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Journal of Natural Gas Chemistry 21(2012)178183

Dry reforming reaction over nickel catalysts supported on nanocrystalline


calcium aluminates with different CaO/Al2O3 ratios
Atiyeh Ranjbar1 ,

Mehran Rezaei1,2

1. Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan, Iran;
2. Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan, Iran
[ Manuscript received September 2, 2011; revised October 17, 2011 ]

Abstract
Nanocrystalline calcium aluminates with different CaO/Al2 O3 ratios were prepared by a facile co-precipitation method using Poly(ethylene
glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG, MW: 5800) as a surfactant. They were employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction
(XRD), N2 adsorption (BET), temperature-programmed reduction and oxidation (TPR-TPO), and scanning electron microscopy (SEM) techniques. Catalysts showed a relatively high catalytic activity and stability. TPR analysis revealed that the catalysts with higher CaO content are
more difficult to be reduced. TPO analysis showed that the 5 wt%Ni/CA and 5 wt%Ni/C12A7 catalysts with higher CaO amount were effective
against coke deposition.
Key words
calcium aluminate; nickel catalyst; dry reforming

1. Introduction
Producing synthesis gas by reforming of methane with
carbon dioxide instead of processes such as steam reforming
and partial oxidation which suffer from limitations, like high
H2 /CO ratio, is of particular interest to the synthesis of valuable oxygenated chemicals. Numerous supported catalysts
have been tested, especially nickel and noble metal based catalysts, and they have been found to exhibit promising catalytic
performance [1]. In case of nickel catalysts major problem is
the deactivation of the catalysts due to carbon deposition, so
suppression of coke formation is very important. Generally
speaking, type of the support [25] and modifiers [6] greatly
affects the coking inclination. An effective way in preventing coke formation is the addition of alkali or alkaline earth
oxides. On the other hand, the increase of 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. Lemonidou et al. [1,7] prepared 5 wt% Ni/CaOAl2 O3 by the deposition of Ni on already formed calcium aluminate. The catalyst exhibited high activity and very good
stability. Goula et al. [8,9] used nickel/calcium aluminate
catalysts for the methane partial oxidation reaction and hy

drocarbons steam cracking, which showed promising performance in both cases. Furthermore, Cheng et al. reported that
the CaO/Al2 O3 molar ratio in support also affects the catalyst stability and reactivity [10]. The aim of present work is
to prepare nanocrystalline calcium aluminates with different
CaO/Al2 O3 ratios and investigate their potential as the support
of nickel catalysts in methane reforming with carbon dioxide.
2. Experimental
2.1. Support preparation
Poly(ethylene glycol)-block-poly(propylene glycol)block-poly(ethylene glycol) (PEG-PPG-PEG, MW: 5800)
was dissolved in distilled water at 60 C under vigorous
stirring for 2 h. After that with respect to molar ratio of
CaO : Al2 O3 (CA(CaOAl2 O3 ) 1 : 1, C12A7(12CaO7Al2O3 )
12 : 7, CA2 (CaO2Al2 O3 ) 1 : 2 and CA6 (CaO6Al2 O3 )
1 : 6), the appropriate amounts of calcium nitrate
(Ca(NO3 )2 6H2 O) and aluminium nitrate (Al(NO3 )3 9H2 O)
were added and dissolved in solution containing PEG-PPGPEG. The mole ratio of PEG-PPG-PEG to the metal ions was
chosen as 0.03. An aqueous solution of sodium hydroxide

Corresponding author. Tel: +98-361-5912469; Fax: +98-361-5559930; E-mail: rezaei@kashanu.ac.ir

Copyright2012, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(11)60351-4

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Journal of Natural Gas Chemistry Vol. 21 No. 2 2012

