international journal of hydrogen energy xxx (xxxx) xxx

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Combined steam and CO2 reforming of methane

(CSCRM) over NiePd/Al2O3 catalyst for syngas
formation

Danial Batebi a, Reza Abedini a,*, Amir Mosayebi b

a
Faculty of Chemical Engineering, Babol Noshirvani University of Technology, Babol, Iran
b
Department of Chemical Engineering, Tafresh University, Tafresh, Iran

highlights

The ANOVA results showed that the quadratic models could well predict the responses.

The effect of CO2/H2O ratio on the CH4 conversion, CO and H2 yield was negligible.

The coke formation was increased by increasing of CO2 portion in the oxidizing agent.

The total conversion was almost accessible at temperatures higher than 850  C.

The effect of temperature on the H2 yield depended on (CO2 þ H2O)/CH4 ratio.

article info abstract

Article history: In order to syngas formation, combined steam and carbon dioxide reforming of methane
Received 27 November 2019 (CSCRM) used in the presence of NiePd/Al2O3 catalysts, which were synthesized by the sol-
Received in revised form gel method. Al2O3 supported NiePd catalyst exhibited the appropriate surface area of
24 February 2020 176.2 m2/g and high dispersion of NiO phase with an average crystallite size of 11 nm,
Accepted 17 March 2020 which was detected on catalyst surface utilizing transmission electron microscopy (TEM).
Available online xxx The influence of three independent operating parameters including reaction temperature
in the range of 500e1000  C; (CO2 þ H2O)/CH4 ratio, in the range of 1e3 and CO2/H2O ratio; in
Keywords: the range of 1e3, were investigated on the responses (i.e., CH4 conversion, H2 yield, CO
CSCRM yield, amount of coke formation on the catalyst surface and H2/CO ratio) in CSCRM by using
Syngas response surface methodologyecentral composite design (RSM-CCD) method. The ob-
Nickel tained results from ANOVA and the proposed quadratic models could fine forecast the
H2 and CO yields responses. It was seen that the total methane conversion and CO yield was almost
CH4 conversion accessible at temperatures higher than 850  C. Moreover, the CO2/H2O ratio exhibited no
Coke deposition significant effect on the CH4 conversion, H2 yield and CO yield of NiePd/Al2O3 catalysts in
CSCRM reaction. However, the high CO2/H2O ratio in inlet feed led to the syngas formation
with a low H2/CO ratio. The results revealed that lower CO2/H2O ratio and higher temper-
ature as well as higher (CO2 þ H2O)/CH4 ratio help to decrease the coke formation.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: abedini@nit.ac.ir (R. Abedini).
https://doi.org/10.1016/j.ijhydene.2020.03.137
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
The vital use of syngas, a mixture of H2 and CO, in both
chemical and petrochemical industries has been widely
recognized since it is currently utilized as the primary feed-
stock for producing environment-friendly synthetic fuels and
methanol via respective Fischer-Tropsch synthesis (FTS) and
methanol production [1,2]. Syngas is a fuel gas mixture that
can be produced from many sources, including natural gas,
coal, biomass, or virtually any hydrocarbon feedstock, by re-
action with steam (steam reforming), carbon dioxide (dry
reforming) or oxygen (partial oxidation) [3]. Methane is an
essential ingredient in natural gas and also the cheapest and
most accessible source of energy. Converting methane into
syngas can occur via three below reactions [1,4]:
CH4 þ0:5O2 /2H2 þ CO ðpartial oxidationÞ DH0298 ¼ 38 KJ=mol
(1)
CH4 þH2 O/CO þ 3H2 ðsteam reformingÞ DH0298 ¼ 206 KJ=mol
(2)
CH4 þ CO2 /2CO þ 2H2 ðdry reformingÞ DH0298 ¼ 248 KJ=mol
(3)
The partial oxidation of methane (POM) is an exothermic
method that can provide a suitable H2/CO ratio for the Fischer-
Tropsch synthesis. Nevertheless, POM needs a high expensive
oxidation plant, which is hard to control, and also its explosion
danger is known as another drawback [2e6]. Steam reforming of
methane (SRM) is recognized as an economic and commercial
approach to produce synthesis gas with the H2/CO ratio of 3 and
generally proceeds in the presence of nickel-based catalysts and
also prefers high temperature and low pressure [2e6]. Moreover,
in dry reforming of methane (DRM), CO2 is used to turn methane
into syngas. In this reaction, two greenhouse gases (CO2 and
CH4) are consumed, which is a principal advantage and this
method produces the H2/CO ratio less than one [7]. The com-
bined steam and carbon dioxide reforming of methane, known
as CSCRM, can be employed to produce syngas with the flexible
H2/CO ratio [1e3,7]. CSCRM offers a significant real advantage to
adjust the H2/CO ratio via controlling the pressure, temperature,
and variation of the feed ratio composition [1,2]. However, the
CSCRM is known as a complex reaction, because the number of
reactions such as reforming reactions, secondary reactions and
cock formation occurs simultaneously.
CO þ H2 O /CO2 þ H2 ðWater Gas ShiftÞ DH0298
¼ 41 KJ=mol (4)
CO2 þ H2 / CO þ H2 O ðReverse Water Gas ShiftÞ DH0298
¼ 41 KJ=mol
(5)
CH4 / C þ 2H2 ðMethane DecompositionÞ DH0298
¼ 75KJ=mol (6)
2CO / C þ CO2 ðboudouardÞ DH0298 ¼ 172 KJ=mol (7)
Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
Active metals used in catalysts for methane reforming can
be classified into transition and noble metals [1]. Although
noble metals (i.e., Pt, Rh, Ru, etc.) are more capable of cleaving
the CeH bond in such a way that the carbon deposition re-
duces, the high price constraints their application and makes
them usually used as a promoter [8]. Nickel-based catalysts
have always been considered as a proper alternative for
reforming processes in which its activity is comparable to
noble metals [9]. Although nickel-based catalysts have been
widely used owing to the modest cost and its availability, their
rapid deactivation due to coke deposition restricts their usage
in the reforming processes. This problem can be solved by
adding noble metals as a promoter. The results of previous
studies showed that the nickel-metal had the most synergistic
effect with palladium [10]. The nickel-based catalyst with
durable metal on alumina was named as a promising catalyst
for reforming processes.
Koo et al. [11] studied the performance of Ni/MgOeAl2O3
catalyst in CSCRM to produce synthesis gas. They evaluated
the effect of adding MgO to Al2O3 support and the formation
of hybrid support with various Mg/Al ratios to improve the
catalyst resistance against coke formation. They reported
that the presence of MgO along with Al2O3 leads to elevate
the coke resistance and found that an appropriate Mg/Al
ratio for good catalytic activity and high coke resistance was
0.5. Besides, they investigated the effect of pre-calcination
temperature on the performance of the Ni/MgOeAl2O3
catalyst. They concluded that increasing pre-calcination
temperature caused an increase in nickel crystallite size
and a decrease in BET surface area due to the collapse of
support.
Ozkara-Aydinoglu et al. [12] carried out a thermodynamic
equilibrium analysis by Gibbs free minimization method to
investigate the effects of operating conditions on the conver-
sion of the reactants and product distribution in CSCRM pro-
cess. Ranges of temperature, pressure and CH4/H2O/CO2 ratios
were set between 200  Ce1200  C, 1e20 bar and 0e0.5,
respectively. Their results revealed that CSCRM was
controlled by the adjusting of operating parameters such as
