Catalysis Today 195 (2012) 93–100

Contents lists available at SciVerse ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Biogas reforming for syngas production over nickel supported on ceria–alumina

catalysts
O.A. Bereketidou a,b , M.A. Goula a,∗
a
Technological Educational Institute of Western Macedonia, Pollution Control Technologies Department, GR-50100 Koila, Kozani, Greece
b
University of Western Macedonia, Department of Mechanical Engineering, Bakola and Sialvera, GR-50100 Kozani, Greece

a r t i c l e i n f o a b s t r a c t

Article history: A series of 8 wt% nickel catalysts supported on alumina and alumina-modified with different amounts
Received 13 January 2012 of ceria were prepared. The effect of the supporting ceria loading at the catalytic performance for
Received in revised form 10 July 2012 the biogas reforming reaction was investigated. The physicochemical properties of the final catalysts
Accepted 10 July 2012
were determined by using different techniques: N2 adsorption–desorption isotherms, X-ray diffraction
Available online 13 August 2012
(XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and transmission electron
microscopy (TEM). Catalytic performance was evaluated for the biogas reforming reaction using a feed gas
Keywords:
mixture of CH4 /CO2 = 1.5, simulating a clean model of biogas. It was shown that nickel catalysts supported
Biogas reforming
Nickel catalysts
on ceria–alumina exhibit slightly higher conversion values, compared to the one supported on alumina
Syngas production above 800 ◦ C, which can be mainly attributed to the redox properties of ceria. In particular, the 8 wt%
Ceria–alumina nickel catalyst supported on 20 wt% ceria–alumina was proven to have the best catalytic performance
with a highest H2 /CO ratio of about 1.3. The biogas reforming reaction catalyzed by nickel–alumina doped
with ceria catalysts seems to be an appropriate process in order to produce syngas suitable for methanol
or Fischer–Tropsch synthesis reactions, which require H2 /CO ratio values between one and two (1 to 2).
© 2012 Elsevier B.V. All rights reserved.

1. Introduction utilization of CO2 as a feedstock for producing chemicals, pauses an

interesting challenge in exploring new concepts and new opportu-
Global climate change caused by CO2 emission is currently nities for catalysis and chemical industry [4].
debated around the world and greener sources of energy are being DRM appears to be advantageous when compared to the SRM
sought as alternatives to the use of fossil fuels. Biogas is a clean and PROX as the hydrogen to carbon monoxide molar ratio of the
and environmental friendly fuel that is typically generated from produced syngas is close to one. This value is considered to be the
anaerobic degradation of biomass. Biogas, consisting mainly of most appropriate for Fischer–Tropsch and other synthesis reactions
CO2 and CH4 , is an attractive renewable carbon source and its for the production of liquid hydrocarbons [5–7].
exploitation would be advantageous from both financial and envi- The network reactions that can be included in the dry reforming
ronmental points of view [1]. A clean model biogas consists mainly process are summarised as follows:
of 55–65% methane (CH4 ), and 30–45% carbon dioxide (CO2 ) [2].
The technologies that could be applied for biogas reforming reac- CH4 + CO2 ↔ 2CO + 2H2 CO2 reforming (1)
tion are the same that have been extensively used for the natural
gas reforming: Steam Reforming (SRM), Partial Oxidation (PROX), CO2 + H2 ↔ H2 O + CO reverse water gas shift (2)
Dry and Autothermal Reforming [3]. For syngas production, the
CH4 ↔ C + 2H2 methane decomposition (3)
CO2 reforming of CH4 or Dry Reforming of Methane (DRM) reaction
has been proposed as the most promising one. DRM has attracted 2CO ↔ C + CO2 Boudouard reaction (4)
considerable scientific interest in the past years, as it offers the pos-
sibility of simultaneous removal of two inexpensive and abundant C + H2 O ↔ CO + H2 carbon gasification (5)
carbon containing sources, which are also greenhouse gases, and
their transformation into useful chemical products. Moreover, the Due to the attention that the DRM process is receiving, major
efforts are being expended in the development of new catalysts
that will exhibit high activity towards synthesis gas formation, and
∗ Corresponding author. Tel.: +30 2461068296; fax: +30 2461039682. be resistant to coking, as well as, displaying stable long-term oper-
E-mail addresses: oberek@kozani.teikoz.gr (O.A. Bereketidou), ation. Generally, noble metals catalysts have been reported to be
mgoula@kozani.teikoz.gr, mgoula@teikoz.gr (M.A. Goula). less sensitive to coking than the nickel-based ones [8–15].

0920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2012.07.006
94 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100