(2 M) was added drop wise into the solution at 30 C under


stirring by careful pH adjustment to 12. When precipitation occurred, the slurry was stirred for another 20 min and
refluxed at 80 C for 20 h under continuous stirring. The
mixture was cooled down to room temperature, filtered and
washed with hot distilled water to remove PEG-PPG-PEG
and the nitrates. Final product was dried at 80 C for 24 h and
heated to 1100 C at a heating rate of 5 C/min and was held
for 4 h.
2.2. Catalyst preparation
Supported nickel catalysts were prepared by excesssolution impregnation using prepared supports and an aqueous
solution of Ni(NO3 )2 6H2 O of the appropriate concentration
to obtain samples with 5 wt% nickel content. After impregnation, the samples were dried at 80 C for 24 h and calcined at
600 C for 4 h.
2.3. Characterization
The surface areas (BET) were determined by nitrogen adsorption at 196 C using an automated gas adsorption analyzer (Tristar 3000, Micromeritics). The XRD patterns were
recorded on an X-ray diffractometer (PANalytical XPert-Pro)
using a Cu K monochromatized radiation source and a Ni
filter in the 2 range of 10o to 80o . Temperature-programmed
reduction of hydrogen (H2 -TPR) was performed using a classical experimental setup with a flow micro reactor and a TCD
detector. The fresh catalyst was submitted to a heat treatment (10 C/min up to 800 C) in a gas flow (30 mL/min) of
the mixture H2 /Ar (10/90). Previous to the H2 -TPR experiment, the samples were outgassed under inert atmosphere at
300 C for 3 h. Temperature-programmed oxidation (TPO)
profiles were recorded in a similar apparatus by introducing
a gas flow (30 mL/min) of the mixture O2 /He (5 : 95) over
the spent catalysts and the temperature was increased with a
heating rate of 10 C/min up to 800 C. Scanning electron
microscopy (SEM) was performed with TESCAN VEGA, operated at 30 kV. The Ni dispersion and Ni metal surface area
were measured by H2 chemisorption at 40 C, assuming that
the chemisorption stoichiometry of H/Ni is 1 and that a Ni
atom occupies 0.065 nm2 on a Ni particle.
2.4. Catalyst testing
Activity measurements were carried out in a fixed-bed
continuous-flow reactor made of a 7-mm-i.d. quartz tube at
atmospheric pressure. The reactor was charged with 200 mg
of the prepared catalyst. Prior to the reaction, the catalyst
was reduced in the reactor at 650 C for 4 h in flowing H2
(30 mL/min) and cooled down to 550 C in a flow of Ar
(30 mL/min). After that a reactant gas feed consisting of CH4
and CO2 was introduced into the reactor and the activity tests
were performed at different temperatures, ranging from 550
to 700 C in steps of 50 C kept for 30 min at each tempera-

ture. The loss in catalyst activity at 700 C was monitored up


to 50 h on stream. The gas composition of reactants and products was analyzed using a gas chromatograph equipped with
a TCD and a Carboxen 1000 column.
3. Results and discussion
The XRD patterns of catalyst support with different
CaO : Al2 O3 ratios are shown in Figure 1. It is seen that
with decreasing of CaO : Al2 O3 ratio the intensity of peaks
in XRD patterns decreased, indicating a decrease in crystallite size. It can be seen that the sample with CaO : Al2 O3 ratio
of 12 : 7 contains free CaO. In addition, different calcium aluminates phases were observed on the samples with different
CaO : Al2 O3 ratios. The results showed that the peak intensity in the XRD pattern of CaO6Al2 O3 is weaker than those
of the other samples, indicating the smaller crystallite size in
this sample. The average crystallite sizes of supports are calculated from the half-width of diffraction peaks using Scherrers formula. The results are presented in Table 1. It is seen
that the supports are in nanocrystalline structures.

Figure 1. XRD patterns of the supports with different CaO/Al2 O3 ratios


Table 1. Structural properties of the prepared catalysts
Catalyst
5 wt%Ni/C12A7
5 wt%Ni/CA
5 wt%Ni/CA2
5 wt%Ni/CA6
Support
DXRD (nm)
Average

SBET
(m2 g1 )
57.3
63.6
137.5
80.3
C12A7
37.4

Ni area
(m2 g1
Ni )
2.9
2.2
1.6
2.6
CA
37.3

Ni size
(nm)
11.6
15.6
21.7
13
CA2
36

Ni dispersion
(%)
8.6
6.4
4.4
7.7
CA6
24.1

crystallite size

XRD patterns of the catalysts are shown in Figure 2. It


is obvious that the crystallite structure of the prepared catalysts is different with that of the catalyst supports after impregnation. The change in support structure could be due to
hydration of the support during the impregnation process. In