pressure, temperature and varying feed composition. By
increasing steam in oxidant agent, CH4 conversion and H2/CO
increased while CO2 conversions decreased and also high
temperature repressed the diminishing effect of pressure in
the CSCRM process.
Roh et al. [13] synthesized NieCeeZrO2 catalysts with
various CeO2/ZrO2 ratios by co-precipitation method and
applied for CSCRM to produce synthesis gas with H2/CO ¼ 2.
NieCe0.8Zr0.2O2 catalyst presented the highest activity as well
as high resistance to the deactivation in CSCRM due to ho-
mogenous dispersed NiO on the support. The results showed
that NieCe0.8Zr0.2O2 catalyst could be a promising candidate
catalyst for synthesis gas preparation for Fischer-Tropsch
synthesis (H2/CO ratio ¼ 2).
The addition of ZrO2 as a modifier for a CoePt/Al2O3 cata-
lyst improves its performance for CSCRM by increasing the
activity, H2 and CO formation, and H2/CO ratio formed in the
range of 0.84e1.43 [14]. Conversion of 100%, along with the
absence of sintering and coke formation, was observed in the
presence of CoePt/Al2O3 (95%)eZrO2(5%) catalyst at 755  C and
atmospheric pressure by Itkulova et al. [14].
 international journal of hydrogen energy xxx (xxxx) xxx
Jang et al. [1] investigated the effect of (CO2 þ H2O)/CH4
(0.9e2.9) and CO2/H2O ratios (0.9e2.9) and process tempera-
ture (500  Ce1000  C) on the equilibrium conversions, H2 and
CO yields, coke yield and H2/CO ratio. They reported that there
is an interaction between temperature and (CO2 þ H2O)/CH4
ratio, which can make it accessible to reach maximum CH4
and CO2 conversion. Coke formation at lower temperatures
close to 700  C was unavoidable even with an extra oxidizing
agent, while at temperatures close to 900  C, coke deposition
can be prevented by increasing (CO2 þ H2O)/CH4 ratio. The
minimum value of (CO2 þ H2O)/CH4 ratio equal to 1.2 with the
aim to intercept coke deposition. Their results revealed that
the H2/CO ratio could be controlled by changing the CO2/H2O
ratio. The proper condition prepared to produce synthesis gas
with an H2/CO ratio of 2 when the CO2/H2O ratio was less than
0.5 at temperatures above 850  C. They carried out the CSCRM
to investigate the accuracy of thermodynamic equilibrium,
which had a proper agreement in terms of almost all consid-
ered parameters.
Although the synergetic effect of nickel with palladium has
been reported, there was no investigation on nickel-palladium
catalytic performance in the CSCRM process. In this work,
NiePd/Al2O3 catalysts were synthesized by the sol-gel method
and then characterized by BET, TEM, EDX, XRD, TPR and TGA
analysis to evaluate the catalysts morphology, elemental
analysis, crystal phase structure, reduction behavior and
amount of deposited carbon for used catalysts in CSCRM.
Moreover, the systematic study through CCD-RSM method
was conducted to study the effect of operating variables (i.e.,
temperature, CO2/H2O and (CO2 þ H2O)/CH4 ratio) on five re-
sponses (i.e., CH4 conversion, H2 and CO yield, amount of coke
formation and H2/CO ratio) in CSCRM reaction which was
carried out in fixed-bed reactor.
Experimental
Catalyst synthesis
NiePd/Al2O3, Pd/Al2O3 and Ni/Al2O3 catalysts were synthe-
sized by the sol-gel method using nickel (II) nitrate hexahy-
drate (99%, Merck), palladium (II) nitrate dehydrate and g-
Al2O3 nanoparticles (Merck, assay 99.9% and particle size less
than 50 nm). The amount of nickel and palladium loadings
were fixed at 15 wt% and 0.5 wt%, respectively. NiePd/Al2O3
catalyst synthesis includes the preparation of an aqueous
solution containing Ni(NO3)2.6H2O (99.8%, Merck) and
Pd(NO3)2.2H2O (Aldrich) in deionized water which was added
to an aqueous solution of alumina and stirred for 2 h. Then,
sodium hydroxide was added to the solution to adjust PH, and
after a while, citric acid C6H8O7 was added to the mixture as a
reduction agent. The prepared solution stirred at 100  C for
12 h and then the resulting solution filtered by filter paper. The
obtained gel was dried at 100  C for 12 h and then calcined at
600  C for 5 h.
Characterization methods
The surface and pore properties of catalysts, including surface
area, average particle size and pore volume were measured by
Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
3
nitrogen adsorption/desorption test conducted by Belsorp
mini II apparatus. The X’Pert MPD X-ray diffractometer (XRD-
Philips Co.) using Cu/Ka radiation with a wavelength of 0.154
nm used to study the XRD pattern of the synthesized cata-
lysts. The average size (d) of NiO particle was calculated using
Sherrer equation as follow:
0:89l
d¼ (8)
bcosq
where l is the X-ray wavelength, and b is the full-width half
maximum of the NiO diffraction peak with 2q ¼ 43.55 . The
temperature-programmed reduction (TPR) experiment was
performed by QuantachromeChemBET-3000, in which the
0.05 g of catalyst is placed in a quartz tubular reactor. Previous
to the TPR measurement, the calcined catalysts were heated
from room temperature to 150  C under a pure N2 atmosphere
and stayed at this condition for 30 min to remove any mois-
ture or impurities. Then each sample was cooled down to the
room temperature, and the gas stream was switched to 5% H2/
Ar, and the temperature rises to 1073 K at a rate of 10 K/min.
Then the sample was cooled down to the room temperature in
N2, and the gas is switched to 5% H2/Ar, then catalyst tem-
perature increases to 1073 K at 10 K/min. To measuring the H2
consumption amounts, equipment is previously calibrated
using AgO2 reduction as the reference. The reduction degree
of catalysts is evaluated based on the hydrogen amount
consumption.
The size distribution of each synthesized catalysts was
measured through particle size analyzer (Nano Tec, analysette
22). The morphology and size of used catalysts were examined
by Zeiss-EM10C-100 KV transmission electron microscopy
(TEM). The composition of the catalysts was analyzed via an
energy-dispersive X-ray spectroscopy (EDX) (JEOL, JED-2300).
The amount of deposited carbon for each used catalyst in
the CSCRM process was determined using a thermogravi-
metric analyzer (TGA, TA instruments SDT 2960). The used
catalysts were collected after a long-term stability test for
400 h. 10 mg catalyst was heated from 30 to 850  C at a heating
rate of 10  C/min in oxygen to oxidize the coke on the used
catalysts in CSCRM reaction.
CSCRM reaction
The CSCRM reaction was conducted in a fixed-bed reactor
with internal/external diameters and lengths of 30/35 mm and
70 cm, respectively, located in the furnace. Previously starting
each test, 0.4 g of catalysts (3.2 cm3) were reduced by pure
hydrogen flow (55 mL/min) at a temperature of 500  C and
atmospheric pressure for 5 h. The mixture of CH4, CO2 and
H2O was used as a reactant feed gaseous. Steam is obtained by
using the evaporator. The CSCRM reactions were carried out at
various operating conditions in the range of 500  Ce1000  C,
(CO2 þ H2O)/CH4 ratio of 1e3, CO2/H2O ratio of 1e3, the gas hour
space velocity of 1030 h1 (55 mL/min) under atmospheric
pressure. Each CSCRM reaction test was carried out for 10 h.
The exit gases were analyzed through the Agilent 7890 A re-
finery gas analyzer.
The catalytic activity was evaluated through the calcula-
tion of two indexes methane conversion (xCH4) and products
selectivity as follows:
4 international journal of hydrogen energy xxx (xxxx) xxx

Results and discussion

moleof methanein inlet  moleof methanein outlet
XCH4 ð%Þ¼  100
moleof methanein inlet
Characterization results
(9)

