i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8

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Methane dry reforming on Ni/Ce0.75Zr0.25O2eMgAl2O4

and Ni/Ce0.75Zr0.25O2eg-alumina: Effects of support
composition and water addition

Hamideh Eltejaei a, H. Reza Bozorgzadeh b, Jafar Towfighi a,*, M. Reza Omidkhah a,

Mehran Rezaei c, Rasoul Zanganeh c, Akbar Zamaniyan b, Abdossamad Zarrin Ghalam a
a
Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran
b
Research Institute of Petroleum Industry (RIPI), P.O. Box 18745/4163, Tehran, Iran
c
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan,
Kashan, Iran

article info abstract

Article history: Nickel catalysts (10wt.%) supported on MgAl2O4 and g-Al2O3 were prepared by the wet
Received 21 August 2011 impregnation method and promoted with various contents of Ce0.75Zr0.25O2. X-ray
Received in revised form diffraction (XRD), BET surface area, scanning electron microscopy (SEM), thermal gravi-
15 November 2011 metric analysis (TGA), H2-temperature programmed reduction (TPR) and CO2-temperature
Accepted 24 November 2011 programmed desorption (TPD) were employed to observe the characteristics of the
Available online 27 December 2011 prepared catalysts. Ni/g-Al2O3 and Ni/Ce0.75Zr0.25O2 (5wt.%)eMgAl2O4 showed better
activity in CO2 methane reforming with 75.7(0.93) and 75.4(0.82) CH4 conversions (and H2/
Keywords: CO ratio). H2O was added to feed in the range of H2O/(CH4 þ CO2): 0.1e0.5 to suppress
CeZrO2 promoter reverse water gas shift (RWGS) effect and adjusting H2/CO ratio. The CH4 conversions (and
Dry reforming H2/CO) increased to 81(1.1) with 0.5 water/carbon mole ratio in Ni/g-Al2O3 and 85(1.2) with
Ni/MgAl2O4 0.2 water/carbon mole ratio in Ni/Ce0.75Zr0.25O2 (5wt.%)eMgAl2O4. The stability of Ni/
Ni/g-Alumina Ce0.75Zr0.25O2 (5wt.%)eMgAl2O4 in the presence and absence of water was investigated.
Coke formation and amount in used catalysts were examined by SEM and TGA, respec-
tively. The results showed that the amount of carbon was suppressed and negligible coke
formation (less than 3%) was observed in the presence of 0.2 water/carbon mole ratio over
Ni/Ce0.75Zr0.25O2 (5wt.%)eMgAl2O4 catalyst.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction producing synthesis gas with a low H2/CO ratio as an impor-

Dry reforming (DR) of methane for the production of syngas
has attracted an interest since 1920(s). This process has three
important advantages: (1) consuming two well-known green-
house gases, (2) storing energy for use in remote areas by
exothermicity of the reverse methanation reaction, and (3)
tant feedstock for both methanol and FischereTropsch
synthesis [1]. One of the obstacles encountered in the appli-
cation of this process is rapid deactivation of the catalyst,
which is mainly due to coke accumulation and sintering of
both the support and the active metal particles. To overcome
these problems in reforming processes, excess amount of CO2

* Corresponding author. Tel./fax: þ98 2182883311.

E-mail address: towfighi@modares.ac.ir (J. Towfighi).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.11.128
4108 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8

