Applied Catalysis A: General 529 (2017) 19

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Feature Article

Synthesis Gas Production by Catalytic Partial Oxidation of Propane on

Mesoporous Nanocrystalline Ni/Al2 O3 Catalysts
Mohammad Peymani a , Seyed Mehdi Alavi b , Mehran Rezaei a,c,
a
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, P.O. Box
8731751117, Kashan, Iran
b
Chemical Engineering Department, Iran University of Science and Technology, Tehran, Iran
c
Institute of Nanoscience and Nanotechnology, University of Kashan, P.O. Box 8731751117, Kashan, Iran

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

Article history: Propane partial oxidation to synthesis gas at various feed conditions was investigated over nickel cat-
Received 18 August 2016 alysts supported on high surface area -alumina. The physicochemical characteristics of the calcined,
Received in revised form 8 October 2016 reduced and spent samples were determined by TPR, BET, XRD, TPO and SEM analyses. The inuences
Accepted 12 October 2016
of Ni content, reduction and reaction temperatures, gas hourly space velocity (GHSV) and feed ratio on
Available online 13 October 2016
the catalytic properties were investigated. The activity measurements revealed that the propane conver-
sion had a direct relation with reaction temperature and nickel loading and increased with increasing of
Keywords:
both these factors. However, there was an optimum value for nickel content and reaction temperature
Propane partial oxidation
Coke formation
in which the H2 and CO yields were maximum. The 7.5 wt% Ni/Al2 O3 exhibited high stability for 12 h
Nickel catalysts without any decrease in activity. However, the selectivity declined gradually with reaction time due to
Mesoporous carbon formation. The TPO analysis revealed that an increase in O2 /C molar ratio from 0.25 to 0.75 caused
-alumina a decrease in the amount of deposited carbon. Also, the amount of accumulated carbon slightly decreased
with rising the reaction temperature. These results were conrmed by the SEM analysis and the lamen-
tous carbon was observed on the catalyst surface. In addition, the increase in reduction temperature
caused an increase in C3 H8 conversion and H2 /CO ratio.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, synthesis gas or syngas (A mixture of H2 and CO with
various ratios), is mainly used for production of chemicals such
as ammonia and methanol in reneries, petrochemicals, in ferrous
industries and gas-to-liquids (GTL) technology [1,2]. Furthermore,
the preferred feedstock for syngas production is methane or natu-
ral gas because of its relatively lower cost of the end product. There
are some problems for natural gas as a fuel source includes dif-
culties in storage and transportation. Hence, light hydrocarbons,
such as propane and butane, can be easily stored, distributed and
transported as a source for production of syngas [36]. Therefore,
in recent years researchers have focused on the synthesis of high
active and stable catalysts for catalytic partial oxidation of light
hydrocarbons.
Corresponding author at: Catalyst and Advanced Materials Research Laboratory,
Chemical Engineering Department, Faculty of Engineering, University of Kashan, P.O.
Box 8731751117, Kashan, Iran.
E-mail address: Rezaei@kashanu.ac.ir (M. Rezaei).
There are three possible routes for the conversion of hydro-
carbons to hydrogen: steam reforming (SMR), catalytic partial
oxidation (POX) and autothermal reforming (ATR). The SMR reac-
tion is a highly endothermic reaction with a high operational
cost. Nowadays, POX has received signicant attention due to its
availability and low-cost. Both catalytic processes suffer from the
deactivation of catalysts, mainly caused by the carbon accumula-
tion on the catalyst surface [3,7,8].
It is known that the metallic coordination depends on the solid
structure and in oxidation reactions, which are structure sensitive,
the structural characteristics of the metal oxide catalysts signi-
cantly inuence the catalytic performance [9,10].
POX reaction has been studied over Ni, Co and noble metal-
based catalysts. Although the precious metals have shown high
performance, but the high cost of them restricts their industrial
usage [11,12]. In contrast, the inexpensively of Ni-catalysts causes
the widespread usage of nickel based catalysts in POX reactions but
they are sensitive to coke formation and sintering [7,13]. The cata-
lyst support can inuence the catalytic performance because it can
improve the active phase dispersion, decrease the inactive spinel
phase formation, increase the active phase reducibility and oxygen

http://dx.doi.org/10.1016/j.apcata.2016.10.012
0926-860X/ 2016 Elsevier B.V. All rights reserved.
2 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19