Table 2 summarizes the BET surface area, total pore volume

molesof COproduced
COYieldð%Þ¼
ðtotalmolesof methaneFeedÞ þ ðtotalmolesof CO2 FeedÞ
 100
molesof H2 produced
H2 Yieldð%Þ¼
2  ðtotal molesof CH4 feedÞ þ ðtotalmolesof H2 OfeedÞ
 100
Experimental design
The statistical analysis of obtained results was performed by
Design-Expert software (Version 7, USA) [15,16]. Reaction
temperature (X1), in the range of 500e1000  C; (CO2 þ H2O)/CH4
ratio (X2), in the range of 1e3 and CO2/H2O ratio (X3), in the
range of 1e3, are the three independent parameters were
chosen to study their effects on the CH4 conversion (Y1), H2
yield (Y2), CO yield (Y3), amount of coke formation on the
catalyst surface (Y4) and H2/CO ratio (Y5) as the response var-
iables. All independent parameters into three coded values of
1, 0 and þ 1, as shown in Table 1.
Statistical analysis
A second-order polynomial model proposed by CCD to express
the effect of operating parameters on each response. The
proposed models for all responses include linear, quadratic
and cross-product terms as follow:
X
4 X
4 X
3 X
4
Y1 ¼ a0 þ ai Xi þ aii X2ii þ aij Xi Xj
i¼1 i¼1 i¼1 j¼iþ1
where Y can be a predicted response (i.e., CH4conversion, H2
yield, CO yield, amount of coke formation on the catalyst
surface and H2/CO ratio), a0, ai and aii are the intercepts, linear,
quadratic and interaction constant coefficients, respectively.
Xi and Xj are the independent parameters by coded or actual
values. Analysis of variances (ANOVA) used to examine the
proposed model accuracy. The value of the determination
coefficient (R2) and the adjusted R2 confirmed the suit of the
fitted polynomial model. Moreover, the significance of model
terms assessed by probability value (P-value) and fisher vari-
ation value (F-value) [17,18].
and average pore size of support and three types of prepared
catalysts, which contained a unique form of metals. The ob-
tained results showed that the BET surface area reduces by
(10) adding Pd or Ni into support. For NiePd/Al2O3 catalyst, the
surface area, total pore volume and average pore size show
lower values compared to g-Al2O3 support without metals,
which demonstrates the support collapse and also crystallite
growth resulting in the uptake of metals into the support
(11) surface well [19].
Fig. 1a shows the crystal structure of the calcined cata-
lysts, which was appraised by the XRD method using the
JCPDS files as a reference. In prepared samples, the peaks at
2q ¼ 25.57 , 37.52 and 80.3 correspond to g-Al2O3 [19e21].
The peaks of 43.55 and 74.55 are ascribed to NiO in the
spectrum of Ni/Al2O3 and NiePd/Al2O3 catalysts [22e26]. Two
weak peaks were observed at 2q ¼ 31.1 and 66.7 , which
imply the spinal structure of NiAl2O4 in spectrum XRD of Ni/
Al2O3. These peaks were due to the interaction between NiO
and Al2O3 support [27,28]. Previous studies reported that the
peaks intensity of NiAl2O4, increased by increasing the
calcination temperature [19]. Furthermore, the appeared
peaks at 2q ¼ 33.6 and 52.7 in Pd/Al2O3 and NiePd/Al2O3
catalysts are assigned to the PdO phase the [29,30]. NiAl2O4
peaks were not observed in the XRD patterns of NiePd/Al2O3
catalyst. The palladium existence in NiePd/Al2O3 sample, it
prevents the formation of interaction between nickel and
alumina support. Generally, XRD analysis suggests that there
was a mixture of Al2O3, NiO and nickel aluminate phases in
the structure of calcined Ni/Al2O3 catalyst and the mixture of
Al2O3, NiO and PdO phases in the structure of calcined NiePd/
(12) Al2O3 catalyst. For the calcined catalysts, after adding palla-
dium to Ni/Al2O3, the intensity of NiO peaks increased, and
the peaks get narrowed. The crystallinity of NiO particles
increased obviously by adding palladium, indicating that the
presence of palladium produced NiO particles with a bigger
size. The XRD patterns of Ni/Al2O3 and NiePd/Al2O3 catalysts
used in CSCRM reaction showed the presence of carbon, NiO
species and for metallic Ni (Fig. 1b). The existence of carbon
in XRD patterns (2q ¼ 27.97 ) indicated that NiO species has a
high tendency to coke deposition in the reforming process
[27]. It was found that the peak of the carbon of NiePd/Al2O3
was weaker than the Ni/Al2O3 catalyst. This case indicated
that adding the noble metals as a promoter to Ni/Al2O3

Table 2 e Characteristics of g-Al2O3, Ni/Al2O3, Pd/Al2O3

and NiePd/Al2O3 catalysts.
Table 1 e The independent parameters and their coded
and actual values. Catalyst Surface area Total pore volume Average pore
(m2/g) (cm3/g) size (nm)
Variables Symbol Coded values
g-Al2O3 221.4 0.517 8.9
1 0 þ1
Pd/Al2O3 195.3 0.497 8.1
Temperature ( C) X1 500 750 1000 Ni/Al2O3 186.7 0.459 7.3
(CO2 þ H2O)/CH4 ratio X2 1 2 3 NiePd/ 176.2 0.427 6.9
CO2/H2O ratio X3 1 2 3 Al2O3

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 1 e XRD patterns of (a) the calcined catalysts and (b) used catalysts in CSCRM reaction (at 900  C).

catalyst, restricted the coke deposition on the catalyst sur-
face during CSCRM reaction.
It should be noted that the intensity of NiO peaks
decreased, and the peaks get narrowed after the CSCRM re-
action. The position of peaks of metallic nickel placed at
2q ¼ 45.2 and 76.59 [27]. For the used catalysts, by adding
palladium to Ni/Al2O3 catalyst, the intensity of peaks assigned
to NiO decreased. However, for metallic nickel, this result was
reversed. The peaks assigned to NiAl2O4 were no seen in the
XRD spectrum of the catalyst after the CSCRM reaction (see
Fig. 1b).
The Scherrer formula used to determine the average nickel
particle size according to the characteristic diffraction peaks
at 43.55 . The obtained data showed that the average particle
size of NiO for Ni/Al2O3 and NiePd/Al2O3 was 5.24 nm and
7.15 nm, respectively. In the literature [19], it was observed
that the average particle size of nickel increases as the palla-
dium added. Moreover, the average particle size of a metallic
nickel for Ni/Al2O3 and NiePd/Al2O3 was 13.1 nm and 17.2 nm,
respectively. It can be concluded that the smaller crystallite
size of Ni makes easier to form NiO, which may strengthen the
negative effect of carbon deposition for the CSCRM reaction,
which was in good agreement with the literature [27].
Fig. 2 demonstrates the H2eTPR patterns of the calcined
catalyst. The TPR patterns reveal the reduction behavior of the
catalysts. Previous studies that have been focused on the TPR
behavior of Ni/Al2O3 interpreted a different reduction
behavior [19,22,23,31e34]. For Ni/Al2O3 catalyst, a broad
reduction peak around 600 K with a large peak area indicates
plenty of hydrogen consumption. This peak is assigned to the
reduction in NiO crystallites [27,31e34].
There was another peak at 932.8 K, which is related to NiO
species reduction, which interacts with support [35,36]. The
high reduction temperature of NiAl2O4 species (at 932.8 K)
made the nickel oxide reduction more difficult [34]. These
findings confirm the results obtained from the XRD test. The

