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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

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Syngas production from methane dry reforming

over Ni/SBA-15 catalyst: Effect of operating
parameters

Osaze Omoregbe a, Huong T. Danh b, Chinh Nguyen-Huy c,

H.D. Setiabudi a, S.Z. Abidin a, Quang Duc Truong d, Dai-Viet N. Vo a,e,*
a
Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300,
Gambang, Kuantan, Pahang, Malaysia
b
Clean Energy and Chemical Engineering, Korea University of Science and Technology (UST), Daejeon, 305-350,
Republic of Korea
c
School of Energy & Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST),
50 UNIST-gil, Eonyang-eup, Ulju-gun, Ulsan, 689-798, Republic of Korea
d
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-Ku,
Sendai, 980-8577, Japan
e
Centre of Excellence for Advanced Research in Fluid Flow, Universiti Malaysia Pahang, 26300, Gambang, Kuantan,
Pahang, Malaysia

article info abstract

Article history: The influence of operating conditions including reactant partial pressure and reaction
Received 4 January 2017 temperature on the catalytic performance of 10%Ni/SBA-15 catalyst for methane dry
Received in revised form reforming (MDR) reaction has been investigated in this study. MDR reaction was carried out
25 February 2017 under atmospheric pressure at varying CH4/CO2 volume ratios of 3:1 to 1:3 and 923e1023 K
Accepted 21 March 2017 in a tubular fixed-bed reactor. SBA-15 supported Ni catalyst exhibited high specific surface
Available online 7 April 2017 area of 444.96 m2 g
1 and NiO phase with average crystallite size of 27 nm was detected on
catalyst surface by X-ray diffraction and Raman measurements. H2 temperature-
Keywords: programmed reaction shows that NiO particles were reduced to metallic Ni0 phase with
Methane dry reforming degree of reduction of about 90.1% and the reduction temperature depended on the extent
Syngas of metal-support interaction and confinement effect of mesoporous silica support. Cata-
Hydrogen lytic activity appeared to be stable for 4 h on-stream at 973e1023 K whilst a slight drop in
SBA-15 support activity was observed at 923 K probably due to deposited carbon formed by thermody-
Ni-based catalysts namically favored CH4 decomposition reaction. Both CH4 and CO2 conversions increased
with rising reaction temperature and reaching about 91% and 94%, respectively at 1023 K
with CO2 and CH4 partial pressure of 20 kPa. CH4 conversion improved with increasing CO2
partial pressure, PCO2 and exhibited an optimum at PCO2 of 30e50 kPa depending on reaction
temperature whilst a substantial decline in CO2 conversion was observed with growing
PCO2 . Additionally, CH4 and CO2 conversions decreased significantly with rising CH4 partial
pressure because of increasing carbon formation rate via CH4 cracking in CH4-rich feed.

* Corresponding author. Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300
Gambang, Kuantan, Pahang, Malaysia. Fax: þ60 9 549 2889.
E-mail address: vietvo@ump.edu.my (D.-V.N. Vo).
http://dx.doi.org/10.1016/j.ijhydene.2017.03.146
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
11284 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

Post-reaction characterization shows that active Ni metal phase was not re-oxidized to
inactive metal oxide during MDR reaction. The heterogeneous nature of deposited carbons
including carbon nanofilament and graphite was detected on catalyst surface by Raman
measurement.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

