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Journal of Industrial and Engineering Chemistry

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Effect of alkaline earth promoters (MgO, CaO, and BaO) on the activity
and coke formation of Ni catalysts supported on nanocrystalline Al2O3
in dry reforming of methane
Zahra Alipour a, Mehran Rezaei a,b,*, Fereshteh Meshkani a
a
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan, Iran
b
Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan, Iran

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

Article history: Ni/Al2O3 promoted catalysts with alkaline earth metal oxides (MgO, CaO, and BaO) were prepared and
Received 25 July 2013 employed in dry reforming of methane (DRM). The catalysts were prepared by impregnation method and
Accepted 4 November 2013 characterized by XRD, BET, TPR, TPO, and SEM techniques. The obtained results showed that the addition
Available online xxx
of MgO, CaO, and BaO as promoter decreased the surface area of catalysts (SBET). The catalysis results
exhibited that adding alkaline earth promoters (MgO, CaO, and BaO) enhanced the catalytic activity and
Keywords: the highest activity was observed for the MgO promoted catalyst. TPR analysis showed that addition of
Nickel
MgO increased the reducibility of nickel catalyst and decreased the reduction temperature of NiO
Alkaline earth promoter
species. The TPO analysis revealed that addition of promoters decreased the amount of deposited coke;
Syngas
Dry reforming of methane and among the studied promoters, MgO has the most promotional effect for suppressing the carbon
Coke formation formation. SEM analysis confirmed the formation of whisker type carbon over the spent catalysts.
ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction and, CO decomposition reaction:

Production of synthesis gas (H2 and CO) by the catalytic reaction
of carbon dioxide reforming of methane has attracted much
attention due to its environmental and industrial importance. Two
important greenhouse gases (CH4 and CO2) are simultaneously
converted into useful synthesis gases (CO and H2) during the DRM
reaction. In addition, this process gives a lower H2/CO ratio, which
is desirable for synthetic reactions of oxygenated compounds, such
as the Fischer–Tropsch and hydroformylation reactions [1–6].
The major drawback of the dry reforming process is the rapid
coke deposition that causes catalyst deactivation, catalyst destruc-
tion, and reactor blockage. The coke originates mainly from two
reactions:
The methane cracking reaction
CH4 $ C þ 2H2 DH0298 ¼ 75 kJ=mol
* Corresponding author at: University of Kashan, Chemical Engineering Depart-
ment, Catalyst and Advanced Materials Research Laboratory, Km 6 Ravand Road,
Kashan, Iran. Tel.: +98 361 5912469, fax: +98 361 5559930.
E-mail address: rezaei@kashanu.ac.ir (M. Rezaei).
2CO $ C þ CO2 DH0 298 ¼ 172 kJ=mol½911; 17: (2)
The deposited carbon could cover the active center and
consequently, result in the deactivation of the catalysts. Until
now, more than 10 kinds of single metals and a large number of
alloys have been reported for the dry reforming reactions [5].
Among them, Ni, Co, Rh, and Pt were the most reported catalysts.
Due to its higher reactivity, availability, and lower price compared
with noble metals, nickel is the most frequently reported metal in
dry reforming of methane. However, Ni-based catalysts deactivate
easily due to carbon deposition and/or metal sintering. Therefore,
much effort has focused on improving the activity and stability of
Ni in the following aspects: changing the nature of the support,
selecting the support, and catalyst preparation method and the
addition of promoters [3,5,11,12]. Al2O3 and SiO2 supported Ni
(1) catalysts have been widely investigated for dry reforming of
methane [5,8,12,13]. Ni/Al2O3 and Ni/SiO2 prepared by impregna-
tion had high initial conversions but deactivated with time due to
carbon deposition or sintering. Many modification methods have
been studied to improve the performance of Ni/Al2O3 and Ni/SiO2
catalysts, which include different preparation methods, pretreat-
ments, and precursors or adding metal or oxide promoters to
influence the acidity and basicity, the dispersion of Ni, and/or the