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
6 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 2 e TPR patterns of the calcined catalysts.
TPR of the Pd/Al2O3 shows a sharp peak at 290K, which can be
ascribed to the PdO species reduction [37]. Moreover, the TPR
pattern of Pd/Al2O3 also has an inverted reduction peak at
339 K that can be attributed to the b-PdH phase decomposition
[38]. A weak interaction between these species and support is
responsible for their complete elimination from the TPR
pattern.
In TPR of NiePd/Al2O3 catalyst, a peak located at 288 K
assigned to the PdO reduction to metallic Pd. The decompo-
sition peak of the b-PdH phase was also presented in NiePd/
Al2O3 at 310 K, where it implies that the presence of nickel
facilitates the PdH phase decomposition. The peak position

assigning to the first reduction (NiO/Ni ) was shifted to a
lower temperature and appeared at 576 K compared to the Ni/
Al2O3. Previous studies also reported a similar peak position
shifting for Ni-based catalysts [19,29]. Moreover, the peak
position of the NiAl2O4 reduction was missing due to the no
interaction existence between nickel and support as the
palladium added [21]. As can be seen in Fig. 2, the peak
reduction is intensified by adding palladium to Ni/Al2O3
catalyst, which was in agreement with previous work [21].
The amount of H2 consumption and reduction degree were
calculated by the TPR test, as depicted in Table 3. Adding
palladium to Ni/Al2O3 leads to considerable growth in the
reduction degree from 69.2% to 83.1%, which can be respon-
sible for excellent catalytic performance. At the same time,
Table 3 e The H2 consumption and reduction degree for
the prepared catalysts.
Sample H2 consumption (mol) Reduction degree (%)
Ni/Al2O3 0.000117 69.2
NiePd/Al2O3 0.000136 83.1
Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
the H2 consumption presents a similar behavior. However,
variation in H2 consumption shows not as much as a reduc-
tion degree. The growth in reduction degree leads to an in-
crease of nickel particle size that is observed by the others
[19,24].
It is evident that the NiePd/Al2O3 catalyst was reduced
more convenient than Ni/Al2O3 catalyst (see Table 3), due to
the hydrogen spillover from palladium to nickel, which results
from high activation and dissociation of H2 by palladium [19].
Therefore, the nickel oxide nanoparticle would be activated
easier to provide active nickel sites over g-Al2O3 for CSCRM
reaction, which results in a higher reduction degree for NiePd/
Al2O3 catalyst.
Fig. 3 demonstrates all the size study of synthesized cata-
lysts. Fig. 3a and b reveal the results from particle size anal-
ysis, which confirms that the Ni/Al2O3 and NiePd/Al2O3
catalysts have mean sizes about 8e10 and 10e12 nm. TEM
images of calcined Ni/Al2O3 and NiePd/Al2O3 catalysts were
displayed in Fig. 3c and d. As can be seen, for both catalysts, a
homogeneous dispersion of NiO nanocrystals on the external
support surface with spherical shape was achieved. It is
apparent that no significant agglomeration occurs during
catalysts synthesis. Similar results have also been reported
previously [20e22]. The NiO average particle size for the Ni/
Al2O3 and NiePd/Al2O3 catalysts was about 9 nm and 11 nm,
which approximately approved with the values calculated by
XRD. However, the average particle sizes, which can be seen
via TEM, are slightly more significant than the corresponding
values obtained by XRD, which indicates some degree of
particle agglomeration during the catalyst synthesis. TEM
images of used Ni/Al2O3 and NiePd/Al2O3 catalysts were dis-
played in Fig. 3e and f. As can be seen in Fig. 3e and f, the
occurrence of one or two smaller particles aggregated to form
one larger particle might due to sintering during the reaction
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 3 e The particle size distribution of (a) calcined Ni/Al2O3 catalyst and (b) calcined NiePd/Al2O3 catalyst; TEM image of (c)
calcined Ni/Al2O3 catalyst, (d) calcined NiePd/Al2O3 catalyst, (e) used Ni/Al2O3 catalyst and (f) used NiePd/Al2O3 catalyst.

(10 h at 900  C). After the CSCRM reaction, the aggregation of
the nickel particles became far more widespread. By
comparing Fig. 3e and f, it is evident that aggregates of Ni/
Al2O3 were more predominant than NiePd/Al2O3 catalyst.
Thereby, the addition of palladium could somewhat prevent
the aggregation of Ni particles at the high reaction
temperature.
It is evident that the average nanoparticle size of catalysts
used in the CSCRM reaction was higher than the calcined
catalysts, which became larger due to the agglomeration of

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
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8 international journal of hydrogen energy xxx (xxxx) xxx

the particles during the reaction. The average particle size of
Ni/Al2O3 and NiePd/Al2O3 catalysts was 29 nm and 38 nm,
respectively, which indicated that for the used catalysts, the
nickel particle size calculated by TEM was remarkably higher
than XRD analysis. However, for calcined catalysts, the dif-
ference between TEM and XRD analysis was very little.
The results of EDX analysis are presented in Fig. 4a and b
for calcined catalysts. The elemental analysis given by EDX
was verified that Ni/Al2O3 catalyst was composed of Ni and Al,
and also NiePd/Al2O3 included Ni, Al and Pd. The O signal in
patterns represents that the oxidation of some surface metal
atoms was occurred [29].
Selecting appropriate catalyst
Using the present catalysts, the CSCRM is carried out at
different temperatures, and the results are shown in Table 4.
The reduction degree is low for Ni/Al2O3 catalysts that lead
to a decrease in the number of accessible nickel active sites
for CH4, and thus, the CH4 conversion reduces. By adding Pd
to Ni catalyst, the CH4 conversion increased from 49.86% to
60.01% and from 83.89% to 97.1% at 500  C and 1000  C,
respectively. According to the TPR analysis results reported
in Table 3, the reduction degree of NiePd/Al2O3 (83.1%) is
higher than Ni/Al2O3 (69.2%), where leads to higher metallic
nickel sites were obtained for CSCRM reaction. Table 4 listed
the comparison between the catalytic performance of Ni/
Al2O3 and NiePd/Al2O3 in CSCRM reaction. Clearly, under the
same process conditions, NiePd/Al2O3 had H2 yield and CO
yield higher than Ni/Al2O3 catalyst. These are closely related
to adding palladium to the Ni/Al2O3 catalyst [19,29]. More-
over, TGA results presented that the amount of coke for-
mation of NiePd/Al2O3 was lower compared to Ni/Al2O3
catalyst and could be related to the palladium presence in
NiePd/Al2O3 catalyst. This result agreed well with XRD
analysis results so that the intensity of the carbon peak for
NiePd/Al2O3 was weaker Ni/Al2O3 catalyst. It should be
noticed that the effect of temperature on the CH4 conver-
sion, product distributions and amount of coke deposition
on the catalyst surface for NiePd/Al2O3 catalyst was more
than Ni/Al2O3. Thereby, NiePd/Al2O3 catalyst was selected
for further studies.

Fig. 4 e EDX spectrums of catalyst for (a) Ni/Al2O3 (b), NiePd/Al2O3.

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 international journal of hydrogen energy xxx (xxxx) xxx 9

Table 4 e Comparison between the catalytic performance of Ni/Al2O3 and NiePd/Al2O3 in CSCRM reaction in CO2/H2O of 1
and (CO2 þ H2O)/CH4 of 1.2.
Catalyst Temperature ( C) CH4 conversion (%) H2 yield (%) CO yield (%) Amount of coke
formation (104  mol)
Ni/Al2O3 500 49.86 22.45 2.37 3.60
600 57.79 42.34 14.29 3.23
700 70.04 60.05 30.14 2.54
800 79.92 72.39 48.55 1.97
900 82.28 75.13 62.17 1.66
1000 83.89 77.88 67.17 1.54
NiePd/Al2O3 500 60.01 35.64 5.64 2.40
600 71.19 59.43 20.05 2.10
700 83.44 78.29 64.38 0.74
800 92.36 85.70 83.47 0.31
900 96.41 88.46 85.53 0.28
1000 97.10 89.77 88.72 0.21

ANOVA study clarify the correlation between independent variables and

ANOVA was accomplished to inspect the statistical signifi-
cance of five offered models presented in Table 5 e 9 for CH4
conversion, H2 yield, CO yield, amount of coke formation and
H2/CO ratio, respectively. As mentioned, F-value, R2, adjusted
R2 and P-value can be used as statistical estimators to check
the model significance. The P-value lower than 0.05, higher F-
value, the R2 and the adjusted R2 values closer to 1 demon-
strate the significance of the model [15,16]. According to
Table 5, F-value and the P-value were 22.61 and lower than
0.0001, respectively, which indicate that the designated
model for CH4 conversion was highly significant and could
response. Moreover, the R2 was 0.9532, which expressed that
more than 95.32% of the predicted data deviation from
experimental data could define the recommended model.
The adjusted R2 was 0.9110, which is closed to 1 and is usu-
ally preferred to examine the model accuracy. In this model,
temperature (T) andT2 with P-value of <0.0001 and 0.005,
respectively, were highly significant terms that exhibited a
strong influence on CH4 conversion. For H2 yield, P-value, F-
value, R2 and adjusted R2 were <0.0001, 70.32, 0.9844 and
0.9704, respectively, which implied the model could coordi-
nate well with experimental data (Table 6). In this case, T
(<0.0001), (CO2 þ H2O)/CH4(<0.0001), T  (CO2 þ H2O)/CH4

Table 5 e ANOVA of the quadratic model for CH4 conversion.