1

CH4 /2H2 þ C DG0 ¼ 89:53
0:11T kJ mol (3)
Introduction
In order to hinder sintering and improve the catalytic
The important role of syngas, a mixture of H2 and CO, in both activity as well as coking resistance of Ni catalyst, different
chemical and petrochemical industries has been widely types of metal oxides such as Al2O3 [19,20], TiO2 [21] and ZrO2
recognized since it is currently utilized as a main feedstock for [22] have been utilized as support of Ni catalyst for increasing
producing environment-friendly synthetic fuels and meth- surface area and metal dispersion. Silica-based SBA-15 sup-
anol via respective FischereTropsch synthesis [1e3] (FTS) and port has recently gained significant interest for hosting and
methanol production [4]. The conventional and large-scale dispersing Ni nanoparticles due to its outstanding physical
production of syngas was by coal gasification [5], partial properties including extremely high specific surface area,
oxidation [6] and steam reforming [7,8] of methane. However, ordered mesoporous channels with thick pore walls and
the major drawback of these processes is the significant and great hydrothermal stability [23e25]. In fact, SBA-15 support
undesirable emission of an anthropogenic greenhouse gas, has been employed for a wide range of heterogeneous cata-
viz., CO2 gas contributing to global warming [9,10]. Hence, dry lytic reactions (including methane steam reforming [8,26],
(or CO2) reforming of CH4 (see Eq. (1)) has been considered as a ethanol steam reforming [27,28] and FischereTropsch syn-
feasible and alluring alternative approach for syngas genera- thesis [29]), and exhibited desirable performance as well as
tion as it not only mitigates CO2 greenhouse gas emission but stability. Interestingly, Arcotumapathy et al. [8] recently
also transfer it to a value-added product [11,12]. Additionally, found that Ni supported on SBA-15 catalyst exhibited the
the steam reforming and partial oxidation of methane pro- great resistance towards carbon deposition during methane
duce syngas with high H2/CO ratio of 3 and 2, correspondingly steam reforming reaction. Wang et al. [30] also reported that
[13] whilst the ratio of H2 to CO in syngas obtained from the high resistance to carbon formation over SBA-15 sup-
methane dry reforming (MDR) reaction is close to unity [10,13] ported Ni catalyst was attributed to the large surface area of
suitable for the production of oxygenated chemicals and long- SBA-15 support which induced great Ni metal dispersion and
chain hydrocarbons in downstream FTS [2,14] as well as hence hindered the formation of large Ni particles favored for
dimethyl ether (DME) [15]. carbon formation.

1

Apart from tuning physicochemical attributes of catalysts
CH4 þ CO2 /2CO þ 2H2 DG0 ¼ 256:67
0:28T kJ mol (1) employed, manipulating the operating conditions such as
with T being temperature (K). reaction temperature and feed composition was a feasible
Although noble metal catalysts, namely, Rh, Pt and Pd are approach for ensuring optimal catalytic performance and
substantially active and resistant to carbon deposition in stability for MDR reaction. Although several studies have
comparison with other transition metals [16]. However, they examined the role of operation parameters on the activity
are not applicable for industrial scale since precious metals and selectivity of MDR over various catalysts, namely, Rh/a-
are less available and not cost-effective [13]. Thus, MDR re- Al2O3 [31], NieCo/La2O3eAl2O3 [32], and Co/CeO2 catalysts
action has been conventionally carried out on Ni-based cata- [33], the impact of operating conditions seemed to be varied
lysts due to their comparable activity to noble metals, depending on the extent of secondary reactions associated
excellent capacity for CeH bond scission and reasonable cost with the physicochemical characteristic of utilized catalyst
[10,13]. Since Ni metal possesses low Tammann temperature [34]. To the best of our knowledge, in-depth research about
of 964 K, the thermal sintering and particle agglomeration the role of process conditions on Ni/SBA-15 catalyst for MDR
may induce catalyst deterioration [17]. Additionally, metallic reaction has not been reported before. Additionally, an un-
Ni0 phase has an unfilled d-orbital capable of accepting CeH s- derstanding of how operating parameters, i.e., reaction
electron of adsorbed CH4 molecule [18]. Thus, this could temperature and feed composition affect the activity of Ni/
weaken or rupture the CeH bond and hence form surface SBA-15 catalyst during MDR reaction is crucial for kinetic
carbonaceous species lessening catalytic activity. The low studies and efficient reactor design. Hence, this work aims to
resistance to carbon deposition formed by the undesirable investigate the effect of operating parameters, i.e., reactant
side reactions, viz., Boudouard and methane decomposition partial pressure and reaction temperature on the MDR per-
reactions (cf. Eqs. (2) and (3), respectively) is one of the main formance of Ni catalyst supported on SBA-15 in order to have
drawbacks of Ni-based catalysts [10,13]. a better understanding. The physical and chemical properties
of fresh and spent Ni/SBA-15 catalysts were also examined in