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Figure 3. TPR profiles of the catalysts

Figure 2. XRD patterns of different catalysts

addition, the peaks corresponding to NiO was not observed on


the catalysts due to low nickel content and high dispersion of
nickel on the support as presented in Table 1.
TPR profiles of the prepared catalysts are presented in
Figure 3. The TPR profiles consist of different peaks ranging from 450 to 750 C, while the nickel reduction occurs
mainly at higher temperatures in all catalysts. TPR analysis
reveals that the interaction of nickel species with support is in
different degree, which directly affects their reduction characteristics. Reduction profile shifts to higher temperatures as interactions between metal and support gets stronger. For example with the increase of calcium content in the catalysts, metalsupport interactions get stronger. It is interesting to notice
that 5 wt%Ni/C12A7 has higher CaO content compared with
5 wt%Ni/CA but it is reduced easily, since the TPR profile
has shifted a bit to lower temperatures for 5 wt%Ni/C12A7.
Perhaps, the surface oxygen vacancies facilitate the reduction
of NiO, since C12A7 has free CaO and so oxygen vacancies
could be formed on its surface which may strongly interact
with a neighboring oxygen of the NiO located in the vicinity;
a such kind of interaction weakens the NiO bond, resulting in

an oxygen species which could be easily removed by


hydrogen [11].
The CH4 and CO2 conversions on the catalysts with various CaO : Al2 O3 molar ratios at different temperatures are
shown in Figure 4(a) and 4(b), respectively. As expected, the
conversion is strongly dependent on the temperature. Both
CH4 and CO2 conversions increased with temperature for
all the catalysts investigated. The results also showed that
the CH4 and CO2 conversions decreased with increasing the
CaO : Al2 O3 molar ratio. This may be due to the fact that the
catalysts with higher CaO : Al2 O3 ratios have lower surface
areas and consequently the nickel dispersion over these catalysts is lower. Figure 4(b) also shows that the CO2 conversion
is higher than CH4 conversion which could be explained by
reverse water-gas shift reaction (CO2 +H2 CO+H2 O).
The H2 /CO molar ratio decreased with the increase of
CaO : Al2 O3 ratios and lower H2 /CO ratios on the catalyst
with higher CaO : Al2 O3 ratios (5 wt%Ni/CA and 5 wt%
Ni/C12A7) were found in Figure 4(c). This indicates that
the extent of reverse water gas shift reaction increases with
CaO : Al2 O3 ratio. It is understandable that the basicity of catalyst increases with CaO : Al2 O3 ratio and therefore improves
the CO2 adsorption amount over the catalyst surface, leading
to more consumption of H2 in reverse water gas shift reaction.

Figure 4. (a) CO2 conversion, (b) CH4 conversion and (c) H2 /CO molar ratio as functions of temperature on different catalysts. Reaction conditions: molar
ratio of CH4 : CO2 = 1 : 1, GHSV = 1.8104 h1

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Figure 5(a) shows the short time stability of the prepared


catalysts at 700 C. It is clear that all the tested catalysts
showed a relatively high stability during the reaction. The
long term stability over the 5 wt%Ni/CA2 catalyst was further
studied. It also showed a high stability during the reaction and
the deactivation of the catalytic activity was about 7% after
50 h on stream as shown in Figure 5(b).

Generally speaking, deactivation of nickel catalysts is


caused by carbon deposition via Boudouard reaction and/or
CH4 decomposition (Equations 1 and 2).
2CO C + CO2

(1)

CH4 C + 2H2

(2)

Figure 5. (a) Stability of the catalysts during 5 h on stream and (b) the long term stability over the 5 wt%Ni/CA2 catalyst during 50 h on stream. Reaction
conditions: 700 C, molar ratio of CO2 /CH4 = 1, GHSV = 1.8104 h1

Carbon species formed during the reforming reaction was


investigated by temperature-programmed oxidation (TPO)
and the results are shown in Figure 6. It was found that the
oxidation of carbonaceous species started at around 400 C.
The highest amount of carbon deposition is observed over
5 wt%Ni/CA6 catalyst which contains the lowest amount of
CaO. It is clear that the addition of CaO to catalyst support
decreases the amount of coke deposited on catalyst since coke
deposition is favored on acidic supports and the addition of
CaO reduces the acidity of supports.

