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 ) 1 2 3 6 e1 2 4 2

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Autothermal reforming of methane over nickel catalysts

supported on nanocrystalline MgAl2O4 with high surface area

Zeinab Mosayebi a,b, Mehran Rezaei a,b,*, Abolfazl Biabani Ravandi a, Narges Hadian a,b
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

article info abstract

Article history: In this paper autothermal reforming of methane (ATR) was carried out over MgAl2O4
Received 10 August 2011 supported Ni catalysts with various Ni loadings. MgAl2O4 spinel with high specific surface
Received in revised form area, as nanocrystalline carrier for nickel catalysts was synthesized by co-precipitation
23 September 2011 method with the addition of pluronic P123 triblock copolymer as surfactant. The
Accepted 27 September 2011 prepared samples were characterized by XRD, BET, TEM, SEM, TPR and TPH techniques.
Available online 26 October 2011 The results demonstrated that methane conversion is significantly increased with
increasing the Ni content and methane conversion of 15% Ni/MgAl2O4 was higher than that
Keywords: of other catalysts in all operation temperatures. Furthermore the influences of H2O/CH4,
Autothermal reforming and O2/CH4 molar ratio in feed and GHSV on activity of 5% Ni/MgAl2O4 catalyst were
MgAl2O4 investigated.
Syngas Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Ni catalyst reserved.
Nanoparticles
Methane

1. Introduction The POX is an exothermic process and may require external

cooling. A lower H2/CO ratio is also obtained in POX (Eq. (2)). In
There has been substantial interest in recent years in alter- addition, the partial oxidation reaction is very fast, which can
native routes for conversion of natural gas (methane) to be started quickly.
syngas, a mixture of CO and H2, which can be used to produce 

chemical products with high added values, such as hydro-
carbons and oxygenated compounds [1]. There are three
major thermochemical techniques used to produce syngas
from hydrocarbon fuels, i.e. steam reforming (SR), partial
oxidation (POX), and autothermal reforming (ATR) [2e4].
The SR gives a high yield of H2, but reaction is endothermic
and requires external heat input (Eq. (1)).

CH4 H2 O 4 CO 3H2 DH298 206:2 kJ=mol
CH4 0:5O2 4 CO 2H2 DH298 36 kJ=mol (2)
ATR is a chemical combination of steam reforming and
partial oxidation and it is an economical process for the
production of hydrogen. Therefore, both the steam reforming
and partial oxidation reactions take place. The hydrocarbon
feed (methane or a liquid fuel) is reacted with both steam and
oxygen to produce a hydrogen-rich gas. In the autothermal
reforming, the partial oxidation reaction supplies all the heat
(1) needed to drive the catalytic steam reforming reaction [5,6].

* Corresponding author. Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engi-
neering, University of Kashan, Kashan, Iran. Tel.: 98 361 5912469; fax: 98 361 5559930.
E-mail address: rezaei@kashanu.ac.ir (M. Rezaei).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.09.141
 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 ) 1 2 3 6 e1 2 4 2 1237

steam to carbon (S/C) ratio improves the syngas composition

and reduces the CO2 recycle, which decreases the investment
and energy consumption. However, the reduction of S/C ratio
favors soot formation in the ATR reactor and carbon forma-
tion in the pre-reformer [11]. Commercial ATR catalyst is
a nickel catalyst adapted to the ATR conditions [12]. Nickel
catalysts supported on alumina (Ni/Al2O3) are commercially
used in steam reforming of methane mainly due to their low
cost [11]. However, these catalysts suffer deactivation,
generally because of coke formation [13e15]. One of the main
challenges of methane reforming process is to decrease the
deleterious effect of coke formation. An effective way in pre-
venting coke formation is addition of alkali or alkaline earth
oxides such as K2O, CaO, MgO and so on to support [16].
Among the catalyst supports, magnesium aluminate
spinel, MgAl2O4, has been widely used in industrial applica-
tions [17]. This material has unique properties, such as high
melting temperature (2135  C), high mechanical strength at
elevated temperature, high chemical inertness, good thermal
Fig. 1 e XRD patterns of calcined catalysts and MgAl2O4
shock resistance and catalyst properties [18]. For many of its
carrier (upper inset).
applications especially as catalyst support, a high surface
area, small crystalline size, high porosity and more active
sites, is more desired. In this paper, nanocrystalline magne-
sium aluminate with high surface area was synthesized by
The side reactions occur in the autothermal reformer are lis-
a simple co-precipitation method by addition of pluronic P123
ted below:
triblock copolymer as surfactant and employed as a support
CH4 3O2 4 2H2 O CO2 Oxidation OX (3) for nickel catalyst in autothermal reforming of methane.