Sources Sum of squares Degrees of freedom Mean square F value P-value
CH4 conversion 5239.27 9 582.14 22.61 <0.0001
T 3194.62 1 3194.62 124.07 <0.0001
CO2/H2O 3.06 1 3.06 0.12 0.7373
(CO2 þ H2O)/CH4 0.59 1 0.59 0.023 0.8829
T  CO2/H2O 0.13 1 0.13 5.206E-003 0.9439
T  (CO2 þ H2O)/CH4 0.050 1 0.050 1.929E-003 0.9658
CO2/H2O  CO2 þ H2O)/CH4 9.870E-003 1 9.870E-003 3.833E-004 0.9848
T2 330.35 1 330.35 12.83 0.0050
[CO2/H2O]2 0.85 1 0.85 0.033 0.8597
[(CO2 þ H2O)/CH4]2 18.09 1 18.09 0.70 0.4215
Residual 257.49 10 25.75

Table 6 e ANOVA of the quadratic model for H2 yield.

Sources Sum of squares Degrees of freedom Mean square F value P-value
H2 yield 6306.76 9 700.75 70.32 <0.0001
T 2167.64 1 2167.64 217.52 <0.0001
CO2/H2O 1.61 1 1.61 0.16 0.6964
(CO2 þ H2O)/CH4 528.52 1 528.52 53.04 <0.0001
T  CO2/H2O 0.46 1 0.46 0.046 0.8339
T  (CO2 þ H2O)/CH4 181.68 1 181.68 18.23 0.0016
CO2/H2O  CO2 þ H2O)/CH4 14.27 1 14.27 1.43 0.2590
T2 1332.92 1 1332.92 133.76 <0.0001
[CO2/H2O]2 3.32 1 3.32 0.33 0.5769
[(CO2 þ H2O)/CH4]2 8.20 1 8.20 0.82 0.3856
Residual 99.65 10 9.97

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10 international journal of hydrogen energy xxx (xxxx) xxx

Table 7 e ANOVA of the quadratic model for CO yield.

Sources Sum of squares Degrees of freedom Mean square F value P-value
CO yield 18308.05 9 2034.23 62.73 <0.0001
T 10037.12 1 10037.12 309.49 <0.0001
CO2/H2O 70.68 1 70.68 2.18 0.1706
(CO2 þ H2O)/CH4 218.52 1 218.52 6.74 0.0267
T  CO2/H2O 36.76 1 36.76 1.13 0.3121
T  (CO2 þ H2O)/CH4 70.67 1 70.67 2.18 0.1707
CO2/H2O  CO2 þ H2O)/CH4 10.98 1 10.98 0.34 0.5735
T2 1798.46 1 1798.46 55.46 <0.0001
[CO2/H2O]2 0.13 1 0.13 4.115E-003 0.9501
[(CO2 þ H2O)/CH4]2 24.81 1 24.81 0.76 0.4023
Residual 324.31 10 32.43

(0.0016) and T2 (<0.0001) were highly significant terms.
Compared to other parameters, the highest F-value and the
lowest P-value of temperature indicated its superior effect on
H2 yield, and also, the effect of quadratic T2 was very
noticeable compared to other interaction parameters.
Furthermore, for CO yield in Table 7, the P-value, F-value, R2
and adjusted R2 were (<0.0001), 62.73, 0.9826 and 0.9669,
respectively, which implied the model data was fitted
perfectly with the experimental one. For the case of CO yield,
all T (<0.0001), (CO2 þ H2O)/CH4 (0.0267) and T2 (<0.0001) were
highly significant parameters, in which owing to the highest
F-value, the temperature had the largest impact on CO yield.
For the amount of coke formation on the catalyst support, P-
value, F-value, R2 and adjusted R2 were 0.0009, 9.07, 0.89 and
0.7926, respectively, which implied the model could coordi-
nate well with experimental data (Table 8). For this case of T
(0.0003) and T2 (0.0076) were highly significant terms.
Compared to other parameters, the temperature indicated a
more eminent effect on the amount of coke formation.
For the H2/CO ratio, P-value, F-value, R2 and adjusted R2
were 0.0006, 10.17, 0.9014 and 0.8128, respectively, which
implied the model is in a good agreement with experimental
data (Table 9). In this case, T (0.0003) and T2 (0.0028) were
highly significant terms. Compared to other parameters, the
lower value of P-value for temperature showed that had a high
effect on the H2/CO ratio, and also the effect of quadratic T2
was very noticeable compared to other interaction
parameters.

Table 8 e ANOVA of the quadratic model for amount of coke formation.

Sources Sum of squares Degrees of freedom Mean square F value P-value
Amount of coke formation 24.43 9 2.71 9.07 0.0009
T 8.45 1 8.45 28.23 0.0003
CO2/H2O 0.31 1 0.31 1.05 0.3298
(CO2 þ H2O)/CH4 0.45 1 0.45 1.5 0.2481
T  CO2/H2O 0.94 1 0.94 3.15 0.1063
T  (CO2 þ H2O)/CH4 0.49 1 0.49 1.63 0.2307
CO2/H2O  CO2 þ H2O)/CH4 0.011 1 0.011 0.037 0.8515
T2 3.32 1 3.32 11.08 0.0076
[CO2/H2O]2 0.045 1 0.045 0.15 0.7056
[(CO2 þ H2O)/CH4]2 0.63 1 0.63 2.09 0.1786
Residual 2.99 10 0.3

Table 9 e ANOVA of the quadratic model for H2/CO ratio.

Sources Sum of squares Degrees of freedom Mean square F value P-value
H2/CO ratio 179.3 9 19.92 10.17 0.0006
T 58 1 58 29.6 0.0003
CO2/H2O 6.95 1 6.95 3.54 0.0891
(CO2 þ H2O)/CH4 4.25 1 4.25 2.17 0.1717
T  CO2/H2O 2.4 1 2.4 1.23 0.293
T  (CO2 þ H2O)/CH4 2.41 1 2.41 1.23 0.2935
CO2/H2O  CO2 þ H2O)/CH4 0.22 1 0.22 0.11 0.7442
T2 30.35 1 30.35 15.49 0.0028
[CO2/H2O]2 3.19 1 3.19 1.63 0.2301
[(CO2 þ H2O)/CH4]2 0.55 1 0.55 0.28 0.6093
Residual 19.59 10 1.96

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
 international journal of hydrogen energy xxx (xxxx) xxx 11