Fig. 1. XRD patterns of the carrier and reduced catalysts.

mobility on surface [14,15]. Alumina is one of the most popular

supports and widely used in industrial catalysts due to low price
and good structural properties and high surface area.
In this work, the activity and selectivity of the mesoporous
nanocrystalline Ni/Al2 O3 catalysts with different Ni contents were
studied in propane partial oxidation reaction. The effects of feed
ratio, GHSV and reduction temperature on the catalytic properties
of the catalysts were also studied. Furthermore, the inuence of
feed ratio and temperature of reaction on carbon deposition was
determined.

2. Experimental

2.1. Materials

The used chemicals for preparing the catalysts were the nitrate
salt of nickel (Ni(NO3 )2 6H2 O, Loba Chemie) and -Al2 O3 (Sasol) as
Ni active phase precursor and catalyst support, respectively. Fig. 2. (a) N2 adsorption-desorption isotherms and (b) Pore size distributions of the
reduced samples.

2.2. Catalyst preparation

determined by a Younglin gas chromatograph (HID detector and

The catalysts were prepared by a wetness impregnation method
Carboxen 1010 column). The values of propane conversions, H2 and
with different nickel loadings. Prior to the impregnation, the sup-
CO yields and CH4 , CO2 , C2 H4 and C2 H6 selectivities were obtained
port was crushed and sieved to obtain the particles with a size
using the following equations [16]:
smaller than 0.25 mm. The prepared particles were stabilized by
calcination at 700 C for 3 h and impregnated with an aqueous solu-
FC3 H6 ,in FC3 H6 ,out
tion of nickel nitrate with appropriate concentration to obtain the XC3 H6 = 100 (1)
desired Ni loading. The slurry was agitated at room temperature FC3 H6 ,in
for 3 h and dried at 80 C and subsequently heat treated at 600 C
for 3 h. FH2 ,out
YH2 = 100 (2)
4(FC3 H6 ,in FC3 H6 out )
2.3. Catalytic evaluation
FCO,out
YCO = 100 (3)
All the experiments were done in a microreactor (length: 70 cm, 3(FC3 H6 ,in FC3 H6 ,out )
inner diameter: 8 mm) under ambient pressure. The microreactor
was loaded with a specic weight (0.1 g) of the catalyst sieved to Fn,out
Sn = 100 (4)
3560 mesh. Prior to injection of feed, the catalysts were reduced (Ftotal,out FH2 ,out )
with pure H2 at 700 C for 3 h. The feed gas stream was consisted of
C3 H8 and O2 with desired molar ratio and diluted with He as carrier Where Fin and Fout are the volumetric ow rates of the components
gas. The activity tests were carried out in the temperature range in the feed and product gas streams, respectively. Fout was calcu-
of 550700 C. The reactor efuent was passed through a water lated with carbon balance. Where n is the component like CO, CH4 ,
trap to remove the moisture and after that its composition was CO2 , C2 H4 and C2 H6 .
 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19
Table 1
Structural properties of the carrier and reduced catalysts.
Sample BET surface area (m2 /g)
Reduced Spent
Al2 O3 191.53
2.5Ni/Al2 O3 169.82 119.42
5Ni/Al2 O3 160.35 92.39
7.5Ni/Al2 O3 157.26 75.57
10Ni/Al2 O3 148.60 65.77
Fig. 3. H2 -TPR proles of the calcined catalysts [24].
2.4. Catalyst characterization
The crystalline phases of the fresh and reduced catalysts were
identied by powder X-ray diffraction (XRD) analysis using a
PANalytical XPert-Pro instrument. The step scans were recorded
between 2 = 1080 . The average crystallite size of metallic
Ni was calculated by using the Scherrer equation. Nitrogen
adsorption-desorption analysis of the reduced catalysts was per-
formed at 196 C in a gas adsorption analyzer (BELSORP mini
II). A Vega@Tescan instrument was used for scanning electron
microscopy (SEM) analysis. TPR (Temperature Programmed Reduc-
tion) and TPO (Temperature Programmed Oxidation) analyses of
the calcined and spent catalysts were done by an automatic appa-
ratus (Chemisorb 2750, Micromeritics). The details of TPR and TPO
procedures could be found in our previous work [17].
3. Results and discussion
3.1. Structural properties of the catalysts
The diffraction patterns of the support and reduced samples