and water vapor were introduced to reformers; this solution content was studied in methane dry reforming. The influence
decreases the coke formation by increasing the size of of addition of small amount of water on CH4 conversion and
instruments which enhances capital cost of synthesis gas H2/CO ratio was investigated on selected catalysts in each
plant. The methane reforming with carbon dioxide reaction group. The long-term tests were performed on the best cata-
can be done near the stoichiometric ratios by developing more lyst in the presence and absence of water.
effective catalysts. Many researchers have studied different
methods to overcome the problem of carbon formation: (1)
using noble metals as an active phase or promoter [2e9], (2)
2. Experimental
elimination of the large ensembles of metal atoms necessary
for carbon deposition by partially poisoned catalysts like
2.1. Preparation of the catalysts
SPARG process [10], (3) addition of alkali or alkaline earth
oxides with strong Lewis basicity [11e15] or other metal
Magnesium aluminate spinel (MgAl2O4) was prepared by
oxides like CeO2, ZrO2 or combination of them [16,17], and (4)
a simple co-precipitation method. Stoichiometric quantities
changing catalysts preparation methods and conditions to
of MgCl2$6H2O (Merck) and AlCl3$6H2O (Merck) were dissolved
affect the catalysts structure [10,18e20].
in distilled water separately. The resulting solutions and an
Changing to the DR process is being investigated in order to
aqueous solution of ammonia (25wt.% Merck) were dropped
improve this reaction like microwave assisted DR [21] and
into a flask simultaneously with constant stirring to maintain
catalytic plasma reaction [22]. Combining DR with steam
the pH value at about 10. The precipitate was continuously
reforming (SR) or partial oxidation reforming (POX) is another
stirred for an hour and then aged overnight. After being
solution and has some advantages like (1) adjustable H2/CO
thoroughly washed with distilled water, the resulting slurry
ratio by changing feed composition, (2) minimizing energy
was then dried at 120  C overnight and according to [33], to
requirement by coupling highly endothermic DR with
obtain pure spinel phase calcined at 800  C for 8 h in air
exothermic POX, and (3) providing additional oxygen source to
atmosphere.
be used in carbon removal from catalyst surface [23].
Alumina powder was synthesized by sol-gel method.
Several authors reported that the support has an important
AlCl3$6H2O (Merck) was dissolved in distilled water. The
role on the stability of catalysts in CO2 reforming of methane
resulting solution and an aqueous solution of ammonia
[24e27]. A promising catalyst system for the reforming reac-
(25wt.% Merck) were dropped into a flask at the same time
tions appears to be a metal on CeeZrO2 support. Ceria is a very
with constant stirring to maintain the pH value at about 10.
interesting catalytic material because of its redox properties
The precipitate was continuously stirred for an hour and then
(switching rapidly between þ3 and þ4 oxidation states), it was
aged for 24 h. After being thoroughly washed with distilled
discovered that the addition of zirconia to the ceria lattice can
water, the resulting slurry was then dried at 120  C overnight
improve its thermal stability and increase the O2 mobility [28].
and calcined at 450  C for 8 h in air. Both supports were
Different Ce/Zr atomic ratios have been reported in CH4
crushed in 25e35 mesh.
reforming; Nawadee Srisiriwat et al. [29] used Ni/Al2O3catalyst
To prepare the Ni/CeZrO2-support catalysts, firstly, the
with CeO2eZrO2 (Ce/Zr: 0.72) as a promoter in oxidative steam
catalyst support was impregnated with an aqueous solutions
reforming of ethanol and reported improved catalytic activity,
of cerium nitrate hexahydrate (Merck) and zirconyl nitrate
increased H2 yield and the H2/CO values and decreased coke
hexahydrate (ACROS-INORGANIC) with an Ce/Zr atomic ratio
formation. N. Laosiripojana et al. [24] tested Ni/CeeZrO2
of 3.The nominal contents of CeZrO2 in the catalysts were
catalysts with different Ce/Zr ratios (1/3, 1/1, and 3/1) in
chosen 0, 5, 10 and 15wt.%. Then, samples were dried in an
methane steam reforming conditions. They reported that the
oven overnight, followed by calcination at 700  C for 6 h in air.
Ce/Zr ratio of 3/1 showed the best performance in terms of
The promoted supports were impregnated by an aqueous
activity and stability. Juan A.C. Ruiz et al. [30] showed that Pt/
solution of Ni(NO3)2$6H2O (Merck) to obtain 10wt.% Ni. After
Ce0.75Zr0.25O2 catalyst presented the best stability in auto-
that the catalysts supported on MgAl2O4 and g-Al2O3 were
thermal reforming of methane. Chen and coworker studied
calcined at 750  C and 850  C for 6 h, respectively.
Ni/Ce0.75Zr0.25O2 [18] and Ru/Ce0.75Zr0.25O2[31] catalysts in DR;
They also found that Ce0.75Zr0.25O2 has activity in DR itself [32].
The major limitations for applying CeeZrO2 in high- 2.2. Characterization of the catalysts
temperature reforming are their low specific surface area
and surface area reduction due to sintering. Coating these The surface areas were measured based on N2 adsorption data
metal oxides on the high surface area supports like MgAl2O4 using an (Micromeritics ASAP 2000) apparatus. The crystal
and Alumina which show good activity, stability and coke structure of catalysts was determined by X-ray powder
resistance in DR [33] has some benefits: Cerium and zirconium diffraction (XRD- Philips PW 1840) with a CuKa irradiation
oxides are more expensive than MgAl2O4 and Alumina and by source (l ¼ 1.5408 Å).
this method the cost of final catalyst will be decreased; Temperature programmed reduction (TPR) analysis was
MgAl2O4 has good basic properties suitable for dry reforming used for evaluating the reduction properties of prepared
[27,33,34]. This work is focused on developing stable Ni catalysts. In the TPR measurement 50 mg catalyst was sub-
(10wt.%) catalysts for DR using MgAl2O4 spinel and high jected to a heat treatment (10  C/min) in a gas flow (30 ml/min)
surface areag-Al2O3 as supports with different cer- containing a mixture of H2:Ar (10:90). Prior to TPR experiment,
iumezirconium (Ce/Zr atomic ratio ¼ 3) contents (0, 5, 10 and the sample was pretreated under an inert atmosphere (Ar) at
15wt.%) as promoters. The effect of support and promoter 200  C for 1 h and then cooled to room temperature. The
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8 4109