Figure 7 shows the XRD patterns of fresh and spent


5 wt%Ni/CA2 after running the reaction for 50 h on stream.
The XRD pattern of spent catalyst exhibited the peak corresponding to graphitic carbon, which is in good agreement with
the TPO result presented in Figure 6.
SEM images of the fresh and spent 5 wt%Ni/CA2 catalyst
after 50 h on stream at 700 C are shown in Figure 8(a) and
8(b), respectively. It is clear from the Figure 8(b) that whisker
type carbon was deposited over the spent 5 wt%Ni/CA2
catalyst.

Figure 6. TPO profiles of the spent catalysts after running the reaction for
5h

Figure 7. XRD patterns of the fresh and spent 5 wt%Ni/CA2 catalysts after
running the reaction for 50 h

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Figure 8. SEM images of (a) the fresh and (b) the spent 5 wt%Ni/CA2 catalysts after 50 h on stream

Catalytic tests were also done using different feed compositions from 550 C to 700 C. In the experiments, the CH4
conversion increased and the CO2 conversion decreased with

CO2 /CH4 feed ratio (FR) as shown in Figure 9(a) and 9(b), respectively. When CO2 /CH4 ratio is set at 0.5, the lowest CH4
and highest CO2 conversions are obtained. The decrease of

Figure 9. Variations of (a) CH4 conversion, (b) CO2 conversion and (c) H2 /CO molar ratio with reaction temperatures over the 5 wt%Ni/CA2 catalyst under
different CO2 /CH4 feed ratios (GHSV = 1.8104 h1 )

H2 /CO ratio in the product stream with the increase of


CO2 /CH4 ratio is due to RWGS reaction (CO2 +H2
CO+H2 O) at higher CO2 concentrations as illustrated in Figure 9(c).
Figure 10 shows the TPO analysis of the spent catalysts
at different CO2 /CH4 ratios. It is obvious that the amount
of deposited carbon on the spent catalysts decreased with the
CO2 /CH4 ratio and the lowest amount of deposited carbon
was observed at CO2 /CH4 ratio of 2.0.
The effect of GHSV on CH4 conversion at 700 C with
constant CO2 /CH4 ratio over the 5 wt%Ni/CA2 catalyst is
shown in Figure 11. The CH4 conversion decreases with
the increase of GHSV. There are two main reasons for
this phenomenon. First, when GHSV is increased, CH4
and CO2 have not enough time to be adsorbed and react on the surface of the catalyst. Second, the CO2 reforming is an endothermic reaction and under higher GHSV
more thermal energy or heat is required to reach the same CH4
conversion.

Figure 10. TPO profiles of the spent 5 wt% Ni/CA2 catalyst under different
CO2 /CH4 feed ratios

Journal of Natural Gas Chemistry Vol. 21 No. 2 2012

183

minate based catalysts to show high activity and stability. Due


to the presence of CaO in the catalysts, carbon formation was
reduced on the catalysts. Operating conditions also effect the
carbon deposition and an increase in CO2 /CH4 ratio decreases
the carbon formation.
References
[1]
[2]
[3]
[4]
[5]
Figure 11. Variation of CH4 conversion with different GHSVs over
5 wt%Ni/CA2 catalyst. Reaction conditions: 700 C, molar ratio of
CO2 /CH4 = 1/1

4. Conclusions
Nanocrystalline calcium oxides with different
CaO : Al2 O3 ratios seem to be very promising as the support of nickel catalysts in dry reforming process. Relatively
high basicity and small metal particle size cause calcium alu-

[6]
[7]
[8]
[9]
[10]
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