with different Ni loadings are shown in Fig. 1. For the catalyst with
2.5 wt.% Ni, because of the small content of nickel, the diffraction
peaks assigned to the nickel and nickel oxide were not seen. Sev-
eral diffraction peaks were observed by increasing of nickel content,
which were located at 44.5, 51.8 and 76.5 , corresponding to (111),
(200) and (220) plans of metallic Ni (JCPDS. 004-0850). As seen,
in all the samples the increase in nickel content intensied the Ni
diffraction peaks.
The XRD results reveal that the support is in the gamma phase
[18]. The observed peaks at 2 = 37.6 and 45.79 are attributed to
3
Pore volume (cm3 /g) Pore diameter (nm) Crystallite size (nm)
Reduced Spent Reduced Spent
0.502 10.50
0.513 0.290 12.09 9.38
0.484 0.187 12.07 8.09 5.1
0.474 0.156 12.04 8.27 9.1
0.451 0.133 12.15 8.10 11.8
Al2 O3 (JCPDS. 01-1303). The small peak at about 2 = 62 is ascribed
to NiAl2 O4 phase (JCPDS. 71-0965). The Al2 O3 and NiAl2 O4 phases
are overlapped at 2 = 67 and 37 .
The reduced Ni/Al2 O3 catalyst at 700 C exhibited two main
crystallite phases: -Al2 O3 and NiAl2 O4 . -Al2 O3 shows a pseu-
dospinel structure and the lattice parameters of -Al2 O3 are very
close to NiAl2 O4 , so it is difcult to recognize these phases because
the overlap between their diffraction peaks [19].
The nickel crystallite sizes calculated by Scherrer equation are
presented in Table 1. The Ni crystallite sizes were increased size
from 5.1 to 11.8 nm by the increase in Ni content.
The textural characteristics of the catalyst carrier and reduced
catalysts with various Ni contents are presented in Table 1. As
shown, the catalyst carrier exhibited high BET area and with
increasing the Ni content, the pore volume and surface area
decreased due to blockage of the pores by Ni particles and/or
destruction in mesoporous structure at high temperature. Enhanc-
ing in Ni loading does not signicantly inuence the pore diameter.
It was suggested that proper nickel content could benet the for-
mation of highly dispersed NiO with high surface area [20].
The isotherms of the reduced catalysts are depicted in Fig. 2a.
They can be classied as the type IV isotherm, typical for meso-
porous structures. Also, for these catalysts, the H2 hysteresis loop
observed at a relative pressure range (P/P0 = 0.60.9), which gener-
ally is assigned to solids made of particles crossed by channels with
cylindrical shape [21,22].
Additionally, Fig. 2b presented the pore size distributions of the
samples. All the samples have a mesoporous structure with distri-
bution of pore in the range of 210 nm. The pore size distribution
was shifted to broader size when nickel loading increased.
3.2. Temperature-programmed reduction
In order to study the redox behavior of the catalysts with dif-
ferent Ni loadings, H2 -TPR analysis was carried out and the proles
are presented in Fig. 3. The reduction of all catalysts was started
at 400 C. As can be seen, three types of peaks are seen in these
patterns, which suggest the existence of three types of Ni species
assigned by , and symbols, respectively. The small peak
located at 400500 C can be assigned to the reduction of bulk
nickel oxide and weakly interacted NiO with the catalyst carrier.
The peak observed around 600 to 750 C is related to the reduction
of strongly interacted NiO with Al2 O3 . The third reduction peak ()
at temperature above 800 C is assigned to the reduction of NiAl2 O4
[11,23,24].
It is clearly observed that with the increase in Ni content, the
reduction peaks were shifted to lower temperatures. It indicated
that more reducible Ni species were formed in higher metal con-
tent. The results showed that increasing in nickel content weakened
the interaction between NiO and Al2 O3 and the reduction peaks
moved to lower temperatures. Furthermore, the area under the
reduction patterns increased with the increase of the nickel content
of catalysts, due to higher hydrogen consumption on the catalyst
with higher nickel content[24].
4 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19