Fig. 1 e Schematic diagram of set-up for activity tests.

amount of H2 uptake during the sample reduction was
measured using a thermal conductivity detector (TCD).
CO2-temperature programmed desorption (CO2-TPD) was
performed using a BELCAT-A instrument to identify the basic
strength distribution of the catalysts. The sample of 50 mg in
a quartz reactor was pretreated with He gas at 700  C for 1 h,
reduced with H2 at 700  C for 3 h and then cooled down. CO2
was adsorbed at 50  C for 1 h and weakly adsorbed CO2 was
removed by purging with He. The sample was heated from
50  C to 700  C at a heating rate of 10  C/min in He flow and the
desorbed amount of CO2 was detected with a thermal
conductivity detector (TCD).
The quantitative analysis of coke amount on the spent
catalyst was performed with a thermogravimetry analyzer

Fig. 2 e X-ray diffraction patterns of different Ni/CeZrO2eMgAl2O4 catalysts. The symbol (*) represents MgAl2O4
characteristic peaks, the solid vertical lines are characteristic of NiO and the broken vertical lines are characteristic of
Ce0.75Zr0.25O2.
4110 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8

Fig. 3 e X-ray diffraction patterns of different Ni/CeZrO2eAlumina catalysts. The symbol (:) represents alumina and ()
NiAl2O4 characteristic peaks, the solid vertical lines are characteristic of NiO and the broken vertical lines are characteristic
of Ce0.75Zr0.25O2.

(TGA, PL-STA 1500). The sample of 50e70 mg was heated from
30 to 800  C with a heating rate of 10  C/min in air.
The morphologies of spent catalyst and of deposited coke
were examined by scanning electron microscopy (SEM, Philips
XL30SREG).
and the space velocity was 14,000 ml/hgcat. Water was injec-
ted using a syringe pump. The effluent was passed through
a trap to condensate residual water and then analyzed by an
on-line gas chromatography (Varian CP-3800) equipped with
FID and TCD detector. Fig. 1 shows the schematic diagram of
catalytic test set-up.

2.3. Activity tests

The catalytic activity was measured over a temperature range 3. Results and discussion
of 550e700  C at atmospheric pressure, using 300 mg catalyst
in a fixed-bed quartz reactor (12 mm i.d.). Activation of the Ni 3.1. Characterizations
catalyst involved reductive treatment with hydrogen at 700  C
for 120 min. The reactant feed ratio in dry reforming was 3.1.1. XRD
CH4:CO2 ¼ 1:1 without reagent dilution and in the presence of Figs. 2 and 3 show the XRD patterns of supports and unre-
water H2O/(CH4 þ CO2) ¼ 0.1e0.5 and a flow rate of 70 ml/min duced catalysts with various cerium and zirconium contents.

Table 1 e Properties of fresh and spent catalysts.