Extensive development and use of catalysts, based on non-noble Table 1

metals, such as Fe, Co, Ni, is considered to be preferred from the
industrial standpoint, mostly due to economical reasons. This kind
of catalysts has been proven to have a high initial activity, with
the drawback that it was completely lost within a couple of hours,
due to extensive carbon formation, originating either from methane
decomposition or CO disproportionation [4]. However, considering
the aspects of high cost and limited availability of noble metals,
it would be more desirable, from the industrial point of view, to
develop nickel-based catalysts which could be resistant to carbon
deposition and exhibit stable operation for an extended period of
time [16–19].
Along with the active metal, the supporting material also plays
an important role in determining the catalytic performance for the
DRM. By dispersing noble (Rh, Ru, Pt, Re and Pd) and transition (Ni,
Fe, Co) metals over various inert and reducible supports (Al2 O3 ,
SiO2 , ZrO2 , La2 O3 , various molecular sieves and active carbon),
it has been reported that metals supported over inert materi-
als (e.g. silica), show much lower activity in terms of turnover
numbers, compared to metals dispersed over Al2 O3 , TiO2 , ZrO2
or CeO2 [4].
Nickel supporting on alumina catalysts with CeO2 as an additive
promoter, was found to improve DRM performance at the operat-
ing temperatures (800–900 ◦ C). The ceria doped catalysts provide
significantly higher reforming reactivity and resistance towards
carbon deposition compared to the conventional nickel supported
on alumina ones. Previous works have proven that these enhance-
ments are mainly due to the influence of the redox properties of
ceria [20–25].
Addition of CeO2 has been reported to prevent metal sinter-
ing due to strong metal support interactions and improve catalyst
thermal stability [4,26]. This is due to the fact that ceria contains
a high concentration of highly mobile oxygen vacancies, which act
as local sources or sinks for oxygen involved in reactions taking
place on its surface [27]. According to the literature [27], during
the dry reforming process, the gas–solid reaction on ceria surface
takes place simultaneously with the reactions on the Ni surface,
which reduces the degree of carbon deposition on catalyst surface
from methane decomposition and Boudouard reactions.
The present work focuses on the synthesis of stable nickel cata-
lysts supported on ceria–alumina. Their characterization using bulk
and surface techniques has provided information for understand-
ing differences in their catalytic performance. This can lead to the
evaluation of the experimental conditions for the biogas reforming
reaction, with the final aim of optimizing the syngas production.
Particular attention has been directed to elucidate the effect of
CeO2 content on the structure and surface properties of alumina
supported nickel catalysts, as well as, on the catalytic behavior of
the samples on the biogas reforming reaction.
2. Experimental
2.1. Catalyst preparation
Physicochemical properties of the ␥-alumina pellets used in the study.
Property Value
Radius (R) 1.58·10−3 m
Mean pore diameter (˛) 7.8·10−9 m
Surface area (SBET ) 281 m2 g−1
Bed density (B ) 5.7·105 g m−3
Pore volume (Vp ) 0.65 ml g−1
Average length (L) 5.2 mm
samples were labeled as 8Ni/xCe–Al where x is the supporting
material concentration on ceria (wt%).
2.2. Catalyst characterization
Metal loading of the samples was determined by inductively
coupled plasma atomic emission spectroscopy (ICP-AES – Perkin-
Elmer Optima 4300DV). The textural properties of the calcined
samples were measured by N2 adsorption–desorption isotherms
using a Micromeretics Tristar apparatus with Micromeretics
VacPrep 061 Sample Degas System. XRD profiles of the oxide sam-
ples were recorded on a Siemens D500 diffractometer using Co K␣
radiation. Transmission electron microscopy (TEM) measurements
on oxide catalysts before reaction were also performed using a JEOL
JE-2010 instrument in order to observe the morphology of the cat-
alyst surface and the determination of the particle size of nickel
catalysts.
2.3. Catalytic activity
The experimental study of the biogas reforming reaction was
carried out at atmospheric pressure in a fixed-bed continuous flow
reactor. The catalytic reactor was made of quartz and was operated
at temperature values ranging from 700 to 900 ◦ C, having a feed
gas mixture with a constant molar CH4 /CO2 ratio of 1.5, simulat-
ing an ideal model biogas. The total flow rate was 200 ml min−1 ,
controlled by mass flow meters (M+W Instruments, MFC) and con-
sisting of a mixture of CH4 /CO2 (100 ml min−1 ) in He (100 ml min−1 )
corresponding to a Gas Hourly Space Velocity (GHSV) of 1200 h−1 .
The reaction temperature was controlled by a thermocouple placed
in the middle of the catalyst-bed. The amount of catalyst used dur-
ing the catalytic runs was 10 cm3 and it was diluted with 10 cm3
␥-Al2 O3 pellets calcined at 800 ◦ C. Product gases were analyzed by
online gas chromatography (Agilent 7890 A) equipped with a Ther-
mal Conductivity Detector (TCD) and a Flame Ionization Detector
(FID). Prior performing catalytic reaction measurements, catalysts
were in situ activated by flowing pure hydrogen for 2 h at 700 ◦ C.
According to the analysis and metering system mentioned
above, the conversion of CO2 and CH4 can be calculated as defined
in Eqs. (6) and (7). Moreover, the selectivity of H2 , the yield of H2
and the yield of CO can be calculated as defined in Eqs. (8)–(10),
respectively:
FCH4 ,in − FCH4 ,out
XCH4 (%) = × 100 (6)
FCH4 ,in

FCO2 ,in − FCO2 ,out

The ceria–alumina supports were obtained by impregnating XCO2 (%) = × 100 (7)
FCO2 ,in
the ␥-alumina pellets (AKZO, SBET = 195 m2 g−1 ) with an aqueous
solution of Ce(NO3 )3 ·6H2 O with appropriate ceria concentration FH2
at room temperature. The physicochemical properties of the ␥- SH2 (%) = × 100 (8)
2(FCH4 ,in − FCH4 ,out )
alumina pellets used in this study are presented in Table 1.
Supported nickel catalysts were prepared following the wet FH2
YH2 (%) = × 100 (9)
impregnation method and by using Ni(NO3 )2 ·6H2 O aqueous solu- 2FCH4 ,in
tions with the proper concentration, in order to obtain a final
FCO
catalyst with Ni content of about 8 wt%. All the catalyst sam- YCO (%) = × 100 (10)
ples were air-dried overnight and calcined at 800 ◦ C for 5 h. The FCH4 ,in + FCO2 ,in
 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100 95

Table 2
Characterization results of the supported catalysts.

