and 10 bar, CH4:H2O:CO2 = 1.0:1.6:0.9.
233
While the CH4 conversion is not affected by the partial pressure
of CO2 and H2O, CO2 conversion rate has an influence on the
catalytic activity and H2/CO ratio in accordance with the partial
pressure of CO2 and H2O. As CO2 partial pressure was increased, the
CO2 conversion increased and the syngas ratio (H2/CO) decreased
from 2.2 to 1.7. However, with the increase in the H2O partial
pressure, the CO2 conversion was decreased and syngas ratio
was increased. It means that H2O may become the dominant
component to react with CO2 and CH4. With the increase of P H2 O ,
the existence of water gas shift reaction in SCR process may also
play a role in decreasing the CO2 conversion rate with the increase
of P H2 O as indicated by Song and Pan [8]. The apparent activation
energy for CH4 conversion is 60.8 kJ/mol and the one for CO2
conversion is 27.9 kJ/mol from Fig. 7.
During the kinetic study of the partial pressure effect of CO2
and H2O, it is found that H2/CO ratio declines with the increase of
CO2 partial pressures and increases with the increase of partial
pressure of H2O over Ni–La2O3/Ce–ZrO2/Al2O3.
Coke analysis
The coke deposition on used catalysts was monitored by SEM
analysis. The effect of La2O3-promoted catalyst can be shown by a
tendency to coke formation in our study. Fig. 8 shows the SEM
images of used catalysts were collected after reforming reaction
under same condition of catalytic reaction. Compared to the
surface of fresh catalyst (Fig. 3), a lot of filamentous carbon species
are presented on the used catalysts.
In order to explain the formation of the carbonate, which can
produce the coking site, and the possible participation of the
surface hydroxyl groups in the SCR reaction, FT-IR measurements
were performed over Ni/Ce–ZrO2/Al2O3 with various contents of
La2O3 (Fig. 9). In most of the samples, there are three IR active
absorption bands arising from the carbonate anion observed at
1050–1080 cm1, 850–880 cm1 and 670–690 cm1. Observation
of IR band at 1050–1080 cm1 and at 850–880 cm1 suggests the
lowering of the symmetry of the carbonate ion [24] and the
formation of a strong interaction between CO2 and the La2O3
additive catalysts to form carbonate. Moreover, the presence of
weak peak with absorbance at 1420 cm1 was observed. This is
due to the deformation and anti-symmetric stretching of uni-
denate carbonate formed by the interaction of CO2 [25]. These
results indicate that the carbonate group over catalyst may be
accelerated to form the coking on the surface of Ni-base catalyst
(Fig. 9).
Fig. 7. Plots of CH4 and CO2 conversion rate and H2/CO ratio vs. 1/T over Ni/Ce–ZrO2/
Al2O3 with 7 wt% La2O3 additives.
234 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235

Fig. 8. SEM images of used catalysts with various contents of support.

The XPS spectra of Ni/Ce–ZrO2/Al2O3 and loading with 7% reported that weak peak indicated Ni surface, which is enclosed
La2O3 catalysts in C 1s and Ni 2p region are shown in by a large amount of coke [21].
Fig. 10. Whereas the C 1s spectra yielded just one peak at
282 eV in Ni/Ce–ZrO2/Al2O3 catalyst, the deconvolution of C 1s
spectra obtained three peaks: peak 1 (279 eV), graphitized
carbon; peak 2 (282 eV) carbide in NiCx; and peak 3 (286 eV),
filamentous carbon and/or carbon in carbonate groups in Ni–
La2O3/Ce–ZrO2/Al2O3 catalyst. The binding energy for Ni0 and
NiCx is the same at 852 eV. The weak peak at 850 eV in Ni/Ce–
ZrO2/Al2O3 was assigned in Ni0 and/or Ni-carbide. The most peak
in Ni–La2O3/Ce–ZrO2/Al2O3 catalyst could be oxidized to Ni2+
(NiO at 854) in Fig. 10(b). The nickel concentration of the surface
of catalyst is very small contents (2–3 wt%) that most of Ni2+ ions
are in the solid framework as a NiAl2O3 phase (BE = 854 eV). It is
observed that XPS can identify Ni0 and/or NiAl2O3. And, nickel
carbide (NiCx) as evidenced both in the Ni 2p and C 1s spectra
(Fig. 10) after SCR reaction.
The BE of C 1s spectra showed high intensity with Ni/Ce–ZrO2/
Al2O3 catalyst which can be assigned to graphitic carbon. The C 1s
spectra shift to higher BE with Ni–La2O3/Ce–ZrO2/Al2O3 catalyst.
However, in the case of Ni/Ce–ZrO2/Al2O3 catalyst, the intensity of Fig. 9. FT-IR spectra of La2O3-promoted Ni/Ce–ZrO2/Al2O3 catalysts with various
Ni 2p peak was more sharp than Ni/Ce–ZrO2/Al2O3 catalyst. It is La2O3 contents Fig. 10 XPS of (a) C 1s and (b) Ni 2p3/2 regions of Ni/Ce–ZrO2/Al2O3.
 W. Cho et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 229–235
Fig. 10. XPS of (a) C 1s and (b) Ni 2p3/2 regions of Ni/Ce–ZrO2/Al2O3.