Sample SBET, Pore volume, Pore diameter, SBET, Pore volume, Pore diameter,
m2/gra cm3/gra A a m2/grb cm3/grb A b

MgAl2O4 113 0.416 147 e e e

Ni/MgAl2O4 61 0.356 233 59 0.169 115
Ni/CeZrO2 (5wt.%)eMgAl2O4 55 0.291 211 53 0.179 135
Ni/CeZrO2 (10wt.%)eMgAl2O4 55 0.279 203 55 0.211 153
Ni/CeZrO2 (15wt.%)eMgAl2O4 56 0.248 177 56 0.157 112
Alumina 356 0.404 45 e e e
Ni/alumina 219 0.296 55 136 0.321 94
Ni/CeZrO2 (5wt.%)ealumina 125 0.318 102 110 0.350 127
Ni/CeZrO2 (10wt.%)ealumina 119 0.337 113 109 0.290 107
Ni/CeZrO2 (15wt.%)eAlumina 105 0.265 101 80 0.227 113

a Fresh catalysts.
b Spent catalysts (reaction conditions: P ¼ 1 atm, temperature ¼ 550e700  C, CH4:CO2 ¼ 1:1, and GHSV ¼ 14,000 ml/hgcat).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8
Fig. 4 e TPR profile of Ni/CeZrO2eMgAl2O4 catalysts with
CeZrO2 contents of (a) 0wt.%, (b) 5wt.%, (c) 10wt.% and (d)
15wt.%.
In Fig. 2 the diffraction lines of Ni/MgAl2O4 catalyst virtually
coincided with those of the as-prepared MgAl2O4 support. The
NiO (200) peak (d ¼ 0.209 nm, I ¼ 100%) is more difficult to be
detected because of the overlap with the MgAl2O4 (400) peak.
However, a shoulder on the low 2q-side of MgAl2O4 (4 0 0) peak
is depicted with the 10%wt. Ni/MgAl2O4. This implies that the
NiO in the as-prepared Ni/MgAl2O4 catalysts was finely
dispersed, which could be responsible for the high stability
performance of the Ni/MgAl2O4 catalyst in dry reforming of
methane [33]. From Fig. 2 it is obvious that NiO (200) peak is
more distinct by increasing the CeZrO2 content.
In Fig. 3 XRD patterns of catalysts with g-Alumina support
were displayed. There are no diffraction peaks ascribed to NiO
in all patterns, indicating the well NiO dispersion. The peak
occurred in Ni/g-Alumina pattern at 60 degree is indicative of
the formation of NiAl2O4 which becomes more indistinct by
increasing promoter contents. CeZrO2 suppresses the
Fig. 5 e TPR profile of Ni/CeZrO2ealumina catalysts with
CeZrO2 contents of (a) 0wt.%, (b) 5wt.%, (c) 10wt.% and (d)
15wt.%.
4111
Fig. 6 e CO2-TPD patterns of Ni/CeZrO2eMgAl2O4 catalysts
with CeZrO2 contents of (a) 0wt.%, (b) 5wt.%, (c) 10wt.%, (d)
15wt.% and (e) MgAl2O4.
interaction between Ni species and Alumina so NiAl2O4
formation decreases.
For each promoted sample, there are four main diffraction
peaks at about 2q¼29 , 33 , 48 , and 57 attributed to the
reflection of (111), (200), (220) and (311) planes, respectively,
which is the characteristics of cubic fluorite structure of
Ce0.75Zr0.25O2 [32]. These peaks become sharper with
increasing promoter contents.
3.1.2. Textural properties
Table 1 shows characteristic properties of catalysts. The pore
volume and surface area of catalysts are much lower than
support but the pore diameters are bigger; in g-alumina sup-
ported catalysts the transition of g-alumina to other phases at
higher temperatures (sintering) is responsible for loss of
surface area. Larger pore size after loading metals on supports
is due to smaller pore blockage with impregnation metal
precursors which makes mean pore diameter of catalysts
change to larger ones and leads to decrease in BET surface
Fig. 7 e CO2-TPD patterns of (a) Alumina and Ni/
CeZrO2ealumina catalysts with CeZrO2 contents of (b)
0wt.%, (c) 5wt.%, (d) 10wt.%, (e) 15wt.%.
4112 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8