Catalyst SBET (m2 g−1 ) ICP (Ni, wt%) Crystalline phase (XRD) Particle size (nm) Mean pore size (Å)

8Ni/Al 163 7.91 ␥-Al2 O3 , NiAl2 O4 14 145

8Ni/10Ce–Al 136 7.7 ␥-Al2 O3 , NiAl2 O4 , cerianite 13 149
8Ni/20Ce–Al 126 8.09 ␥-Al2 O3 , NiAl2 O4 , cerianite 10 150

where Fi,in or Fi,out is the flow rate of each component in feed or 800
effluent. * γ-Al2O3
700 + NiAl2O4
2.4. Carbon deposition

The amount of carbon deposited on the surface of the catalyst 600

would theoretically be equal to the difference between the inlet
carbon containing components (CH4 and CO2 ) and the outlet carbon 500
containing components (CO, CO2 , and CH4 ). The amount of carbon
* *
deposited per gram of catalyst is given by the following equation:

Intensity
400
moleCarbon(in) − moleCarbon(out) + +
Cdeposition = . (11)
mcatalyst
300 +
3. Results and discussion
* *
200
3.1. Sample characterization * +

100
3.1.1. Physicochemical properties
In Table 2 the physicochemical properties of Ni/␥-Al2 O3 and
Ni/CeO2 –Al2 O3 catalysts are presented. The lower surface area val- 0
ues of the CeO2 modified alumina nickel catalysts compared to 0 10 20 30 40 50 60 70 80 90
those supported on pure alumina, could be attributed to a blockage
2 theta
of the alumina pores by cerium oxide species. Indeed the mean pore
size of Ni/CeO2 –Al2 O3 catalysts is higher than the one of Ni/Al2 O3 Fig. 1. XRD pattern of the unpromoted catalyst 8 wt% Ni/␥-Al2 O3 .
catalyst (Table 2), which is probably related to the presence of par-
ticles with larger pores and a possible blockage of the pores with
low diameter due to the cerium oxide addition on alumina surface. with an error range of 1–2%, due to the regulations of TEM itself.
ICP results revealed that for all the catalyst samples nickel loading Moreover, the mean size of the characteristic nickel particles was
was approximately 8 wt%. estimated measuring several particle sizes.
It is seen from Table 2 that Ni/CeO2 –Al2 O3 catalysts have smaller
3.1.2. XRD nickel particle sizes than that of unpromoted 8%Ni/Al2 O3 catalyst.
XRD patterns of Ni/␥-Al2 O3 and Ni/CeO2 /␥-Al2 O3 catalysts are
shown in Figs. 1 and 2. From XRD patterns it is clear that NiAl2 O4
peaks are different among unpromoted and promoted catalysts.
800
Characteristic peaks at 2 = 46◦ and 66.9◦ assigned to ␥-Al2 O3 are ^ cerianite 8Ni/10Ce-Al
^
observed for all samples. Moreover, according to the XRD analysis, * γ-Al2O3 8Ni/20Ce-Al
no reflections belonging to transition aluminas, -alumina (25.6◦ 700
+ NiAl2O4
and 43.3◦ ) or ␣-alumina (31.2◦ and 36.6◦ ) were observed on the
calcined catalysts, indicating that alumina transformation was not 600
promoted at the temperatures employed in the calcinations treat-
ment. The intensity of diffraction lines at 2 = 36.5◦ and 65.2◦ due to
500
the NiAl2 O4 phase, decrease with increasing CeO2 content. This is
Intensity

an indication that interaction between NiO species and Al2 O3 sur-

face is prevented by the cerium oxide addition [27]. No diffraction 400 ^
peaks of NiO were determined in all samples by the XRD analy-
sis due most probably to the overlapping by reflections of NiAl2 O4 300 ^
*
peaks or due to the good dispersion of Ni species on the catalyst + +
surface [28]. Previous studies reveal that using the wet impregna- *
200 *
tion method for the Ni/CeO2 /␥-Al2 O3 catalyst preparation, there is
no evidence of a formation of a mixed oxide of CeNiO3 type [28], + ^
which is consistent with our results in this investigation. In addi- 100
tion, catalyst preparation with co-precipitation or sol gel method,
lead to the formation of mixed oxides by the type of CeNix Oy after 0
calcinations at high temperatures [29–31]. 0 10 20 30 40 50 60 70 80 90