Table 10 e Experimental plan of Central Composite Design (CCD) and obtained results from suggested models for CH4
conversion, H2 yield and CO yield.
NO. T ( C) CO2/H2O (CO2 þ H2O)/CH4 CH4 Conversion H2 Yield (%) CO Yield (%)
(%)
Exp. Pred. Exp. Pred. Exp. Pred.
1 500.00 1.00 1.50 52.3 54.8599 35.6 38.1421 5.7 3.8087
2 1000.00 1.50 1.00 96.4 96.0701 91.2 90.8152 83.4 84.6566
3 700.00 2.50 1.00 81.3 81.7546 80.0 80.8414 63.4 64.7619
4 1000.00 3.00 1.00 98.4 97.321 90.6 89.9504 97.2 97.5675
5 500.00 1.00 3.00 51.6 51.752 32.5 33.447 5.3 1.29319
6 900.00 1.00 3.00 95.8 34.5183 61.8 64.1067 66.7 67.1195
7 500.00 3.00 1.00 50.1 54.408 37.5 37.9842 6.3 3.86833
8 1000.00 3.00 3.00 97.7 96.8095 61.5 59.1866 71.6 71.7478
9 600.00 1.50 2.50 71.5 70.5485 57.5 53.863 31.4 34.3005
10 1000.00 2.00 2.00 97.7 99.3099 69.3 70.1716 82.3 81.6681
11 800.00 1.00 2.50 90.1 91.9827 75.4 72.5613 65.9 69.2077
12 800.00 3.00 2.50 91.4 93.1757 72.4 75.7634 74.6 75.1561
13 600.00 2.00 1.50 76.5 71.1723 60.1 59.4219 27.7 37.7946
14 500.00 2.50 1.50 63.4 55.7291 38.7 35.7664 5.8 4.60064
15 800.00 2.00 2.00 91.6 92.9224 75.6 77.9988 78.4 76.5395
16 700.00 1.00 2.00 88.4 84.1428 73.6 71.6885 58.6 58.8387
17 750.00 2.50 2.00 93.7 89.5182 77.5 75.8929 74.7 71.5505
18 900.00 2.00 1.50 95.6 97.2463 83.7 85.5497 91.6 87.0071
19 750.00 2.00 1.50 87.6 88.3515 83.4 80.8061 81.7 72.0655
20 600.00 2.00 2.00 62.3 71.8072 52.3 56.2427 31.3 37.0477

Table 11 e The test run of Central Composite Design (CCD) and obtained results from suggested models for the amount of
coke formation and H2/CO ratio.
NO. T ( C) CO2/H2O ratio (CO2 þ H2O)/CH4 ratio Amount of coke formation H2/CO ratio
(104  mol)
Experimental Predicted Experimental Predicted
1 500.00 1.00 1.50 2.60 2.57 13.2 11.39
2 1000.00 1.50 1.00 0.36 0.23 1.3 1.43
3 700.00 2.50 1.00 0.44 0.88 2.1 1.76
4 1000.00 3.00 1.00 0.21 0 1.4 1.81
5 500.00 1.00 3.00 0.27 0.99 8.2 7.92
6 900.00 1.00 3.00 0.22 0 1.7 1
7 500.00 3.00 1.00 3.94 3.89 7.3 7.67
8 1000.00 3.00 3.00 0.18 0.083 1.27 2.32
9 600.00 1.50 2.50 2.26 1.12 3.7 4.14
10 1000.00 2.00 2.00 0.19 0.4 1.5 1.51
11 800.00 1.00 2.50 0.29 0.28 1.96 1.96
12 800.00 3.00 2.50 0.33 0.51 1.78 0.57
13 600.00 2.00 1.50 2.06 1.89 3.0 4.32
14 500.00 2.50 1.50 3.42 3.56 7.9 7.43
15 800.00 2.00 2.00 0.28 0.52 1.65 0.51
16 700.00 1.00 2.00 0.67 0.79 1.72 3.65
17 750.00 2.50 2.00 0.78 0.84 1.43 0.87
18 900.00 2.00 1.50 0.21 0.31 1.38 0.49
19 750.00 2.00 1.50 0.51 0.68 1.39 1.26
20 600.00 2.00 2.00 2.2 1.78 2.7 3.7

Model analysis
Central Composite Design (CCD) with 20 different runs are
listed in Tables 10 and 11, which designed to evaluate the
influence of parameters on the CH4 conversion, H2 yield, CO
yield, amount of coke formation on the catalyst surface and
H2/CO ratio in the CSCRM reaction.
The fitted polynomial second-order models in terms of
actual factors for CH4 conversion (Y1), H2 (Y2) and CO yields
(Y3), coke deposition (Y4) and H2/CO ratio (Y5) is as follow:

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
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12 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e Three-dimensional response surface plots for combined effect of (a) temperature and CO2/H2O ratio, (b) temperature
and (CO2 þ H2O)/CH4 ratio, and (c) CO2/H2O ratio and (CO2 þ H2O)/CH4 ratio on the CH4 conversion.

Y1 ¼ e92:09916 þ 0:36397X1 e1:17633 X2 þ 12:78674 X3 e8:34579  104 X1 X2

(13)
e0:054781 þ 5:05663  104 X1 X3 X2 X3 e1:84095  104 X1 2 þ 0:64436 X2 2 e3:34595 X3 2

Y2 ¼ e188:95871 þ 0:68455 X1 e9:94339 X2 e0:060998 X3 þ 1:54848  103 X1 X2

(14)
e0:030583X1 X3 þ 2:08304 X2 X3 e3:69790  104 X1 2 þ 1:27451 X2 2 þ 2:25315 X3 2

Y3 ¼ e311:21334 þ 0:80932 X1 e4:53568 X2 þ 27:31846 X3 þ 0:013820 X1 X2

(15)
e0:019074 X1 X3 e1:82750 X2 X3 e4:29540  104 X1 2 þ 0:25573 X2 2 e3:91803 X3 2

Y4 ¼ 11:97522 þ 0:030892 X1 þ 0:89954 X2 þ 1:16161 X3 þ 0:00158413 X1 X2

(16)
e0:00221338 X1 X3 þ 0:057973 X2 X3 þ 1:8445  105 X1 2 e0:62254 X2 2 þ 0:14890 X3 2

responses in CSCRM reaction, which are shown in Fig. 5 a-c

Y5 ¼ 59:22  0:1095 X1  9:1747 X2  1:7154 X3 þ 3:5343 X1 X2
þ3:5212 X1 X3 þ 0:2589 X2 X3 þ 5:58 X1 2 þ 1:25 X2 2  0:58 X3 2
(17)
As presented in Tables 10 and 11, the wide ranges of CH4
conversion, H2 yield, CO yield, coke deposition and H2/CO ratio
(50.1e98.4%, 35.6e91.2%, 5.3e97.2%, 0.18e3.94 104  mol and
1.27e13.2), were observed which indicate that three inde-
pendent variables had remarkable effect on the responses.
Effect of independent process variables on the responses
Three-dimensional response surface graphs are useful and
assist the learning about the influence of independent vari-
ables (i.e., Temperature, CO2/H2O ratio and (CO2 þ H2O)/CH4
ratio) and also the effect of their interaction on the
and 9 a-c.
Effect of temperature
The effect of temperature on three desired responses is pre-
sented in Fig. 5a and b. Rising temperature is one of the most
effective and accessible strategies to achieve higher CH4
conversion.
Since the CSCRM reaction is naturally highly endothermic;
thus, as the temperature increased, the reactions tend to the
higher CH4 conversion. This increment was based on Le
Chatelier’s principle. According to Fig. 5a and b, CH4 conver-
sion increased gradually by raising the temperature in the
range of 500  Ce1000  C, while other variables (i.e.,
(CO2 þ H2O)/CH4 and CO2/H2O ratio) adjusted at any values and
also it can be seen that the total conversion is almost acces-
sible at temperatures higher than 850  C. This indicated that
the high reduction degree of NiePd/Al2O3 (see Table 3) and the

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 international journal of hydrogen energy xxx (xxxx) xxx 13

Fig. 6 e Three-dimensional response surface plots for combined effect of (a) temperature and CO2/H2O ratio, (b) temperature
and (CO2 þ H2O)/CH4 ratio, and (c) CO2/H2O ratio and (CO2 þ H2O)/CH4 ratio on the H2 yield.

Fig. 7 e Three-dimensional response surface plots for combined effect of (a) temperature and CO2/H2O ratio, (b) temperature
and (CO2 þ H2O)/CH4 ratio, and (c) CO2/H2O ratio and (CO2 þ H2O)/CH4 ratio on the CO yield.

meager amount of coke deposition on the catalyst surface (see
Fig. 1b), which leads to higher metallic nickel sites, were ob-
tained for CSCRM reaction.
Shinde et al. [39] represented the effect of temperature on
the CH4 conversions in CSCRM reaction. Their obtained results
showed that by raising the temperature, CH4 conversion had
an increasing trend. Moreover, Maestri et al. [40] reached
similar results. Aydinoglue et al. [12] observed that CH4 con-
version increased from 40.7% to 99.5% in the temperature
range of 600e1200  C at the atmospheric pressure and
(CO2 þ H2O)/CH4 ratio of 1.