area. The catalyst surface area was not affected with various
promoter contents.
3.1.3. TPR
Temperature programmed reduction profiles of samples are
shown in Figs. 4 and 5. TPR peak of free NiO species, appearing
at low temperature (400  C) is absent in these figures. In Fig. 4
the peaks appearing at 600e800  C are assigned to the reduc-
tion peaks of complex NiOx species, which have strong inter-
action with support in agreement with [33]. In the sample with
10wt.% CeZrO2 another peak is observed at 550  C which is
attributed to another surface Ni oxides that is in high inter-
action with support. Promoting MgAl2O4 supported catalyst
with 5wt.% CeZrO2 does not decrease reduction temperature
but with increasing promoter loading the catalysts show more
reducibility which is in agreement with previous results [35].
This is due to suitable interaction of acidic CeZrO2 with basic
MgAl2O4 that causes good dispersion of promoters on support
and makes high interaction with Ni species.
As shown in Fig. 5, for all samples only one peak was
observed. In general, three types of Ni species can exist over
Al2O3: bulk or free NiO (reduction temperature <400  C); NiO
bonded to Al2O3 (reduction temperature 400e690  C); and NiO
incorporated into Al2O3, i.e., formation of NiAl2O4 (reduction
temperature >700  C, with the maximum reduction temper-
ature in the range of 780e830  C) [36]. Ni/g-alumina catalysts

Fig. 8 e Effect of temperature on activity of catalysts in dry reforming, P [ 1 atm, CH4:CO2 [ 1:1, and GHSV [ 14,000 ml/hgcat.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8 4113

with the addition of 5e15wt.% CeZrO2 show similar TPR
patterns. It is obvious from the results of XRD patterns in Fig. 3
that as the CeZrO2 content increases, NiAl2O4 formation
decreases, but the higher reduction temperature could be
explained by some overlapping of the peaks due to reduction
of CeZrO2 and NiOx simultaneously. CeZrO2and g-alumina
have some acidic properties and this could be the reason of
low interaction of CeZrO2 with g-alumina so the free CeZrO2 is
reduced around 800  C by elimination of O2 anions of the
lattice and formation of Ce2O3 [26,37]. Increasing promoters’
content does not show significant change in reduction
temperature of g-alumina supported catalysts and could
confirm the low interaction of g-alumina and CeZrO2.
The effect of promoter addition in increasing reducibility of
catalysts is more obvious in catalysts with MgAl2O4 support; it
would be in connection with acidicebasic properties of
support. MgAl2O4 with higher basicity than g-alumina inter-
acts more with CeZrO2 promoter and causes better Ni oxides
reduction because of redox property of CeZrO2.
strong basic site is at 430  C. In Fig. 7 only two weak sites can
be seen in supported catalysts. According to TPD analysis in
Figs. 6 and 7 MgAl2O4 supported catalysts have stronger basic
properties than g-Al2O3 supported ones and could show more
resistance against carbon formation. MgAl2O4 exhibits various
basic functionalities at the surface: weakly basic OH groups,
medium to medium strong sites connected to the oxygen of
Mg2þeO2 pairs and strong basic sites related to isolated O2
anions. The increased adsorbed amount of CO2because of
high basicity would provide more oxygen species on the
surface of the catalysts, which is helpful for the gasification of
intermediated carbon from CH4 dehydrogenation and would
result in a coke-free reforming process. This occurs because
the increase of the Lewis basicity of the support enhances the
ability of the catalyst to chemisorb CO2 in the CO2 reforming of
methane, and the adsorbed CO2 reacts with C to form CO,
resulting in the reduction of coke formation [11,33].
3.2. Activity test of catalysts

3.1.4. CO2-TPD 3.2.1. CH4eCO2 reforming

CO2-TPD results of supports and catalysts are presented in In Fig. 8 activity tests of all catalysts were shown. With
Figs. 6 and 7. From Fig. 6 it can be known that MgAl2O4 sup- increasing the reaction temperature, CH4 and CO2 conversions
ported catalysts have two weak and one strong basic sites. increased. Since CH4eCO2 reforming (Eq. (1)) is endothermic,
Two weak basic sites are recognized at 150 and 160  C and high temperature favors the reaction. Over every catalyst, CO2