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metal support interaction [12]. As carbon formation occurs easily
during dry reforming process, it was suggested that increase in
adsorption and activation of CO2 would accelerate the gasification
of the surface carbons, and retard the formation of inactive carbon
[5,9]. In order to increase the alkalinity of the catalyst, a lot of basic
materials were selected to support Ni catalysts. At the same time,
alkali-, alkaline-, and rare-earth metals promoted Ni catalysts were
also reported extensively. Certain amount of alkaline-earth metal
oxide MgO and CaO could improve the catalytic performance of Ni/
Al2O3 and Ni/SiO2 because of the strong interaction between Ni and
support; and the basic property of metal oxide could depress
carbon formation in the dry reforming process [3,12].
The objective of this study is to prepare supported Ni-based
catalysts that maintain high activity and stability while minimiz-
ing the formation of coke during the dry reforming of methane. We
investigated the influence of MgO, CaO, and BaO as promoters on
the activity, stability, and coke formation of Ni/g–Al2O3 catalysts in
CO2 reforming of methane. In addition, the effect of feed ratio and
GHSV on the catalytic performance of DRM over the catalysts was
studied.
10 8C/min. Scanning electron microscopy (SEM) analysis was
performed with VEGA TESCAN that was operated at 30 kV.
2.3. Catalytic evaluation
The catalytic evaluation was performed in a tubular fixed-bed
continuous-flow reactor of quartz under atmospheric pressure.
The reactor was charged with 200 mg of the crushed and sieved
(35–60 mesh) catalyst. Prior to the reaction, the catalysts were
reduced in situ at 600 8C for 4 h in flowing H2 (20 ml/min). After
that, the reactant gas feed containing a mixture of CH4 and CO2 was
introduced into the reactor, and the activity tests were carried out
at different temperatures ranging from 550 to700 8C in steps of
50 8C that were kept for 30 min at each temperature. The gas
composition of reactants and products were analyzed using a gas
chromatograph equipped with a TCD and a carboxen 1000 column.
3. Results and discussion
3.1. Structural properties of the catalysts

2. Experimental
2.1. Catalysts preparation
The catalysts employed in the present work were prepared by a
wet impregnation method. Nickel nitrate (NiN2O6.6H2O),
MgN2O6.6H2O, CaN2O6.4H2O, and BaN2O6 were used as Ni, Mg,
Ca, and Ba precursors, respectively. g-Al2O3 as catalyst support was
prepared by sol–gel method. For this purpose, aluminum tri
isopropylate (98% purity, Merck) was first hydrolyzed in distillated
water by stirring for 1 h at 80–85 8C. Subsequently, HNO3 was
added drop wise with HNO3 to Al molar ratio of 1:1 and refluxed for
12 h at 98 8C. After that, the sol was kept for 2 h at 98 8C in air. After
this step the sol was became so viscous. The formed gel was dried
overnight at 80 8C and calcined at 600 8C for 4 h. Then, prepared g-
Al2O3 was impregnated with an aqueous solution of salt promoter
with appropriate concentration to obtain 3 wt.% of promoter. After
impregnation, the promoted support was dried at 80 8C overnight
and calcined at 500 8C for 4 h. After that, the promoted g-Al2O3 was
impregnated with nickel nitrate with the same procedure as
described above.
Fig. 1 shows the XRD patterns of the promoted and unpromoted
catalysts. It is seen that all catalysts have crystalline structure and
as shown in Fig. 1 with addition of alkaline earth promoters (MgO,
CaO, and BaO) into the catalysts, no additional diffraction peak
could be clearly observed. This result implies that all of these
promoters were highly dispersed as small particles on support.
Also all XRD patterns did not show the diffraction peaks of NiO; and
this indicates that Ni was highly dispersed on the catalyst support
and hence could not be obviously detected by XRD analysis.
Nevertheless, three peaks with high intensity were appeared in all
the catalysts. These peaks were related to Al2O3 (JCPDS Card No.
01-130). Crystallite size of Ni particles at 2u = 468 and 2u = 668 was
calculated according to the Scherrer equation, and presented in
Table 1.
The structural properties of catalysts are summarized in
Table 1. It is seen that addition of promoters reduced the surface
areas due to pore filling of catalyst support. Furthermore, addition
of promoters decreased the pore volume as indicated in Table 1.
The N2 adsorption/desorption isotherm of prepared samples are
displayed in Fig. 2a. For all the samples, all the isotherms belonged
to IV type isotherms with H1 shaped hysteresis loops, which were