2 theta
3.1.3. TEM
The nickel particle size was calculated by characteristic TEM Fig. 2. XRD pattern of the catalysts 8 wt% Ni/10%CeO2 –Al2 O3 and 8 wt%
images where discrete enough nickel particles were detected, Ni/20%CeO2 –Al2 O3 .
96 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100
The decrease in the mean particle size is higher in the 20 wt% CeO2
loading, in comparison to the catalyst with 10 wt% CeO2 in the pro-
moted catalyst. The changes in the size of the particle size in doped
with ceria catalysts, is also verified by previous bibliographic results
[23,28]. Thus, high ceria loading (20 wt%) results in a mean particle
size of approximately 10 nm.
The observation is consistent with the literature [27] which
reveals that the presence of CeO2 enhances the nickel dispersion
and suppresses the aggregation by forming strong nickel–support
interaction with the help of CeO2 incorporation. It is well known
that the role of CeO2 component on nickel-based reforming cat-
alyst is to enhance the catalytic activity with low coke formation
during reforming reaction, by easily donating lattice oxygen due
to its high oxygen capacity [22]. In addition, the catalytic perfor-
mance on CeO2 -promoted Ni/Al2 O3 catalyst is closely related to
the high dispersion of nickel particles by forming a strong inter-
action of nickel with Al2 O3 and CeO2 , as well as, the well-proven
character of lattice oxygen contribution by CeO2 [22].
Previous studies have shown that the CeO2 could improve
the activity of the Ni/Al2 O3 catalysts. Moreover, this rare-earth
oxide favors the coke gasification and water gas shift reaction,
and it improves the redox reversibility of metallic phase. These
last characteristics of the CeO2 , which presents basic character, are
due to its capacity to store, release and transport oxygen and its
ability to adsorb steam. According to our results, as the ceria con-
tent increases, the relative proportion of nickel aluminate species
becomes lower. Apart from nickel aluminate formation in the pro-
duced catalysts, and the fact that there is no evidence of the
presence of mixed oxide CeO2 –Al2 O3 (XRD analysis), there is also
a possibility of the formation of NiO species interacting with CeO2 .
According to Iriondo et al. [28] the reduction temperature of this
type of species rises with the decrease of the ceria content in the Ni
catalysts supported on ceria-promoted alumina. This fact indicates
that the interaction among NiO and CeO2 seems to be stronger at
low ceria contents. This strong interaction possibly inhibits the Ni
particles stabilization, especially at low ceria loadings.
Moreover, according to the literature [28], the increase of ceria
content from 10 to 20 wt%, reduces the binding energies of Ni0
species at the ceria-promoted alumina catalysts prepared by the
wet impregnation method, resulting in higher reduction temper-
atures. Thus, the reduction temperature is probably higher in the
8Ni/10Ce–Al, with an impact on catalytic activity.
Furthermore, at high temperatures (above 750 ◦ C), a new nickel
phase could be likely stabilized on the ceria surface, related with
the reducibility of the Ce(IV) to Ce(III) species at this high tempera-
ture and the subsequent mobility of oxygen species, a well-known
feature specially favored on the ceria surface. This effect of ceria
modifying the state of the nickel particles, that can be considered as
part of the so-named strong metal–support interaction (SMSI) has
been recently considered by other authors [32]. The rate determin-
ing step of both the methane reforming reaction and the formation
of carbon deposits are the dissociative absorption of the hydrocar-
bon on the metal. Highly unsaturated nickel atoms have a higher
reactivity for this dissociative step, which are also the most active
sites for carbon formation catalytic system. The formation of flat-
tened nickel particles at high temperature as a consequence of a
SMSI effect, could account for the higher stability of the catalyst
under dry reforming reaction conditions, as the number of unsatu-
rated nickel atoms decreases with this morphology.
3.2. Thermodynamic equilibrium analysis of CH4 –CO2 mixture
In order to elucidate the biogas reforming reaction, theoretical
values of product gas concentration for temperature values ranging
from 300 to 1000 ◦ C were calculated.
0,6
H2
CO
Equilibrium Composition (molar fraction)
0,5 C
H2O
CH4
CO2
0,4
0,3
0,2
0,1
0,0
300 400 500 600 700 800 900 1000
o
T( C)
Fig. 3. Thermodynamic equilibrium composition of CH4 /CO2 = 1.5 (molar) mixture
as a function of temperature at P = 1 atm.
The software that has been used was the HSc Chemistry 5.11 and
in order to calculate the conversion rates at the given operating
reaction conditions, the concept of minimizing the free energies
has been applied.
The calculations were performed at atmospheric pressure and
stated temperature range. Fig. 3 depicts the thermodynamic equi-
librium compositions of CH4 /CO2 = 1.5 mixture at the temperature
range of 300–1000 ◦ C and at atmospheric pressure.
It is evident from Fig. 3 that performing the reaction at a con-
stant pressure of 1 atm and the stated temperature range, methane
conversion increases with increasing temperature. Hydrogen con-
centration increases with increasing temperature, due to the
reforming reaction and methane decomposition reaction at the
entire temperature range.
Carbon monoxide appears at 500 ◦ C and increases with increas-
ing temperature due to the reforming reaction, the RWGSR and
carbon gasification reaction. An increase in carbon dioxide concen-
tration at the temperature range of 400–600 ◦ C is due to the water
gas shift reaction. Above 600 ◦ C, carbon dioxide decreases with
increasing temperature, mainly due to the reforming and RWGS
reactions. Moreover, a substantial amount of carbon and water is
produced at low temperatures (300–500 ◦ C) due to the reverse car-
bon gasification reaction, which remains in the product mix over
the entire range of temperature. It is noteworthy that at the upper
range of temperatures, the gas mixture produces the syngas with
an elevated H2 /CO molar ratio of 1.5, compared to H2 /CO molar
ratio of 1.0, produced from the equimolar mixture [33].
3.3. Catalysts performance
3.3.1. Catalytic activity and selectivity
The methane and carbon dioxide conversions as well as the
hydrogen yield for the catalysts tested in biogas reforming reac-
tion, carried out at temperature values ranging between 700 and
900 ◦ C, are shown in Figs. 4–6. It should be mentioned that the
experimental data are in good agreement with the results of the
thermodynamic equilibrium analysis for the clean model gas mix-
ture, with methane to carbon dioxide molar ratio equal to 1.5.
This is a strong indication that nickel supporting on alumina or
 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100 97

ceria–alumina catalysts exhibit high activity for both CH4 –CO2 100
reforming and methane decomposition reactions. Specifically, as
predicted by equilibrium calculations, the dry reforming activity of 90
biogas increases with increasing temperature for the whole tem-
perature range. 80
At high temperature of 900 ◦ C, stoichiometric equilibrium is
not reached for all the samples, as the conversions increase with 70
increasing temperature, probably reaching the equilibrium values
at temperature above 900 ◦ C. In all cases, the thermodynamic con- 60