Fig. 9 e The catalytic performance exhibited by catalysts under the following reaction conditions: T [ 700  C, P [ 1 atm,
CH4 [ 35 ml/min, CO2 [ 35 ml/min, H2O/(CH4 D CO2) [ 0.1e0.5 mole ratio, wcat [ 300 mg. Equilibrium data are obtained by
Aspen simulation.
4114 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8

catalyst with no promoter showed conversion like catalyst

Fig. 10 e The stability over Ni/CeZrO2 (5%wt)eMgAl2O4
catalysts with (B) and without water (A) (reaction
conditions T [ 700  C, CH4:CO2 [ 1:1, H2O/(CH4 D CO2)
[ 0.2, and GHSV [ 14,000 ml/hgcat).
conversion is higher than CH4 conversion and H2/CO ratio is
less than 1, especially at lower temperature. This is attributed
to reverse water gas shift (RWGS) (Eq. (2)) reaction that occurs
simultaneously, which leads to higher CO2 conversion and
less H2/CO ratio [38].
CO2 þ CH4 42H2 þ 2CO (1)
CO2 þ H2 4H2 O þ CO
As shown in Fig. 8(A) in catalysts with MgAl2O4 support, at
all temperatures by increasing promoter content from 5% to
15% there is a decrease in CH4 conversion. Up to 650  C, the
with 10% CeZrO2, but at 700  C its conversion was less than
others; this fact shows that the addition of promoter at higher
temperature is more significant. As can be seen in Fig. 8(C)
from 600  C to 700  C, CO2 conversions of promoted catalysts
were similar. Considering their activity trend in DR, by
increasing promoter contents activity of these samples in
RWGS reaction were increased, so to minimize the effect of
this side reaction lesser promoter content is necessary.
Fig. 8(E) presents the H2/CO ratio of these samples in DR;
unprompted catalyst showed lesser H2/CO ratio at all
temperatures. By increasing the temperature the effect of
promoter content on H2/CO ratio became negligible.
The CH4 conversions of high surface g-alumina supported
catalysts are presented in Fig. 8(B); unprompted catalyst
showed better activity at all temperatures. At lower temper-
ature the catalyst with 5% CeZrO2 showed higher CH4
conversion than other promoted catalysts, as temperature
increased the catalysts with 15% CeZrO2 exhibited better
activity. From TPR results in Fig. 5, it is difficult to fully reduce
the Ni/g-alumina catalysts with 5e15wt.% CeZrO2 under
reduction condition at 700  C for 2 h due to the high reduction
temperature over 800  C, this could be the explanation of
lower conversion of promoted Ni/Alumina in DR. g-Alumina is
amphoteric oxide and able to exchange either cations or
anions but some researchers indicated that by introducing
some acidic oxides like ZrO2 to g-alumina support its acidic
properties are increased [39]. It could be the good reason for
lesser activity of promoted g-alumina supported catalysts
in DR.
From Fig. 8(D) it can be known that higher CO2 conversion
was on 15% promoted g-alumina supported catalyst; this
means that although this catalyst showed better CH4
conversion among promoted catalysts at higher temperature
but its highest CO2 conversion indicates that this sample has
contributed in RWGS reaction too. H2/CO ratios in Alumina
group pass through maximum at 650  C (Fig. 8(F)); similar
results were reported by [40]. Ni/g-alumina showed higher H2/
CO at lower temperature by increasing temperatureNi/CeZrO2
(15%)eg-alumina showed higher H2/CO.
It can be concluded that in this reaction conditions,
promoting MgAl2O4 supported catalysts with CeZrO2 is more
profitable than g-alumina supported catalysts due to the
(2)
higher basicity of MgAl2O4 concluded from CO2-TPD results
causes better interaction between CeZrO2 and support. The
more reducibility of MgAl2O4 supported catalysts in the pres-
ence of CeZrO2 confirms this activity results.

Table 2 e Stability of Ni/CeZrO2 (5%wt)eMgAl2O4.