Fig. 4. (a) C3 H8 conversion, (b) H2 /CO ratio, (c) H2 yield and (d) CO yield, O2 /C = 0.5, Fig. 5. (a) CH4 selectivity, (b) CO2 selectivity, (c) C2 H4 selectivity and (d) C2 H6
GHSV = 60,000 (ml/h gcat ),C3 H8 = 10%. selectivity, O2 /C = 0.5, GHSV = 60,000 (ml/h gcat ), C3 H8 = 10%.
 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19 5

Fig. 6. Effect of GHSV on the activity and selectivity of 7.5%Ni/Al2 O3 ,O2 /C = 0.5,T

= 600 C.

Fig. 9. (a) N2 adsorption-desorption isotherms and (b) Pore size distributions of

Fig. 7. Effect of O2 /C ratio on the activity and selectivity of 7.5%Ni/Al2 O3 , 7.5% Ni/Al2 O3 reduced at different temperatures.

GHSV = 60000 mL/(gcat h),T = 600 C.
Table 2
Textural properties of 7.5% Ni/Al2 O3 catalyst at different reduction temperatures.

Reduction BET surface area Pore volume Pore diameter

temperature ( C) (m2 /g) (cm3 /g) (nm)

500 159.12 0.474 11.91

600 158.53 0.474 11.96
700 157.26 0.474 12.04

3.3. Catalytic performance

3.3.1. Effect of reaction temperature and Ni content

Fig. 8. Stability of C3 H8 conversion, H2 yield and CO, C2 H4 and C3 H6 selectivities of
7.5%Ni/Al2 O3 , GHSV = 60000 mL/(gcat h),T = 700 C,O2 /C = 0.5.
The inuences of temperature and nickel content on the activ-
ity of catalysts in propane partial oxidation reaction were studied
and the results are presented in Fig. 4a. The propane conversions
enhanced when the temperature increased from 550 to 700 C due
to increasing in the rate of reaction with the increase of tempera-
ture. The results showed that C3 H8 conversion increased with the
enhancement of Ni content from 2.5 to 10 wt.% due to increase of
available nickel to reactants. With increasing in reaction temper-
ature the product ratio (H2 /CO ratio) for all samples except of the
catalyst with 2.5% Ni decreased due to occurrence of the reverse
6 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19
Fig. 10. (a) C3 H8 conversion and (b) H2 /CO ratio of 7.5% Ni/Al2 O3 catalyst, O2 /C = 0.5,
GHSV = 60,000 (ml/h gcat ).
Fig. 11. TPO proles of 7.5% Ni/Al2 O3 evaluated under different O2 /C ratios
(T = 600 C, GHSV = 60000 mL/(gcat h)).
Fig. 12. Effect of reaction temperature on the TPO prole of 7.5% Ni/Al2 O3 (O2 /C = 0.5,
GHSV = 60000 mL/(gcat h),).
water gas shift reaction (RWGS) [25] as shown in Fig. 4b. Also, The
7.5 Ni/Al2 O3 catalyst exhibited maximum H2 /CO ratio at various
reaction temperatures. The yields of H2 and CO of the catalysts
are shown in Fig. 4c and 4d, respectively. The H2 and CO selectivi-
ties improved with the increase of the reaction temperature up to
600 C and the further increase in temperature declined the H2 and
CO yields due to formation of by-products. Also, with increasing in
Ni loading from 2.5 to 5 wt%, H2 and CO selectivities increased and
then decreased at nickel loadings higher than 5 wt%.
The by-product selectivities are shown in Fig. 5. The selectiv-
ity to methane is between 0.5 to 17% at different temperatures
as shown in Fig. 5a. The minimum selectivity to methane was
observed at 600 C in catalysts with various Ni loadings. The results
in Fig. 5b showed the decrease in CO2 selectivity with increasing in
the reaction temperature, due to reverse water gas shift and CO2
consumption [26]. As shown in Fig. 5c and 5d, the by-product for-
mation occurred at 650 C. The optimal temperature for propane
partial oxidation is the temperature with maximum hydrogen yield
and the lowest byproducts production. The results showed the
maximum hydrogen production was occurred at a temperature of