X (CH4), %
version was higher than the experimentally obtained, as it was
expected. 50
It is seen that all Ni/CeO2 –Al2 O3 catalysts show higher con-
versions than Ni/Al2 O3 at temperature above 800 ◦ C. In the lower 40
temperature range (700–800 ◦ C), Ni/CeO2 –Al2 O3 with 10 wt% ceria,
gave slightly lower methane and CO2 conversions. Before 850 ◦ C, 30
methane and CO2 conversions increased as the temperature 8Ni/Al
increased, and then they remained almost constant beyond that 20
8Ni/10Ce-Al
temperature, especially for the Ni/CeO2 –Al2 O3 with 20 wt% ceria
loading. For the alumina supported catalyst and Ni/CeO2 –Al2 O3 10 8Ni/20Ce-Al
with 10 wt% ceria, the conversions increase with increasing tem- equilibrium
0
perature, probably reaching the equilibrium value at temperature
700 750 800 850 900
above 900 ◦ C.
o
It should be mentioned here that in the present study the cat- T( C)
alysts used were in the form of extrudates (cylindrical pellets),
resulting probably in the presence of mass transport phenomena Fig. 4. Effect of reaction temperature to methane conversion on the promoted and
in the reactor system. Reliable kinetic data can only be obtained unpromoted catalysts (CH4 /CO2 = 1.5).
in the absence of mass and heat transport resistances. Moreover,
the catalytic performance of the samples was evaluated at high
Ceria favors the coke gasification and water gas shift reaction
methane and CO2 conversions (especially at the range 800–900 ◦ C).
at the temperature range of 500–850 ◦ C. The differences observed
As a result, it was not feasible to calculate the reaction rate
below 800 ◦ C can be related to the low capacity of the 8Ni/10Ce–Al
and calculate activation energy values in this study. Furthermore,
catalyst to transform CO into H2 and CO2 by the WGS reaction at the
the above, could give a possible explanation to the fact that the
above temperature range and the ability of the 8Ni/20Ce–Al catalyst
rates do not seem to increase exponentially with temperature,
to promote CH4 dry reforming and the water gas shift reaction as
as expected.
it can be concluded from the lower CO content, compared to the
Previous studies [34–36] have reported that fuel (CH4 ) activa-
other catalysts used in the study.
tion/conversion is independent of the amount of co-reactant (CO2 )
Therefore, the 8Ni/10Ce–Al catalyst presented the lower hydro-
and is generally considered as the rate determining step in CH4 –CO2
gen molar ratio compared to the unpromoted and the high ceria
reforming reaction. Hence, CH4 concentration in the feed stream
promoted catalyst.
determines methane reforming rate, while on the other hand CO2
concentration affects the extent of RWGS reaction. Higher CO2 con-
centration seems to help shifting the RWGS reaction towards its 100
equilibrium composition. In this study, biogas was used as feed-
stock, consisted of CH4 /CO2 molar ratio of 1.5. As a result, the low 90
CO2 concentration in the feed, probably inhibits the shifting of
RWGS towards equilibrium composition. 80
However, the behavior of ceria-modified catalysts towards H2
production depends on the amount of ceria modifier added. The 70
H2 /CO value studies are quite helpful in understanding the behavior
of the catalysts and their selectivity. In line with other studies on 60
X (CO2), %

Ni based catalysts, a value close to 1 is a result of their significantly

higher capacities to deliver active oxygen species compared with 50
the other solids.
Based on Mars Van Krevelen mechanism, ceria play a key role 40
in supplying oxygen from its lattice and replacing it through the
dissociation of carbon dioxide on its surface in dry reforming [37]. 30
Ceria-based catalysts may be good candidates for improved
water gas shift activities because of their strong interactions with 20 8Ni/Al
the active metal and because of the facile transition between 8Ni/10Ce-Al
Ce3+ and Ce4+ . In addition, CeO2 has a high oxygen-storage capac- 10 8Ni/20Ce-Al
ity (OSC) because of its oxygen vacancy that is closely linked to equilibrium
its water gas shift activity [38]. Furthermore, from Figs. 4 and 5 0
in our manuscript, it can be seen that the catalyst 8Ni/10Ce–Al 700 750 800 850 900
depicts a lower activity only at low temperatures (below 800 ◦ C). o
T( C)
For 8Ni/10Ce–Al catalyst, which has the lowest ceria content, the
hydrogen production is low. H2 yield increases for higher ceria Fig. 5. Effect of reaction temperature to carbon dioxide conversion for catalysts
contents (Fig. 6). doped with ceria and unpromoted catalyst (CH4 /CO2 = 1.5).
98 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100

100 2,0

90 1,8
8Ni/Al
8Ni/10Ce-Al
80 1,6 8Ni/20Ce-Al

70 1,4
Hydrogen Yield (%)

60 1,2

50 1,0

H2/CO
40 0,8

30 0,6

20 8Ni/Al 0,4
8Ni/10Ce-Al 0
10 8Ni/20Ce-Al 0,2 T=860 C
-1
equilibrium GHSV=1200 h
0 0,0
700 750 800 850 900 0 50 100 150 200 250 300
o
T ( C) Time On stream (min)