2.2. Characterization

X-ray diffraction (XRD) analysis were performed using an X-ray

diffractometer (PAN alytical X’Pert-Pro) with a Cu-Ka monochro-
matized radiation source and an Ni filter in the range 2u = 10–808
to examine the crystallinity of the prepared samples. The N2
adsorption/desorption analysis was carried out at boiling temper-
ature of nitrogen (196 8C) using an automated gas adsorption
analyzer (Tristar 3020, Micromeritics). The samples were purged
with nitrogen gas for 2 h at 200 8C using VacPrep 061 degas system
(Micromeritics). Temperature programmed reduction (TPR) anal-
ysis was used for evaluating the reduction properties of prepared
catalysts with Micromeritics chemisorb 2750 gas-adsorption
equipment. In the TPR measurement, 50 mg catalyst was subjected
to a heat treatment (10 8C/min) in a gas flow (30 ml/min)
containing a mixture of H2:Ar (10:90). Prior to TPR experiment,
the samples were heat treated under an inert atmosphere (Ar) at
200 8C for 1 h. The H2 uptake amount during the reduction was
measured using a thermal conductivity detector (TCD). Tempera-
ture-programmed oxidation (TPO) of the spent catalysts was
carried out using a similar apparatus by introducing a gas flow
(30 mL/min) containing a mixture of O2:He (5:95) and the Fig. 1. XRD patterns of: (1) 5%Ni/Al2O3, (2) 5%Ni–3%MgO/Al2O3, (3) 5%Ni–3%CaO/
temperature was increased upto 800 8C at a heating rate of Al2O3, (4) 5%Ni–3%BaO/Al2O3.

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Table 1
Structural properties of the catalysts.

Catalyst SBETa (m2 g1) Pore volumeb (cm3 g1) Pore widthc (nm) Crystallite sized (nm)

2u = 468 2u = 668

5%Ni/Al2O3 173 0.47 8.7 9 5

5%Ni–3%MgO/Al2O3 155 0.42 8.4 10 4
5%Ni–3%CaO/Al2O3 154 0.43 8.3 9 8
5%Ni–3%BaO/Al2O3 169 0.46 8.3 12 10
a
Calculated by the BET equation.
b
BJH desorption pore volume.
c
BJH desorption average pore diameter.
d
Average NiO crystalline diameter using Scherer equation from XRD.

the significant features for ordered mesoporous materials. The H1
shaped hysteresis loops also illuminated that all the mesopores
were cylindrical-shaped channels. Furthermore, the pore size
distributions of these materials are exhibited in Fig. 2b and the
position of the peaks of the curves was all located in the range of
5.5–16 nm. It is seen that the addition of promoters shifted the
pore size distribution to smaller sizes.
3.2. Temperature-programmed reduction (TPR)
TPR profiles of Ni/g-Al2O3 catalysts with and without promo-
ters are shown in Fig. 3. All the patterns demonstrated three
reduction peaks. It is seen that addition of promoters increased the
intensity of reduction peaks, indicating the increasing in reduc-
ibility of NiO species in promoted catalysts. The first peak at 550 8C
is ascribed to NiO species with weak interaction with catalyst
support [3,7]. It is seen that with adding CaO and BaO, the intensity
of this peak increased. But, by addition of MgO, the intensity of this
peak slightly decreased. The second peak is assigned to NiO species
strongly interacting with support [3]. As can be seen, the second
peak is shifted into the lower temperature by adding MgO. It
means that MgO causes the weak interaction between support and
active phase. The last peak located at 850 8C is attributed to
NiAl2O4 reduction [7,14]. It is clear that addition of MgO reduced
the NiAl2O4 reduction temperature compared to CaO, BaO, and
unpromoted catalysts. Also, the intensity of this reduction peak in
CaO and BaO promoted catalysts is more than unpromoted
catalysts. Adding CaO and BaO cause the strong interaction
between active phase and the support; hence, hardly to be reduced
but addition of MgO causes the weak interaction between active
phase and support.