Conclusions
The effect on La2O3 as additives of Ni/Ce–ZrO2/Al2O3 catalyst for
the improvement of the catalytic activity and carbon tolerance in
SCR process was investigated. The catalysts were prepared by co-
impregnation using La2O3 with various content from 0 to 20 wt%.
235
In the SCR process, loading with 7 wt% La2O3 catalyst showed
higher activity and stability. The conversions and product yield
increased with the rise in reaction temperature and contact time
(W/Fi) and reached equilibrium at W=FCH4 ¼ 0:49 g cat h=g CH4 and
W=FCO2 ¼ 1:68 g cat h=g CO2 in the SCR reaction. The 1.98 of syngas
ratio (H2/CO) was produced at a CO2/CH4 ratio of 0.9 and H2O/CH4
ratio of 1.6 in the Ni–La2O3/Ce–ZrO2/Al2O3 catalyst system. The
apparent activation energy for CH4 conversion is 60.8 kJ/mol and
the one for CO2 conversion is 27.9 kJ/mol from the kinetic study
based on the power rate law. And, the carbonate group over
catalyst may be accelerated to form the coking on the surface of Ni-
base catalyst.
Acknowledgment
This study was supported by ‘‘Korea Gas Corporation R&D
program’’ and ‘‘Ministry of Trade, Industry and Energy’’.
References
[1] D.T.B. Leather, A. Bahadori, C. Nwaoha, D.A. Wood, J. Nat. Gas Sci. Eng. 10 (2013)
68–88.
[2] H. Arakawa, M. Aresta, J.N. Armor, Chem. Rev. 101 (2001) 953–996.
[3] A.M. De Groote, G.F. Froment, Appl. Catal. A: Gen. 138 (1996) 245–264.
[4] D.L. Hoang, S.H. Chan, Appl. Catal. A: Gen. 268 (2004) 207–216.
[5] W. Cho, S. Kim, J. Korean Ind. Eng. Chem. 20 (2009) 355–362.
[6] C.S. Song, Catal. Today 115 (2006) 2–32.
[7] M. Halmann, A. Steinfeld, Catal. Today 115 (2006) 170–178.
[8] C. Song, W. Pan, Catal. Today 98 (2004) 463–484.
[9] W. Cho, T.Y. Song, A. Mitos, J.T. McKinnon, G.H. Ko, J.E. Tolsma, D. Denholm, T. Park,
Catal. Today 139 (2009) 261–267.
[10] D.S. Song, W.J. Cho, G.B. Lee, D.K. Park, E.S. Yoon, Ind. Eng. Chem. Res. 47 (2008)
4553–4559.
[11] W. Cho, Y. Mo, T. Song, Y. Baek, S. Kim, Trans. Korean Hydrogen New Energy Soc.
25 (2014) 105–113.
[12] W. Cho, H. Yu, Y. Mo, W.-S. Ahn, Trans. Korean Hydrogen New Energy Soc. 25
(2014) 105–113.
[13] H.-S. Roh, H.S. Potdar, K.-W. Jun, Catal. Today 93–95 (2004) 39–44.
[14] K.Y. Koo, H.-S. Roh, Y.T. Seo, D.J. Seo, W.L. Yoon, S.B. Park, Int. J. Hydrogen Energy
33 (2008) 2036–2043.
[15] K.Y. Koo, S.-H. Lee, U.H. Jung, H.-S. Roh, W.L. Yoon, Fuel Process. Technol. 119
(2014) 151–157.
[16] P.A. Kumar, M.P. Reddy, K.J. Lee, J. Mol. Catal. A: Chem. 291 (2008) 66–74.
[17] A. Nandini, K.K. Pant, S.C. Dhingra, Appl. Catal. A: Gen. 308 (2006) 119–127.
[18] H.-S. Roh, K.-W. Jun, S.-E. Park, Appl. Catal. A: Gen. 251 (2003) 275–283.
[19] S.-H. Lee, W.I. Cho, W.-S. Ju, B.-H. Cho, Y.-C. Lee, Y.-S. Baek, Catal. Today 87 (2003)
133–137.
[20] S. Wang, G.Q.M. Lu, Appl. Catal. B: Environ. 16 (1998) 269–277.
[21] K.Y. Koo, H.-S. Roh, Y.T. Seo, D.J. Seo, W.L. Yoon, S.B. Park, Appl. Catal. A: Gen. 340
(2008) 183–190.
[22] H.-S. Roh, H.S. Potdar, K.-W. Jun, J.-W. Kim, Y.-S. Oh, Appl. Catal. A: Gen. 276
(2004) 231–239.
[23] A.K. Avetisov, J.R. Rostrup-Nielsen, V.L. Kuchaev, J.-H. Bak Hansen, A.G. Zyskin,
E.N. Shapatina, J. Mol. Catal. A: Chem. 315 (2010) 155–162.
[24] L. Zhang, F. Li, D.G. Evans, X. Duan, Mater. Chem. Phys. 87 (2004) 402–410.
[25] K. Sutthiumporn, S. Kawi, J. Int. Hydrogen Energy 36 (2011) 14435–14446.