Fig. 6. Effect of reaction temperature to hydrogen yield for catalysts doped with Fig. 7. H2 /CO ratio for 300 min time on stream for catalysts doped with ceria and
ceria and unpromoted catalyst (CH4 /CO2 = 1.5). unpromoted catalyst (CH4 /CO2 = 1.5).

hydrogen production and CO consumption, which leads to a high

(H2 /CO) ratio.
It can be seen from Figs. 4 and 5, that only slight differ- It can be concluded that the positive effect of the addition of
ences on CH4 or CO2 conversion values for catalysts supported 20 wt% ceria to Ni/Al2 O3 catalyst is clearly indicated by the signif-
on ceria–alumina compared to the one supported on alumina are icantly higher reforming reactivity, hydrogen yield and hydrogen
observed, at least for the temperature range of 800–900 ◦ C. to carbon monoxide (H2 /CO) ratio, compared to the conventional
Conversely, hydrogen yield values are enough higher for Ni/Al2 O3 .
ceria–alumina supported Ni catalysts and for the same temperature Due to the faster reaction rate of carbon species formed on
range (Fig. 6). Ni/CeO2 /␥-Al2 O3 catalysts, these systems exhibit higher activ-
This can be also attributed to the fact that at 800–1000 ◦ C and by ity than Ni/Al2 O3 catalyst [11]. Moreover, the selectivity towards
applying CeO2 , the Boudouard and methane decomposition reac- hydrogen increases with an increase in ceria loading, reaching the
tions could be inhibited by the redox reactions between methane value of 92% for the 20 wt% CeO2 doped Al2 O3 nickel catalyst.
and carbon monoxide (produced during the dry reforming process),
with the lattice oxygen (Ox) at CeO2 surface (forming hydrogen and
100
carbon dioxide) resulting in an increase in hydrogen yield. Accord-
-1
ing to the literature [24], for temperature values ranging from 800
90 GHSV=1200 h
to 900 ◦ C, there is evidence for carbon formation that would be
formed via the decomposition of methane and Boudouard reaction, 80
especially at high inlet CH4 /CO2 ratio.
The addition of cerium oxide (CeO2 ) by impregnation to the 70
supporting material, influences the reaction rate of both reactions
Hydrogen selectivity (%)

(Eqs. (3) and (4)), that may be inhibited by the gas–solid reactions 60
between methane and carbon monoxide with the lattice oxygen
(Ox) at CeO2 surface, forming hydrogen and carbon dioxide, which 50
is thermodynamically unfavored to form carbon species [24].
The improvement of dry reforming reactivity and resistance 40
towards carbon formation for CeO2 doped Ni/Al2 O3 could be mainly
due to the redox property of ceria. Fig. 7 shows the variation of the 30
(H2 /CO) ratio for the catalysts used in the present study, whereas
Fig. 8 shows the effect of reaction temperature to hydrogen selec- 20 8Ni/Al
tivity for the Ni/Al2 O3 and CeO2 doped Ni/Al2 O3 catalysts. It can 8Ni/10Ce-Al
be seen that H2 /CO ratio increases significantly with an increase in 10 8Ni/20Ce-Al
CeO2 loading from 0.65 (10Ce–Al) to 1.3 (20Ce–Al). During the dry
reforming, in addition to the reactions on Ni surface, the solid–gas 0
reaction between CeO2 and CH4 also produces synthesis gas with 800 820 840 860 880 900
H2 /CO ratio of 2, while the reduced ceria, CeO2−x , can react with o
T ( C)
CO2 producing CO [24,35].
Moreover, the gas–solid reactions between methane and carbon Fig. 8. Effect of reaction temperature to hydrogen selectivity for catalysts doped
monoxide with the lattice oxygen at the surface of ceria, enhance with ceria and unpromoted catalyst (CH4 /CO2 = 1.5).
 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100 99

Table 3
Results of dry reforming of a clean model biogas over Ni/Al2 O3 and Ni/CeO2 –Al2 O3 catalysts at 860 ◦ C.

Catalyst X (CH4 ), % X (CO2 ),% Y (H2 ), % Y (CO), % H2 /CO Coke (gC/gcat.)a

8Ni/Al 71.5 96 48.5 99 0.55 0.180

8Ni/10Ce–Al 72.65 96.85 50.5 95 0.65 0.170
8Ni/20Ce–Al 70.55 97.05 76.5 60 1.30 0.168
a
Calculated for 300 min time on stream and reaction temperature of 860 ◦ C.