3.3. Catalytic performance

The conversions of CH4 and CO2 are shown in Fig. 4a and b,

respectively. With increasing reaction temperature, the conversions

Fig. 2. (a) N2 adsorption/desorption isotherms of (1) 5%Ni/Al2O3, (2) 5%Ni–3%MgO/

Al2O3, (3) 5%Ni–3%CaO/Al2O3, (4) 5%Ni–3%BaO/Al2O3 catalysts and (b) pore size Fig. 3. TPR patterns of (1) 5%Ni/Al2O3, (2) 5%Ni–3%MgO/Al2O3, (3) 5%Ni–3%CaO/
distributions of calcined catalysts. Al2O3, (4) 5%Ni–3%BaO/Al2O3 catalysts.

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catalysts is less than one because of reverse water gas shift reaction
accruing in CO2 reforming of methane. As can be seen in Fig. 4a and b,
MgO can improve catalyst activity due to formation of MgAl2O4
phase [16].
Xu et al. [3] reported that NiO–MgO–Al2O3 catalyst was
displaying high catalytic activity and long catalytic stability.
Mónica Garcı́a-Diéguez et al. [15] expressed that the Mg
incorporation to Ni/Al2O3 catalysts improves the Ni dispersion
by surface rearrangement and further reduces the carbon
formation.
Helvio Silvester A. Sousa et al. [16] reported that better catalytic
performance was found in case of Ni-containing MgAl2O4 and
NiAl2O4 phases due to the increased resistance against physical
degradation, but the coking was found to decrease the perfor-
mance to a minor extent.
The results showed that the addition of CaO and BaO caused a
decrease in catalytic activity.
A short time stability test was carried out at 700 8C and the
results showed that all the catalysts had good stability during the
test period of 300 min (Fig. 5a). Also, the long term stability of

Fig. 4. (a) CH4 conversion, (b) CO2 conversion and (c) H2/CO ratio. Reaction
conditions: CH4/CO2 = 1/1, GHSV = 12,000(ml/h gcat).

of CO2 and CH4 increased. It is also obvious that the conversion

of CO2 is higher than that of CH4 on the unpromoted and
promoted catalysts due to the reverse water-gas shift reaction Fig. 5. (a) short time stability of the Ni/Al2O3, Ni–Mg/Al2O3, Ni–Ca/Al2O3 and Ni–Ba/
(CO2 + H2 $ CO + H2O). The H2/CO molar ratio on all the catalysts is Al2O3catlystst and (b) long time stability of Ni–Mg/Al2O3 catalyst. Reaction
displayed in Fig. 4c. It is clear that the H2/CO molar ratio for all condition: T = 7008C, CH4:CO2 = 1/1, GHSV = 12,000(ml/h gcat).

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Fig. 6. Effect of GHSV on the catalytic activity. Reaction conditions: CH4/CO2 = 1:1,
T = 6508C.

5%Ni–3%Mg/Al2O3 catalyst exhibited very high stability during

15 h time on stream (Fig. 5b)
Fig. 6 shows the effect of gas hour space velocity (GHSV) over
the prepared catalysts at 650 8C and with constant feed ratio (CH4/
CO2 = 1). As it is obvious, for all the catalysts, both CH4 and CO2
conversion decreased with increasing GHSV because of reduced
contact time, and the amount of adsorbed reactant.
The effect of feed ratio on the catalytic performance of
5 wt.%Ni–3 wt.%Mg/Al2O3 catalyst at 650 8C is plotted in Fig. 7.
The acquired results show that with increase in the CH4/CO2 from
1:2 to 4:1, the CH4 conversion decreased; whereas, the CO2
conversion increased, as a result of the presence of excess CO2 in
the main reaction of dry reforming (CH4 + CO2 $ 2CO + 2H2). The
H2/CO ratio also decreased with the increase of CO2/CH4 ratio;
since the RWGS reaction took place seriously at a higher ratio of
CO2/CH4.