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
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14 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 8 e Three-dimensional response surface plots for combined effect of (a) temperature and CO2/H2O ratio, (b) temperature
and (CO2 þ H2O)/CH4 ratio, and (c) CO2/H2O ratio and (CO2 þ H2O)/CH4 ratio on the H2/CO ratio.

Based on the ANOVA study (See Table 6), a significant
interaction between temperature and (CO2 þ H2O)/CH4 ratios
was seen, which influenced on H2 yield (P-value ¼ 0.0016). As
can be seen in Fig. 6 (a), at higher (CO2 þ H2O)/CH4 ratio; first,
the H2-yield increases as the temperature increases and then
decreases (show a maximum point). At lower temperature
intervals, increasing temperature results in a higher rate of
CSCRM reaction, which produces hydrogen, and also, the WGS
reaction leads to hydrogen production as well. Thus, the H2
yield increases. This behavior can be assigned to the
exothermic nature of the WGS reaction (Eq. (4)) [1]. At lower
temperatures, the rate of WGS reaction was more than RWGS
[1]. Conversely, at higher temperature interval, the H2 yield
decreases as the temperature increases. For higher
(CO2 þ H2O)/CH4 ratio, the significant CO2 is available to react
with hydrogen in RWGS reaction, and also methane as a
limiting agent in CSCRM has a limited quantity, the rate of H2
consumption surpasses its generation and thus the overall H2-
yield decreases by increasing temperature. It should be noted
that the rate of RWGS, which consumes hydrogen is more
than WGS at higher temperatures. Obtained results from Fig. 6
(b) demonstrates that for lower (CO2 þ H2O)/CH4 ratio, the H2-
yield curve shows ascending trend as the temperature in-
creases in the range of 500e1000  C. At higher temperature
intervals, the high quantity of methane led to an increase in
the rate of hydrogen production, which is almost similar to
the rate of H2 consumption in RWGS. Thereby, the H2 yield
was almost fixed at the higher temperatures. Jang et al. [1] also
mentioned the interaction between temperature and
(CO2 þ H2O)/CH4 ratio, and the same results for H2 yield vari-
ation were obtained. H2 yield increased from 39.4% to 99.6% in
the temperature range of 600  Ce1200  C at the atmospheric
pressure (CO2 þ H2O)/CH4 ratio of 1 and CO2/H2O ratio of 2 [12].
In Fig. 7(a and b), CO yield raised by raising temperature due
to CO formation in CSCRM and RWGS reaction. At high tem-
peratures, the RWGS reaction is more favored than WGS (Eq.
(4)) to be accomplished; thus, more CO was produced by raising
the temperature. At proximity of the initial point, CO yield was
almost equal zero because, at this temperature range, the rate
of CSCRM was slow contrary to WGS; thus, the produced CO in
CSCRM immediately consumed in WGS reaction. As can be
seen in Fig. 7(a and b), CO yield about 100% was accessible at
temperatures higher than 850  C. Soria et al. [41] reported that
the variation of CO yield with temperature was an increment
trend. In the literature [12], CO yield increased from 33% to
99.7% in the temperature range of 500  Ce1200  C at the at-
mospheric pressure (CO2 þ H2O)/CH4 ratio of 1 and CO2/H2O
ratio of 0.5. However, in this study, CO yield increased from
5.3%e97.2% in the temperature range of 500  Ce1000  C.
Therefore, it might conclude that the effect of temperature on
the CO yield was remarkably higher than literature.
According to Fig. 8a and b, the values of high H2/CO ratios
were obtained in the temperature region of below 600  C due to
the formation of hydrogen via the CH4 decomposition (Eq. (6))
and the consumption of CO by the Boudouard reaction (Eq. (7))
and WGS (Eq. (4)) [1,13,14]. H2/CO ratio gradually approached the
range of 1e2 with an increase in temperature at any values of
other independent variables (i.e., CO2/H2O ratio and (CO2 þ H2O)/
CH4 ratio). This could be due to the tendency of RWGS (Eq. (5)) in
the higher temperatures [1,14], which leads to the consumption
of hydrogen and the formation of monoxide carbon. Thereby,
the low H2/CO ratio obtained in the high temperatures. Also, the
decrease of the H2/CO ratio at higher temperature could be
assigned to the favored dry reforming than the steam reforming
reaction at high temperatures [13,14]. H2/CO ratio decreased in
the range of 2.69-2 with increasing of temperature from 500  C to

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
 international journal of hydrogen energy xxx (xxxx) xxx 15

Fig. 9 e Three-dimensional response surface plots for combined effect of (a) temperature and CO2/H2O ratio, (b) temperature
and (CO2 þ H2O)/CH4 ratio, and (c) CO2/H2O ratio and (CO2 þ H2O)/CH4 ratio on the amount of coke formation.

1000  C [12], while variations of H2/CO ratio against temperature
was significant in this work.
Effect of CO2/H2O ratio
The CH4 conversion, H2 and CO yields variation in terms of
CO2/H2O ratio are shown in Fig. 5a and c, Fig. 6a and c, Fig. 7a
and c, respectively. As can be seen, CH4 conversion, H2 and CO
yields almost remained constant for all values of the CO2/H2O
ratio. Previous studies also reported this trend for all re-
sponses. Jang et al. [1] stated the low impact of CO2/H2O ratio
on CH4 conversion, H2 and CO yields. However, their study
showed that at temperatures lower than 800  C, the change in
CO2/H2O ratio influenced on the CH4 conversion. Their ob-
tained results exhibited that the feed stream containing more
CO2 resulted in more CH4 conversion. On the other hand, at
the temperatures higher than 800  C, the type of oxidation
agent had no significant effect on CH4 conversion, which
agreed with the results presented in this study. Besides, the
ANOVA study confirms the negligible effect of the CO2/H2O
ratio on CH4 conversion, H2 and CO yields (Tables 5e7).
Fig. 9 a and c depicts the variation of H2/CO ratio against the
CO2/H2O ratio. When the portion of CO2 was more significant
than that of H2O, synthesis gas with a low H2/CO ratio was
produced via dry reforming of methane [1,13,14]. The H2/CO
ratio increased with the increase of H2O amount in inlet feed
due to the occurrence of steam reforming of methane. Thus, it
can be concluded that the H2/CO ratio decreased by increasing
of CO2/H2O ratio at any values of variables of CO2/H2O ratio and
(CO2 þ H2O)/CH4 ratio.
Effect of (CO2þH2O)/CH4 ratio
As can be seen in Fig. 5b and c, the methane conversion
remained unchanged versus (CO2 þ H2O)/CH4 ratio for all
temperatures and CO2/H2O values. Jang et al. [1] also investi-
gated the effect of (CO2 þ H2O)/CH4 ratio on CH4 conversion.
Their results exhibited that the (CO2 þ H2O)/CH4 ratio has no
significant effect on CH4 conversion versus temperature
variation so that CH4 conversion was in the range of 95%e99%
[1]. In fact, their results implied that at 500  C, the CH4 con-
version decreased in the range of 50%e39% by increasing
(CO2 þ H2O)/CH4 ratio from 0.9 to 2.9. While at temperature
900  C, the opposite trend was seen, and the CH4 conversion
increased slightly by increasing (CO2 þ H2O)/CH4 ratio from 0.9
to 2.9 [1].
For H2 yield, as mentioned earlier, an interaction between
(CO2 þ H2O)/CH4 ratio and the temperature was recognized. Ac-
cording to Fig. 6b and c, H2 yield totally decreased by increasing
(CO2 þ H2O)/CH4 ratio and, also this trend was intensified at
higher temperatures (i.e., 1000  C). This conclusion was similar
to the different reports [13,14]. Jang et al. [1] reached to H2 yield
approximately 100% with (CO2 þ H2O)/CH4 ratio of 0.9 at above
900  C. At the temperature of 1000  C, due to the high activity of
RWGS, the rate of decreasing trend of H2 yield against
(CO2 þ H2O)/CH4 ratio amplified. In contrast, at the temperature
of 500  C, (CO2 þ H2O)/CH4 ratio had less impact on H2 yield due to
the lower CSCRM and RWGS activity. Lower (CO2 þ H2O)/CH4
means higher methane fed to process, which consequences to
higher H2 yield. Nevertheless, as the (CO2 þ H2O)/CH4 ratio in-
creases, more amount of oxidizing agent is available. Indeed, the
hydrogen consumed by the RWGS reaction, which led to the H2
yield decline. As shown in Fig. 7b and c, the CO yield decreased
gradually by increasing (CO2 þ H2O)/CH4 ratio for all temperature
and CO2/H2O ratio values. Since the primary source of CO pro-
duction is CSCRM reaction, lower (CO2 þ H2O)/CH4, which means
more methane existence in process feed, can result in higher CO
yield. Jang et al. [1] examined the effect of (CO2 þ H2O)/CH4 ratio

Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
16 international journal of hydrogen energy xxx (xxxx) xxx
on CO yield. Their results were the same with outcomes ob-
tained by present work.
The effect of (CO2 þ H2O)/CH4 ratio on the H2/CO ratio was
seen in Fig. 8 (b and c). H2/CO ratio decreased by increasing of
(CO2 þ H2O)/CH4 ratio at all values of CO2/H2O ratios and
temperatures. Generally, it should be noted that (CO2 þ H2O)/
CH4 ratio had a little effect on the H2/CO ratio because of the
high p-value (see Table 9). H2/CO ratio decreased to the
beneath of 2.0 for (CO2 þ H2O)/CH4 ratios of higher than 2 at
temperatures above 800  C [1,13,14]. However, H2/CO ratio was
higher than 2.0 below 800  C at all values of (CO2 þ H2O)/CH4
ratios, because of the SRM reaction was dominant than DRM
[1,13,14]. These results were in good agreement with this
work. In the literature [1,13], it described that the effect of
(CO2 þ H2O)/CH4 ratio on the H2/CO ratio was higher at the
lower temperatures.
Stability
As mentioned, the main problem of Ni-based catalysts in the
reforming process is deactivation due to the coke deposition.
Table 11 illustrated the amount of accumulated coke on the
surface of catalysts spent in CSCRM reaction for different
operating conditions by using TGA. The coke deposition on Ni-
based catalysts is assigned to CH4 decomposition (Eq. (6)) and
the Boudouard reaction (Eq. (7)) [1,13].
The effect of temperature, (CO2 þ H2O)/CH4 ratio and CO2/
H2O ratio on the amount of coke formation has been presented
in Fig. 9a, b and c. According to Table 8, it is obvious that
temperature had the most sustainable influence on the coke
deposition (P-value: 0.0009) so that the higher temperature is a
favor for the inhabitation of coke formation on the catalyst
surface (see Fig. 9a and b). The XRD analysis results confirmed
that the amount of coke formation on the used catalyst sur-
face in CSCRM reaction (at 900  C) was meager, which was in a
good agreement with TGA results (see Fig. 1b). Jang et al. [1]
founded that the coke deposition was about zero above 800  C
ignoring (CO2 þ H2O)/CH4 ratio and CO2/H2O ratio. It is reported
that the Boudouard reaction was suitable at low temperatures
and did not occur above 900  C [13,14]. This is because of
Boudouard reaction is an exothermic reaction. However, in
the high-temperature region, the portion of methane
decomposition in the coke formation of the CSCRM reaction
was significantly higher than the Boudouard reaction [1]. This
indicated that the methane decomposition is an endothermic
reaction. According to the obtained results, it could conclude
that the Boudouard reaction in the low-temperature region is
the fundamental factor of coke formation on the catalyst
surface.
According to Fig. 9a and c, when the portion of CO2 was
more significant than that of H2O, the coke formation was
intensified. This proved that the H2O could be more effectively
prevent the formation of coke than CO2. It was reported that
the notable aspects which affect the coke formation are the
type and amount of the oxidizing agent as well as the tem-
perature [1,13,14]. The amount of deposited carbon decreased
by increasing the (CO2 þ H2O)/CH4 ratio at all values of tem-
peratures and CO2/H2O ratios. This outcome proved that the
higher (CO2 þ H2O)/CH4 ratio can decrease the coke formation
(Fig. 9b and c). Generally, three factors of temperature, type
and amount of the oxidizing agent could affect the coke
Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137
formation. Thereby, these results revealed that lower CO2/H2O
ratio, higher temperature and (CO2 þ H2O)/CH4 ratio might
prevent the coke formation.
Conclusion
As indicated by this work, the accompanying ends can be
drawn:

The NiePd/Al2O3 and Ni/Al2O3 catalysts were synthesized
by the sol-gel method and their performance evaluated in
CSRM for syngas formation. The BET, TEM, EDX, XRD and
TPR characterization analysis have been used to evaluate
the morphology of the catalysts, elemental analysis and
crystal phase structure and reduction behavior. Charac-
terization results emphasized that a notable enhancement
in reduction degree observed from 69.2% to 83.1% by add-
ing of palladium to Ni/Al2O3, where lead to a significant
increase in CH4 conversion, H2 and CO yield of NiePd/Al2O3
compared to Ni/Al2O3 catalyst. Also, TGA and XRD results
of the used catalysts showed that the amount of coke
deposition of NiePd/Al2O3 was lower than Ni/Al2O3.
Thereby, NiePd/Al2O3 catalyst was selected for further
studies.

Five mathematical models by second-order polynomial
equation were used to investigate the effect of three in-
dependent operating variables such as reaction tempera-
ture, (CO2 þ H2O)/CH4 ratio and CO2/H2O ratio on the
responses (CH4 conversion, H2 yield, CO yield, amount of
coke formation on the catalyst surface and H2/CO ratio) in
CSCRM reaction by using response surface methodology
(RSM), Central Composite Design (CCD) method. The values
of R2 and P-value obtained from ANOVA for responses were
described that the presented models could well predict the
experimental data.

The methane conversion, H2 yield, CO yield and H2/CO ratio
were very sensitive to the working parameters, particularly
reaction temperature. ANOVA results presented that the P-
value of temperature was very little for all responses,
where indicated to the stronger influence of temperature
than other independent variables. CH4 conversion and CO
yield raised by raising the temperature. CH4 conversion
and CO yield about 100% was achieved at temperatures
higher than 850  C. The effect of temperature on the H2
yield depended on (CO2 þ H2O)/CH4 ratio. For lower
(CO2 þ H2O)/CH4 ratios, H2 yield gradually increased by
increasing temperature. While for higher (CO2 þ H2O)/CH4
ratios, H2 yield passed a maximum point.

According to high P-value of CO2/H2O variable in ANOVA of
three response of CH4 conversion, H2 and CO yields, each
three response were fixed by changing of CO2/H2O ratio.
However, the syngas with a low H2/CO ratio was produced
when the portion of CO2 was more significant than H2O in
the inlet feed.

The methane conversion remained unchanged versus
(CO2 þ H2O)/CH4 ratio. The CO yield and H2 yield decreased
gradually by increasing (CO2 þ H2O)/CH4 ratio in the range
of 1e3. H2/CO ratio. However, for H2 yield, this decreasing
trend was intensified at higher temperatures (i.e., 1000  C).
 international journal of hydrogen energy xxx (xxxx) xxx

Three factors of temperature, type and amount of the
oxidizing agent could affect the coke formation, especially
temperature. The amount of coke formation decreased by
increasing the temperature and the (CO2 þ H2O)/CH4 ratio.
The amount of coke formation decreased by increasing the
portion of H2O in the oxidizing agent.
Acknowledgment
The authors acknowledge Babol Noshirvani University of
Technology for financially support of this project (Grant NO.
BNUT/393054/2019).
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Please cite this article as: Batebi D et al., Combined steam and CO2 reforming of methane (CSCRM) over NiePd/Al2O3 catalyst for syngas
formation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.137