H2 O CO 4 H2 CO2 Water gas shift WGS (4)

3H2 CO 4 CH4 H2 O Methanation
2CO 4 CO2 CS Boudouard
CH4 4 2H2 CS Carbon deposition
The main features of ATR are: (1) Low energy requirement,
due to the opposite contribution of the exothermic methane
oxidation and endothermic steam reforming [7,8]; (2) Low
specific consumption; (3) High gas space velocity (at least one
order of magnitude higher than the traditional steam
reforming); and (4) Preset H2/CO ratio easily regulated by inlet
CH4/H2O/O2 ratios and CO2 recycling [9,10]. Operation at low
2. Experimental
(5)
2.1. Preparation of support
(6)
MgAl2O4 nanopowder was prepared by co-precipitation
method with surfactant-assisted. In a typical preparation,
(7)
desired amount of pluronic P123 block copolymer surfactant
(Poly(ethylene glycol)-block, Poly(propylene glycol)eblock,
Poly(ethylene glycol), MW: 5800, Aldrich) was dissolved in
distillated water under vigorous stirring to form a transparent
solution. The P123/MgAl2O4 molar ratio was chosen 0.01. After
that, stoichiometric amounts of Mg(NO3)2$6H2O (Merck) and
Al(NO3)3$9H2O (Merck) were added to water containing P123.
Then an ammonia solution was added dropwise to the well

Table 1 e The structural properties of catalyst support and calcined catalysts.

Sample Pore volume Pore size Crystallite size (nm)
(cm3 g1) (nm)
(311) (400) (440)

MgAl2O4 0.64 11.16 5.53 5.68 4.47

Sample MgAl2O4 5% Ni/MgAl2O4 10% Ni/MgAl2O4 15% Ni/MgAl2O4

2 1
S BET (m g ) 184 139 121 104
Ni area e 2.41 2.65 1.86
(m2 g1Ni)
Ni size e 11.15 25.35 54.21
(nm)
Dispersion e 8.96 3.94 1.84
(%)
1238 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 ) 1 2 3 6 e1 2 4 2
stirring solution for adjusting pH value around 10.5. After
precipitation, the resulting mixture was refluxed at 80  C for
20 h under continuous stirring. The mixture then was cooled
to room temperature and filtered and washed thoroughly by
distilled water. The precipitate was dried at 80  C for 24 h and
then calcined at 700  C for 4 h.
2.2. Preparation of catalyst
The Ni/MgAl2O4 catalysts were prepared by the wet impreg-
nation method. An aqueous solution of appropriate concen-
tration of nickel nitrate (Ni(NO3)2$6H2O, Merck) was used to
obtain different contents of nickel. After impregnation at
room temperature, the powder was dried at 80  C and calcined
at 600  C for 4 h.
Fig. 2 e (a) and (b) TEM pictures and (c) Electron diffraction
pattern of the MgAl2O4 calcined at 700  C for 4 h.
2.3. Characterization
X-ray diffraction (XRD) analyses were performed using an
X-ray diffractometer (PANalytical XPert-Pro) with a Cu-Ka
monochromatized radiation source and a Ni filter in the range
2q 20e80 . The N2 adsorption/desorption analysis (BET) was
carried out at 77 K using an automated gas adsorption
analyzer (Tristar 3000, Micromeritics). The nickel dispersion
was measured by H2 chemisorption at 40  C, assuming that
chemisorption stoichiometry is H/Ni 1 and that a Ni atom
occupies 0.065 nm2 on a Ni particle. In order to evaluate the