Feed Time-on-stream (h) Initial conversiona Initiala H2/CO Final conversionb Finalb H2/CO Stability c (%)

CH4 CO2 CH4 CO2

CH4, CO2 31 70 77.2 0.8 60 73.5 0.75 0.86

CH4, CO2, H2O 30 75.8 71.9 1 75.3 61.9 0.95 0.99

Reaction condition: 700  C, CH4 ¼ 35 ml/min, CO2 ¼ 35 ml/min, H2O/(CH4 þ CO2) ¼ 0.2, catalyst wt ¼ 300 mg.
a After 3 h.
b After 30 h.
c Final CH4 conversion/initial CH4 conversion.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8 4115

3.2.2. Reforming in the presence of water

In Fig. 9 the performance of selected catalysts in the presence
of water is displayed. Water/carbon mole ratio in feed was
changed in the range of H2O/(CH4 þ CO2): 0.1e0.5. Although
steam reforming reaction (Eq. (3)) is probable at DR condition
but by adding water to feed its occurrence is certain.

H2 O þ CH4 43H2 þ CO (3)

As shown in Fig. 9 on Ni/CeZrO2 (5wt.%)eMgAl2O4 CH4

conversion increased from 75.4% to 80e85% and H2/CO ratio
increased from 0.82 to 1.05e1.4 based on water amount in feed
respect to DR. By inducting more water, water gas shift reac-
tion promoted so CO2 conversion decreased.
As can be seen in Fig. 9(A), Ni/g-alumina exhibited strange
activity in the presence of water. The increase in the water/
carbon ratio from 0 to 0.5 has not affected the CO2 conversion
significantly but did cause an increase in CH4 conversion and
the H2/CO ratio. Unexpectedly adding water up to 0.4 showed
lower CH4 conversion with respect to DR. Research will be
conducted to further explain this effect and to elucidate the
role of the water on the structure and catalytic activity of Ni/g-
alumina. The stable CO2 conversion in Ni/g-alumina
compared to decreasing CO2 conversion in Ni/CeZrO2
(5wt.%)eMgAl2O4 is indicative of promoting effect of CeZrO2 in
WGS.
In general, the adsorption of H2O and CO2 takes place
competitively on the support in reforming reactions [11]. Song
and Pan [41] reported that basic supports prefer to interact
with CO2 than with H2O and O2 in tri-reforming of methane,
because CO2 is more acidic compared with H2O and O2. It
could be the explanation of lower H2/CO ratio than equilib-
rium H2/CO ratio in Fig. 9(C) in reaction with Ni/CeZrO2
(5wt.%)eMgAl2O4catalyst. This observation in the case of Ni/g-
alumina is attributed to higher activity of catalysts in DR and
WGS than steam reforming.
Ni/CeZrO2 (5wt.%)eMgAl2O4 exhibited higher methane
conversion and higher H2/CO ratio than Ni/g-alumina so the
time-on-stream reaction was studied with this catalyst.

Fig. 11 e SEM images of 10% Ni/CeZr (5wt.%)eMgAl2O4

catalysts (A) fresh, (B) after reaction without water and (C)
with water.