3.3.2. Catalysts stability
In order to examine this catalyst application in the targeted reac-
tion, stability tests of 5 h time on stream are provided. Fig. 9 shows
the reforming products of the CH4 /CO2 = 1.5 mixture catalyzed by
8%Ni–20%CeO2 –Al2 O3 catalyst at 860 ◦ C.
The objective of the stability tests was to explore the catalyst sta-
bility and process sustainability issues at the conditions favorable
for carbon lay down (via decomposition of methane). Furthermore,
the conversions of methane and carbon dioxide at the temperature
of 860 ◦ C are high and below the equilibrium values. The CO2 con-
version obtained after 5 h of reaction corresponds to approximately
90% of the equilibrium value, a result that suggests that the cata-
lyst stability is not due to the possibility that part of the catalyst
bed may not participate in the reaction; this possibility could exist
if the reforming reaction were studied under equilibrium condi-
tions [16,35]. However, the stability tests were performed at nearly
100% CO2 conversion, which probably implies that the catalyst is
too active at 5 h reaction time investigated.
Thus, deactivation phenomena possibly do not affect the final
conversions. The catalyst remains stable in 300 min time on stream,
producing no significant carbon deposition after 300 min time
on stream (coke deposition calculated by mass balances), which
implies that probably no catalyst “coke” deactivation takes place
during the reaction.
However, the catalyst could be less active in higher reaction
time (e.g. 10 h on stream) or lower reaction temperatures, where
an excess of catalyst would not take place.
The main reforming products are H2 , CO, CO2 and CH4 , at con-
centrations 51%, 38.55%, 0.65% and 9.8% respectively in the product
mixture. It can be seen that the process produces a syngas with the
100
90
80 CH4
70
CO2
H2
Reforming products, vol %
H2 /CO ratio of about 1.3 (by volume), whereas the catalyst is stable
in 300 min time on stream.
Table 3 depicts the results of the biogas reforming reaction for
all catalysts at atmospheric pressure and reaction temperature of
860 ◦ C. Although slight differences on CH4 or CO2 conversion values
for catalysts supported on ceria–alumina compared to the one sup-
ported on alumina are observed, hydrogen yield values are higher
for ceria–alumina supported Ni catalysts at the reaction temper-
ature of 860 ◦ C. Moreover, the carbon monoxide yield decreases
significantly with an addition of 20 wt% ceria on nickel–alumina
catalysts, which can be attributed to the redox reactions between
methane and carbon monoxide (produced during the dry reforming
process), with the lattice oxygen (Ox) at CeO2 surface.
The results above (Table 3) also reveal that H2 /CO ratio increases
significantly with an increase in CeO2 loading from 0.65 (10Ce–Al)
to 1.3 (20Ce–Al).
Furthermore, it can be concluded that there is no significant car-
bon deposition after 300 min time on stream for all the samples,
which implies that probably no catalyst deactivation takes place
during the reaction. However, the amount of coke deposited on
catalyst surface decreases with increasing the ceria loading. During
the process, the first step in CO2 reforming of methane is believed
to proceed via CH4 decomposition to produce hydrocarbon species
and carbon atom.
Carbon deposited on catalyst surface mainly comes from
CH4 dissociation. Because of the addition of CeO2 , carbon atom
reacted with oxygen-containing species from the dissociation
of adsorbed CO2 , resulting in less carbon deposition. Moreover,
the gas–solid reaction on ceria surface takes place simultane-
ously with the reactions on the Ni surface, which reduces the
degree of carbon deposition on catalyst surface from methane
decomposition and Boudouard reactions [24]. It is widely known
that filamentous carbon is formed on supported Ni catalysts
by superficial intermediates that act as precursors for differ-
0 ent carbon types and a minimum assembly of metallic atoms is
T=860 C
-1 required for the formation of surface species. It can be assumed
GHSV=1200 h that CeO2 favors the metallic dispersion and inhibits the for-
mation of these assemblies, improving the resistance to carbon
formation [26].

60 CO 4. Conclusions

50
Nickel catalysts supported on ␥-Al2 O3 and CeO2 –Al2 O3 sys-
tems were tested for syngas production via the biogas reforming
40
reaction. Ni on CeO2 /Al2 O3 catalysts exhibited better catalytic per-
formance than the ␥-Al2 O3 supported Ni catalyst.
30
Specifically, the 20 wt% CeO2 doped Al2 O3 nickel catalyst seems
20 to be a very promising one for the biogas reforming reaction,
as it provides significantly higher reforming reactivity, hydrogen
10 yield and hydrogen to carbon monoxide (H2 /CO) ratio compared
to the conventional Ni/Al2 O3 . Moreover, this catalyst is stable for
0 300 min time on stream, producing a syngas of about 1.3 (by
0 50 100 150 200 250 300 volume).
The addition of CeO2 into Ni/␥-Al2 O3 systems not only increases
Time On stream (min)
the catalytic activity but also suppresses the carbon deposition
Fig. 9. Effect of time on stream to reforming products for catalyst 8Ni/20Ce–Al because CeO2 enhances the Ni dispersion on alumina surface,
(CH4 /CO2 = 1.5). reducing the nickel species particle size.
100 O.A. Bereketidou, M.A. Goula / Catalysis Today 195 (2012) 93–100