reduction properties of prepared catalysts, Temperature-pro-
grammed reduction (TPR) analysis was carried out. In the TPR
measurement, 100 mg catalyst was subjected to a heat treat-
ment (10  C/min) in a gas flow (30 ml/min) containing
a mixture of H2:Ar (10:90). Temperature-programmed hydro-
genation (TPH) of the spent catalysts was also carried out. The
spent catalyst (25 mg) was subjected to heat treatment
(10  C/min up to 800  C) in a gas flow (30 ml/min) containing
Fig. 3 e (a) CH4 conversion and (b) H2/CO ratio of catalysts
with different Ni loadings at different temperatures,
GHSV [ 1.2 3 105 ml/g.h, CH4: H2O: O2 : 4:2:1.
 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 ) 1 2 3 6 e1 2 4 2
a mixture of H2:Ar (10:90) and the H2 uptake amount during
the process was measured using a thermal conductivity
detector (TCD). Surface morphology of samples was investi-
gated by using scanning electron microscopy (SEM, VEGA@-
TESCAN) and transmission electron microscopy (TEM, JEOL
JEM-2100UHR).
2.4. Catalytic evaluation
Autothermal reforming of methane was performed under
atmospheric pressure in a continuous flow reactor made of
a 7-mm-i.d. quartz tube at different temperatures. For ATR
reaction study, 100 mg of the catalyst sample was charged to
the reactor. Prior to the reaction, the catalysts were reduced
at 600  C for 2 h in flowing H2 (30 ml/min) and cooled down to
550  C. After that, a reactant gas feed consisting of a mixture
of CH4 and O2 was introduced into the reactor. The flow rates
of the gases were measured by Bronkhorst High-Tech (EL-
FLOW series) mass flow controllers. Water was fed by means
of a syringe pump. The activity tests were performed at
different temperatures, ranging from 550 to 700  C in steps of
50  C that were kept for 30 min at each temperature. A cold
Fig. 4 e (a) Short time stability of catalysts with different Ni
loadings and (b) long-term stability of 15% Ni/MgAl2O4 at
700  C, GHSV [ 1.2 3 105 ml/g.h, CH4: H2O: O2 : 4:2:1.
1239
trap was used for separating water vapor from the flowing
out gas. The product was monitored by a Varian 3400 gas
chromatograph equipped with a Carboxen 1000 column and
a thermal conductivity detector (TCD).
3. Results and discussion
X-ray diffraction pattern (XRD) of the synthesized MgAl2O4
powder, Fig. 1 (upper inset), shows that all of the peaks can be
attributed to a pure phase of nanocrystalline MgAl2O4 spinel.
The XRD patterns of the prepared catalysts shown in Fig. 1,
presented that the intensity of peaks corresponding to NiO
increased by increasing in nickel content. For 5% Ni/MgAl2O4
the peaks related to NiO was not observed due to low nickel
content or high nickel dispersion.
Fig. 5 e CH4 conversion of 5% Ni/MgAl2O4 catalyst (a)
varying the H2O/CH4 feed ratio at O2/CH4 [ 0.25, (b) varying
the O2/CH4 feed ratio at H2O/CH4 [ 0.5, Reaction
conditions: GHSV [ 1.2 3 105 ml/g.h and reaction
temperature: 700  C.
1240 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 ) 1 2 3 6 e1 2 4 2