Ni/CeZrO2 (5%)eMgAl2O4 and Ni/Alumina showed higher

CH4 conversion (75.4% and 75.7%) and suitable H2/CO ratio
(0.82 and 0.92), respectively, so they were selected to investi-
gate the effect of water addition to feed.
In Table 1 the textural properties of spent catalysts are
presented. According to this table, the specific surface area of
all catalysts did not change significantly after DR reaction
unless in the case of Ni/g-alumina. Ni/g-alumina lost its high
surface area because of g-alumina phase transformation at
high reaction temperature. The pore volume and pore diam-
eter of catalysts decreased due to pore blockage by carbon Fig. 12 e DTA for spent Ni/CeZrO2 (5wt.%)eMgAl2O4after
species. 30 h in the presence and absence of water.
4116 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8
Table 3 e Characteristics of Ni/CeZrO2 (5%wt)eMgAl2O4 after 30 h reaction with and without water.
Process SBET, m2/gr Pore volume, cm3/gr
Fresh 55 0.291
Without water 59.6 0.15
With water 45.9 0.18
3.2.3. Catalyst stability
Further studies on the stability of selected catalyst were con-
ducted on dry reforming of methane in the presence of water
and without water at 700  C for 30 h. In both conditions the
catalyst showed good stability (Fig. 10). In Table 2 the
conversion and H2/CO ratio of catalysts during time-on-
stream reaction were presented. In the presence of small
amount of water the higher stability is observed and the H2/
CO ratio was near unity because of controlling side reaction
like reverse water gas shift. Excess water plays a role of
oxidant and removes carbon species from the surface of
catalyst. The result of SEM in Fig. 11 and DTA in Fig. 12
affirmed this.
In Table 3 textural properties of catalysts and amount of
deposited coke on catalyst surface after time-on-stream
reaction displayed. The Boudouard reaction (Eq. (4)) and the
CH4 disproportionation (Eq. (5)) are responsible for coke
accumulation on the catalyst surface during reaction, leading
to deactivation or destruction of the catalysts and a plugged
catalyst bed.
2CO4C þ CO2
CH4 42H2 þ C
It has been reported that the properties of support, espe-
cially basicity, are very important in CO2 reforming of
methane. MgAl2O4 could show strongly basic property which
will favor the activation of CO2 and accelerate the elimination
of surface carbonaceous species such as CHx, which comes
from the dehydrogenation of CH4. Oxygen storage/release
capacity of CeZrO2 promotes the mechanism of continuous
removal of carbonaceous deposits from the active sites, which
takes place at the metalesupport interfacial perimeter [28]. So
the conversions of both CH4 and CO2 are improved and the
high CO2 adsorption capacity improves the resistance of
catalyst against the carbon formation. On the other hand, it is
clear from Eq. (4) which is related to carbon formation that the
more CO2 adsorbed the less carbon formed.
The surface area of sample in reaction without water in
feed increased because of filamentous carbon formation. With
interning water in feed the surface area decreased due to
sintering.
Fig. 11 shows SEM pictures of the fresh catalyst and spent
catalyst in the presence and absence of water. Carbon fila-
ment structures can be seen in case without water. Fig. 9
shows the good stability even though in the absence of
water this is attributed to the well-known fact that Ni can
dissolve carbon and generate carbon filaments. During this
process, metallic sites remain uncovered despite the deposi-
tion of carbon, thus resulting in much lower deactivation rates
than those expected if metal-covering coke deposits occurred
Pore diameter, A Total amount of coke (%)
211 e
99 13
159 <3
[42]. The carbon formed on the catalyst with water is much
lower, even after long-time-on-stream at 700  C. These results
are in agreement with DTA in Fig. 12.
DTA analysis of the spent catalysts after long-time stream
reaction is presented in Fig. 12. It is seen that the temperature
of coke combustion as well the intensity of catalyst with water
in feed is lower compared to that without water. In both
conditions the peak occurred at 350  C was indicative of
carbon active species responsible for the formation of
synthesis gas [43]. The peak at around 500  C is absent in
catalyst with introducing water in feed. The amount of coke
on catalysts surface is reported in Table 3. The 13%wt coke
was deposited after DR reaction without water but in the
presence of water less than 3%wt coke was detected. It can be
concluded that the ability of catalyst to eliminate carbon is
high in the presence of water.
4. Conclusions
(4) The following conclusions can be drawn on the basis of the
characterization and catalytic activity results.
(5)
(i) XRD patterns of catalysts showed that in the presence of
CeZrO2 formation of NiAl2O4 decreased.
(ii) MgAl2O4 supported catalysts showed higher reducibility
and stronger basic sited in the presence of CeZrO2
promoters due to higher basicity of MgAl2O4 than g-
alumina.
(iii) 5wt.% CeZrO2 promoted Ni/MgAl2O4 and unpromoted Ni/
g-alumina exhibited highest activity and suitable H2/CO
ratio in DR. The different activity levels of the catalysts
clearly showed that the catalytic performances of
promoted catalysts strongly depended on the nature of
support.
(iv) Water was added to feed for adjusting H2/CO ratio and
coke elimination. Ni/CeZrO2 (5wt.%)eMgAl2O4 showed
higher CH4 conversion and H2/CO ratio than Ni/g-alumina
with lesser amount of water.
(v) The stability was investigated by Ni/CeZrO2 (5wt.%)e
MgAl2O4 catalyst in the presence and absence of water.
Introducing H2O in feed increased stability and decreased
coke formation.
Acknowledgments
The authors appreciate a great support by the RIPI, Research
Institute of Petroleum Industry in Iran.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 4 1 0 7 e4 1 1 8 4117

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