600 C for propane [4].
The textural properties of the spent catalysts with various nickel
contents are reported in Table 1. It is clearly observed that the
BET area and pore volume decreased after reaction due to ther-
mal sintering of catalyst particles at high temperature and also the
carbon formation. The accumulated carbon on the catalyst surface
can block the pores and reduce the BET area.
3.3.2. Effect of GHSV
Fig. 6 presents the inuence of GHSV on the catalytic activity and
selectivity of 7.5% Ni/Al2 O3 catalyst for partial oxidation at 600 C
and C3 H8 :O2 = 1: 1.5. The graphs show that with increasing in GHSV
from 15000 to 60000 mL/(gcat h), the C3 H8 conversion increased
from 53 to 70% and further increase in GHSV does not have a sig-
nicant effect on propane conversion. It may be due to increasing
in the amount of heat released from the bed of catalyst by enhanc-
ing the space velocity. It is noted that the catalyst bed temperature
was controlled with inserted thermocouple in bottom of the cata-
lyst bed. However, the enhancement of the temperature of the inner
surface of the catalyst particles was inevitable. In fact, enhancing
of the space velocity indirectly leads to increase the temperature
 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19
Fig. 13. SEM images of 7.5%Ni/Al2 O3 catalyst at (a) O2 /C = 0.75, (b) O2 /C = 0.5 and (c) O2 /C = 0.25.
of the catalyst particles [27]. The same trend was also seen for the
selectivities of H2 and CO.
3.3.3. Effect of feed ratio
Fig. 7 shows the inuence of the molar feed ratio on the activity
and selectivity of the catalysts. It is clear that increasing in oxygen
content of feed caused to consuming propane due to occurring of
both partial and complete oxidation. It is known that the total com-
bustion is more favorable than the partial oxidation at higher O2 /C
ratios, and at these conditions the high quantities of CO2 and H2 O
were formed. The CO2 selectivities increased signicantly while the
CH4 selectivities were nearly the same. The higher O2 /C molar ratios
caused a decrease of the H2 selectivity. Due to the low content of
CH4 , hydrogen might be reacted by the excess O2 , which led to
higher H2 O selectivity (not shown in Fig. 7) [26].
3.3.4. Catalytic stability
The stability of C3 H8 conversion, H2 yield, CO, C2 H4 and C3 H6
selectivities for 7.5% Ni/Al2 O3 catalyst during 12 h time on stream
at 700 C are shown in Fig. 8. The catalyst possessed high stabil-
ity without any decline in propane conversion. It is seen that with
increasing time, the H2 yield and CO selectivities were decreased
due to the formation of byproducts such as ethylene and propylene.
7
3.3.5. Effect of reduction temperature
Table 2 presented the textural characteristics of the 7.5%
Ni/Al2 O3 catalyst with different reduction temperatures. It can be
seen that increasing in reduction temperature caused a decline in
the BET area. However, it did not have a signicant inuence on
the pore volume and pore size. The nitrogen adsorption/desorption
isotherms of the reduced catalysts at different temperatures are
shown in Fig. 9a. As shown, IV type isotherms with H2 shape
hysteresis loop were observed in all catalysts. The pore size dis-
tributions of these catalysts are shown in Fig. 9b.
The effects of reduction temperature on the catalytic perfor-
mance of the 7.5% Ni/Al2 O3 catalyst were investigated and the
results are shown in Fig. 10a and 10b. As expected, the increase in
reaction temperature leads to increase in propane conversion. The
increase in reduction temperature slightly increased the propane