The structural properties of catalyst support and calcined

catalysts are presented in Table 1. It can be seen that the
catalyst support shows a high surface area and a nano-
crystalline structure, which cause the catalysts to reach a high
dispersion of nickel in the preparation steps.
The crystallite sizes of MgAl2O4 powder were determined
by Scherrers formula and the obtained results showed an
average crystallite size of about 5 nm, Table 1.
In addition the specific surface area of calcined catalysts
decreased with increasing Ni content, probably due to
blockage of the support pores. The H2 chemisorption analysis
revealed that the nickel crystallite size increased by increasing
in nickel content, which caused a decrease in nickel disper-
sion, Table 1.
The TEM images of support (MgAl2O4) calcined at 700  C are
shown in Fig. 2a and b. As it can be seen, the support shows
a nanocrystalline structure with a hollow cylindrical shape Fig. 6 e Effect of GHSV on the catalytic performance of 5%
which can cause a high specific surface area for well nickel Ni/MgAl2O4 catalyst, Reaction conditions: CH4: H2O: O2:
dispersion. In addition, the electron diffraction pattern 4:2:1, temperature: 700  C.
(Fig. 2c) clearly displays several distinct rings, which is indic-
ative of nanocrystalline prepared sample.
Fig. 3a and b show the effect of temperature on the CH4
conversion and H2/CO ratio of different Ni/MgAl2O4 catalysts Fig. 6 shows the effect of GHSV on the catalytic perfor-
for ATR reaction, respectively. As it can be seen in Fig. 2a, from mance over 5% Ni/MgAl2O4. The obtained results show that
550 to 700  C, the CH4 conversion of Ni/MgAl2O4 was increased increasing the GHSV causes a decrease in methane conversion
with reaction temperature and also the conversion of methane due to decrease in residence time and also amount of adsor-
increased by increasing Ni loading from 5% wt. to 15% wt. in bed reactants. In addition with increasing the GHSV, firstly the
operation temperatures. The results shown in Fig. 2b demon- molar ratio of H2/CO slightly decrease and then increase with
strated that H2/CO ratio for all the samples is more than three, more increasing in GHSV amount and/or consequently
due to the water-gas shift reaction. According to the results the decreasing in CH4 conversion. It can be due to occurrence of
observed higher H2/CO ratio (>6.0) at low temperature, sug- WGS reaction in higher GHSV amounts.
gested that the water-gas shift reaction occurred extensively Fig. 7 shows the temperature-programmed reduction (TPR)
as reported in the literature [1,2]. In addition, increasing the profiles of the catalysts with various nickel loadings. For all
system operation temperatures leads to decrease in H2/CO due catalysts, the major peak was observed around 800  C, which
to the fact that water-gas shift reaction was thermodynami- could be related to the reduction of NiO with high interaction
cally unfavorable at elevated temperatures. with catalyst support. As it can be seen, the intensity of H2
Fig. 4a presents the short time stability of ATR reaction on uptake peak was increased with increasing in nickel content.
Ni/MgAl2O4 catalysts at 700  C. As it can be observed, all
catalysts show a high stability without any decrease in CH4
conversion during the reaction time of 300 min. In addition,
the long-term stability of 15% Ni/MgAl2O4 catalyst is shown in
Fig. 4b and as it can be seen this catalyst has a high stability
during 50 h time on stream.
The effect of H2O/CH4 molar ratio on CH4 conversion was
investigated for 5% Ni/MgAl2O4 at 700 C at a constant feed
ratio of O2/CH4 0.25. Fig. 5a shows CH4 conversion increases
when the ratio of H2O/CH4 increases until H2O/CH4 1.0.
Furthermore, in order to evaluate the influence of adding O2
on ATR reaction, the experiment was carried out at a constant
feed ratio of H2O/CH4 0.5 and increasing the ratio of O2/CH4
from 0.25 corresponding to the stoichiometric amount of
autothermal reforming to 1.5. Fig. 5b presents the CH4
conversion for the 5% Ni/MgAl2O4 catalyst. The results show
that the CH4 conversion increases when the ratio of O2/CH4
increases until O2/CH4 0.5. The increase in CH4 conversion
with O2 addition can be related to combustion of part of
methane with all O2 in the feed. In addition, it can be clearly
observed that as O2/CH4 ratio increases more than 0.5, the
conversion of CH4 significantly decreases, which could be Fig. 7 e TPR profiles of nickel catalysts with different nickel
related to oxidation of nickel. loadings.
 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 ) 1 2 3 6 e1 2 4 2
Fig. 8 e SEM analysis of the (a) fresh and (b) spent 15% Ni/
MgAl2O4 after 50 h of reaction, Reaction conditions:
GHSV [ 1.2 3 105 ml/g.h, temperature: 700  C for CH4: H2O:
O2: 4:2:1.
The SEM images of fresh and spent 15% Ni/MgAl2O4 cata-
lyst after 50 h time on stream at 700  C are shown in Fig. 8a and
b respectively. As it can be seen, the significant amount of
carbon was not observed over the spent catalyst.
However, in order to investigate the carbon formation, the
TPH analysis was carried out after 50 h of reaction on the 15%
Ni/MgAl2O4 catalyst (Fig. 9). The TPH profile of this catalyst
shows two major peaks, which are related to the two types of
1241
Fig. 9 e TPH profile of spent 15% Ni/MgAl2O4 after 50 h of
reaction.
carbonaceous species, deposited on the catalyst surface
during ATR reaction. The first peak around 450  C which might
be amorphous carbon located in interior active nickel sites,
while the second peak at above 600  C is identified as whisker-
type carbon [19,20].
4. Conclusions
Ni catalysts with various nickel loadings supported on nano-
crystalline magnesium aluminate oxide with high surface
area were employed in autothermal reforming of methane.
Our results demonstrated that the increase in Ni content
brought about a positive effect on the activity of reduced
catalysts and the methane conversion of 15% Ni/MgAl2O4
catalyst was higher than that observed on the catalysts with
lower nickel content. The 15% Ni/MgAl2O4 catalyst showed
very high stability during 300 min time on stream. The results
showed that the feed ratio plays a decisive role on catalytic
activity during ATR reaction and the increase in O2/CH4 feed
ratio until O2/CH4 0.5 and also increase in H2O/CH4 until
H2O/CH4 1 increases the CH4 conversion. The activity results
also indicate that increasing the GHSV leads to a decrease in
CH4 conversion due to decrease of residence time and amount
of adsorbed reactants.
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