Furthermore, the interaction between NiO and Al2 O3 is pre- [16] M.A. Goula, A.A. Lemonidou, A.M. Efstathiou, Journal of Catalysis 161 (1996)
vented by the introduction of CeO2 , inhibiting the formation of 626–640.
[17] N. Sahli, C. Petit, A.C. Roger, A. Kiennemann, S. Libs, M.M. Bettahar, Catalysis
NiAl2 O4 , which as proven form previous works, is inactive for the Today 113 (2006) 187–193.
reforming reactions. [18] J. Juan-Juan, M.C. Roman-Martınez, M.J. Illan-Gomez, Applied Catalysis A 355
In view of the production of useful chemicals and synthetic (2009) 27–32.
[19] A.S.A. Al-Fatish, A.A. Ibrahim, A.H. Fakeeha, M.A. Soliman, M.R.H. Siddiqui, A.E.
fuels, the reforming reaction of biogas, catalyzed by nickel–alumina Abasaeed, Applied Catalysis A 364 (2009) 150–155.
doped with ceria catalysts, seems an appropriate way to produce [20] N. Laosiripojana, S. Assabumrungrat, Applied Catalysis B 60 (2005) 107–116.
syngas, which is suitable for methanol or Fischer–Tropsch synthesis [21] N.A. Pechimuthu, K.K. Pant, S.C. Dhingra, Industrial and Engineering Chemistry
Research 46 (2007) 1731–1736.
reactions, which require H2 /CO ratio of 1 to 2.
[22] S.-C. Baek, J.-W. Bae, J.Y. Cheon, K.-W. Jun, K.-Y. Lee, Catalysis Letters 141 (2011)
224–234.
References [23] S. Wang, G.Q. (Max) Lu, Applied Catalysis B 19 (1998) 267–277.
[24] N. Laosiripojana, W. Sutthisripok, S. Assabumrungrat, Chemical Engineering
Journal 112 (2005) 13–22.
[1] J. Xu, W. Zhou, Z. Li, J. Wang, J. Ma, International Journal of Hydrogen Energy
[25] A. Kambolis, H. Matralis, A. Trovarelli, C. Papadopoulou, Applied Catalysis A 377
34 (2009) 6646–6654.
(2010) 16–26.
[2] A. Effendi, Z.-G. Zhang, K. Hellgardt, K. Honda, T. Yoshida, Catalysis Today 77
[26] M. Ocsachoque, F. Pompeo, G. Gonzalez, Catalysis Today 172 (2011) 226–231.
(2002) 181–189.
[27] S. Wang, G.Q.M. Lu, Applied Catalysis B 16 (1998) 269–277.
[3] S. Damyanova, B. Pawelec, K. Arishtirova, J.L.G. Fierro, International Journal of
[28] A. Iriondo, V.L. Barrio, J.F. Cambra, P.L. Arias, M.B. Guemez, M.C. Sanchez-
Hydrogen Energy 36 (2011) 10635–10647.
Sanchez, R.M. Navarro, J.L.G. Fierro, International Journal of Hydrogen Energy
[4] P. Djinovi, J. Batista, A. Pintar, International Journal of Hydrogen Energy 37
35 (2010) 11622–11633.
(2012) 2699–2707.
[29] L. Jalowiecki-Duhamel, H. Zarrou, A. D’Huysser, International Journal of Hydro-
[5] Y.H. Hu, E. Ruckenstein, Advances in Catalysis 48 (2004) 297–345.
gen Energy 33 (2008) 5527–5534.
[6] X.E. Verykios, International Journal of Hydrogen Energy 28 (2003) 1045–1063.
[30] L. Jalowiecki-Duhamel, C. Pirez, M. Capron, F. Dumeignil, E. Payen, Catalysis
[7] A.H. Fakeeha, A.S. Al-Fatish, A.A. Ibrahim, Hypothesis VIII Proceedings, Lisbon,
Today 157 (2010) 456–461.
Portugal, April 1–3, 2009.
[31] D.K. Kim, K. Stöwe, F. Müller, W.F. Maier, Journal of Catalysis 247 (2007)
[8] P. Ferreira-Aparicio, M. Fernandez-Garcia, A. Guerrero-Ruiz, I. Rodríguez-
101–111.
Ramos, Journal of Catalysis 190 (2000) 296–308.
[32] V.M. Gonzalez-DelaCruz, J.P. Holgado, R. Pereniguez, A. Caballer, Journal of
[9] Z. Hou, P. Chen, H. Fang, X. Zheng, T. Yashima, International Journal of Hydrogen
Catalysis 257 (2008) 307–314.
Energy 31 (2006) 555–561.
[33] N. Muradov, F. Smith, A.T. Raissi, International Journal of Hydrogen Energy 33
[10] M. Nagai, K. Nakahira, Y. Ozawa, Y. Namiki, Y. Suzuki, Chemical Engineering
(2008) 2023–2035.
Science 62 (2007) 4998–5000.
[34] M.C.J. Bradford, M.A. Vannice, Catalysis Reviews Science and Engineering 41
[11] A.I. Tsyganok, M. Inaba, T. Tsunoda, S. Hamakawa, K. Suzuki, T. Hayakawa,
(1) (1999) 1–42.
Catalysis Communications 4 (2003) 493–498.
[35] E. Florez, P. Fuentealba, F. Mondragon, Catalysis Today 133–135 (2008)
[12] M. Rezaei, S.M. Alavil, S. Sahebdelfar, Z.-F. Yan, Journal of Natural Gas Chemistry
216–222.
15 (2006) 327–334.
[36] J. Wei, E. Iglesia, Journal of Catalysis 225 (1) (2004) 116–127.
[13] K. Tomishige, M. Nurunnabi, K. Maruyama, K. Kunimori, Fuel Processing Tech-
[37] F.F. de Sousa, H.S.A. de Sousa, A.C. Oliveira, M.C.C. Junior, A.P. Ayala, E.B. Barros,
nology 85 (2004) 1103–1120.
B.C. Viana, J.M. Filho, A.C. Oliveira, International Journal of Hydrogen Energy 37
[14] S. Irusta, J. Múnera, C. Carrara, E.A. Lombardo, L.M. Cornaglia, Applied Catalysis
(2012) 3201–3212.
A 287 (2005) 147–158.
[38] Y. Zhang, G. Zhang, Y. Zhao, X. Li, Y. Sun, International Journal of Hydrogen
[15] B. Pawelec, S. Damyanova, K. Arishtirova, J.L.G. Fierro, L. Petrov, Applied Catal-
Energy 37 (2012) 6363–6371.
ysis B 323 (2007) 188–201.