conversion due to more reduced Ni on the catalyst surface.
The increase in reduction temperature also enhanced the prod-
uct ratio (H2 /CO molar ratio) in all temperatures, Fig. 10b.
3.4. TPO analysis
The TPO analyses of the 7.5% Ni/Al2 O3 catalysts after reaction
with various O2 /C ratios are presented in Fig. 11. The results indi-
cated that the amount of accumulated carbon decreased with the
increase of the O2 /C ratio. No detectable carbon was observed at
8 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19
Fig. 14. SEM images of 7.5%Ni/Al2 O3 catalyst at (a) T = 500 C, (b) T = 600 C and (c) T = 700 C.
O2 /C ratio of 0.75. The low amount of accumulated carbon could
be related to high dispersion of nickel in high surface area of alu-
mina and the excess of oxygen content respect to the stoichiometric
value can increase oxygen species in surface and therefore reduce
the deposited carbon. The highest content of carbon was observed
at O2 /C = 0.25, due to the highest area under the TPO prole. The
elementary chemical potential calculations in a free energy mini-
mization technique showed that, the potential of carbon formation
was increased with decreasing the O2 /C ratio [13,28].
The carbon deposition over the 7.5% Ni/Al2 O3 at various reac-
tion temperatures at O2 /C = 0.5 was studied and the TPO curves are
presented in Fig. 12. It is clearly seen that an increase in temper-
ature of reaction leads to decrease in the intensity and the area of
the TPO curves. It means lower amounts of carbon formation at
higher reaction temperature, due to exothermic nature of CO dis-
proportionation, which is thermodynamically unfavorable at high
reaction temperature [2830].
3.5. SEM analysis
SEM images of the spent 7.5% Ni/Al2 O3 catalysts evaluated under
different O2 /C ratios are presented in Fig. 13. It is clear that the
amount of whisker carbon increased with the decrease of O2 /C ratio.
As shown in Fig. 13, no observable carbon was seen at O2 /C = 0.75.
This conrms the results of TPO analysis, which showed lower con-
tent of carbon deposition at higher O2 /C ratio. Fig. 14 shows the SEM
images of the 7.5% Ni/Al2 O3 evaluated under various reaction tem-
peratures. As shown, the content of whisker carbon decreased with
the increase of reaction temperature.
4. Conclusions
The Ni/Al2 O3 catalysts with various nickel loadings were pre-
pared by a wetness impregnation method. The results showed that
these catalysts possessed mesoporous structure with a distribu-
tion of pores in the range of 210 nm. The synthesized catalysts
with various Ni contents (2.510 wt%) were evaluated in partial
oxidation of propane. The catalytic results showed that increas-
ing in nickel loading increased the catalytic activity but H2 and CO
selectivities have an optimum depending on the Ni content and
reaction temperature. The optimal temperature for partial oxida-
tion of propane was 600 C. These catalysts exhibited high stability
for 12 h without any decline in conversion but H2 and CO selec-
tivities decreased during time on stream. Increasing in reduction
temperature from 500 C to 700 C led to increase the catalyst activ-
ity and selectivities. TPO results showed that the decreasing the
feed ratio and reaction temperature led to increasing the content
of accumulated on the catalyst surface. SEM analyses showed the
formation of whisker type carbon over the catalyst surface.
 M. Peymani et al. / Applied Catalysis A: General 529 (2017) 19
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