Fig. 8. TPO profiles of (a) the spent catalysts with and without promoters (1) Ni/
Al2O3, (2) Ni–Mg/Al2O3, (3) Ni–Ca/Al2O3 and (4) Ni–Ba/Al2O3catlyststs, (b) Ni–Mg/
Al2O3 spent catalyst after running the reaction for 15 h at 700 8C.

3.4. Coke formation

3.4.1. Temperature-programmed oxidation (TPO)

Fig. 7. Effect of feed ratio on the catalytic performance of 5%Ni–3%Mg/Al2O3 at
650 8C and GHSV = 12,000(ml/h gcat).
TPO profiles of carbon deposition on the spent catalysts are
illustrated in Fig. 8a. The TPO profiles of all the catalysts show three
peaks, indicative of three kinds of carbonaceous species formed on
the catalysts. The first observed peaks on 5%Ni/g-Al2O3 and 5%Ni–
3%Ca/-Al2O3 occur around 180 8C while they are appearing at
210 8C for 5%Ni–3%Mg/g-Al2O3 and 5%Ni–3%Ba/g-Al2O3 catalysts,
attributed to active carbon species or reaction intermediates that
reacted with oxygen at low temperatures. Among these catalysts,
MgO promoted catalyst has the lower active carbon species. The
second peak occurred at 350–400 8C, ascribed to amorphous and/
or graphite forms of carbon. The high temperature peak around
680 8C could be assigned to filamentous form of carbon [2]. As it is
obvious, the highest amount of coke deposition was corresponding
to filamentous carbon. It is seen that by adding promoters (Mg, Ca,

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Fig. 9. SEM images of spent (a) Ni/Al2O3, (b) Ni–Mg/Al2O3 catalysts. Reaction
condition: CH4/CO2 = 1, GHSV = 12,000 ml/g h, time on the stream = 300 min.
and Ba) into the Ni/Al2O3 catalysts, carbon formation is decreased.
The decrease in carbon formation is related to enhance basic
properties of the catalysts and CO2 adsorption, resulting in coke
resistance [14]. Based on Fig. 4, MgO promoted catalyst had the
highest activity compared with Ca and Ba promoted catalysts;
hence, these catalysts have higher degree of coke formation.
Temperature-programmed oxidation (TPO) was carried out
after 15 h of reaction on the 5%Ni–3%Mg/Al2O3 catalyst (Fig. 8b).
The TPO profile of this catalyst clearly demonstrates that three
kinds of carbon species deposited on the catalyst surface during
DRM reaction. One small peak observed at a 200 8C could be
ascribed to active carbon species or reaction intermediates that
reacted with oxygen at low temperatures. The peak which is
observed between 400–500 8C is related to amorphous type of
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carbon, and the last peak at 900 8C can be assigned to filamentous
carbon. As it is shown, the major amount of coke deposition was
corresponding to amorphous and filamentous carbons.
3.4.2. SEM images
Fig. 9a and b shows the SEM images of spent Ni/Al2O3 and
promoted nickel catalyst with MgO, respectively. As can be seen, in
both catalysts, filamentous carbon was observed. The SEM results
showed that the addition of MgO promoter significantly decreased
the amount of deposited carbon. These results are in agreement
with those observed from TPO analysis.
4. Conclusions
The Ni/Al2O3 without and with MgO, CaO, and BaO promoters
were prepared and tested in dry reforming of methane. The BET
results showed that the addition of these promoters decreased
SBET. From TPR profile, it can be understood that an addition of MgO
into the Ni/Al2O3 catalyst decreased the reduction temperature of
NiO species; and the catalyst reduced well in reaction condition
compared to other studied catalysts. Based on activity tests and
TPO results, it can found that adding MgO into the Ni/Al2O3 catalyst
enhanced methane conversion and decreased the coke formation
compared with unpromoted catalyst. Adding CaO and BaO into the
Ni/Al2O3 reduced the methane conversion, but decreased the coke
formation in CO2 reforming of methane.
Acknowledgment
The authors are grateful to University of Kashan for supporting
this work by Grant No. 158426/16),.
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