1

2CO%CO2 þ C DG0 ¼
170:34 þ 0:18T kJ mol (2) this research.
 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4 11285

H2 temperature-programmed reduction (H2-TPR) was also

Experimental carried out in an AutoChem II-2920 system. After a pre-
treatment at 373 K for 30 min in flowing He gas
Catalyst preparation (50 mL min
1) to remove moisture and volatile compounds,
about 0.1 g of sample placed in a quartz U-tube was heated
SBA-15 support was prepared by the dissolution of about 16 g with a linear rate of 10 K min
1 from 373 to 1173 K under the
of triblock-poly(ethylene glycol)-block-poly(propylene glycol)- 50 mL min
1 flow of 10%H2/Ar mixture. The Raman spectra of
block-poly(ethylene glycol), commonly known as Pluronic® P- fresh and spent catalysts were obtained with a DXR Raman
123 (EO20PO70EO20 with an average molecular weight of 5800 Microscope (Thermo Fisher Scientific) using a 532 nm laser
purchased from Sigma-Aldrich Chemicals) in 416 mL of 2 M excitation.
HCl solution (with pH of about 1) at 303 K. The white mixture Additionally, in order to quantify the amount of deposited
was rigorously stirred at 1000 rev. min
1 for 2 h followed by carbon on used catalyst after MDR reaction, temperature-
the dropwise addition of 32 g of tetraethyl orthosilicate (TEOS programmed oxidation (TPO) was conducted on a TGA Q500
supplied by Merck Millipore). The resulting mixture was unit (TA Instruments). Approximately 5 mg of used catalyst
further stirred thoroughly for 24 h at 310 K. The precipitated mounted in a ceramic crucible was initially dehydrated at
powder was subsequently filtered out and rinsed with deion- 373 K for 30 min in N2 flow (100 mL min
1). Pre-treated sample
ized water. After being dried in an oven at 373 K overnight, it was then heated up to 1023 K with purging 20%O2/N2 mixture
was calcined in stagnant air at 823 K for 6 h in the same oven (100 mL min
1) at a heating rate of 10 K min
1 [20]. It was
with a ramping rate of 2 K min
1 to obtain SBA-15 support. further kept isothermally at the same temperature for 30 min
The incipient wetness impregnation method [35] was to ensure the complete oxidation of carbonaceous deposits
employed for producing a 10%Ni/SBA-15 catalyst. An accu- followed by cooling down to room temperature in N2 flow. The
rately balanced amount of as-synthesized SBA-15 support was amount of deposited carbon was also verified for selected
mixed with a calculated quantity of Ni(NO3)2$6H2O (procured spent catalyst using scanning electron microscopy (SEM)
from Sigma-Aldrich Chemicals) aqueous solution and stirred coupled with energy dispersive X-ray analysis (EDX) on a
carefully in a rotary evaporator (BÜCHI Rotavapor R-200) for Hitachi Tabletop Microscope TM3030Plus, and CHNS
2 h at 338 K under vacuum condition. The impregnated solid elemental analysis on Elementar vario Micro cube unit.
was then dried at 373 K in an oven for 24 h followed by
calcination in air at 973 K for 5 h with a heating rate of Methane dry reforming reaction
2 K min
1. The calcination temperature of 973 K was selected
to ensure the complete decomposition of Ni(NO3)2 metal pre- The MDR runs were carried out in a quartz tube fixed-bed
cursor to NiO phase during air-calcination based on previous continuous flow reactor at a temperature range of
temperature-programmed calcination (TPC) measurement 923e1023 K and varied CH4:CO2 volume ratios of 3:1 to 1:3
(see Fig. S1 in supplementary data). under atmospheric pressure. The 10%Ni/SBA-15 catalyst with
loading of 0.15 g was mounted in the middle of reactor by
Catalyst characterization quartz wool. The quartz tube reactor (O.D. ¼ 3/8 in. and length,
L ¼ 17 in.) was placed vertically in a split temperature-
The BrunauereEmmetteTeller (BET) surface area measure- controlled furnace and reaction temperature was continu-
ment for both SBA-15 support, and 10%Ni/SBA-15 catalyst was ously measured with time-on-stream (TOS) during reaction.
performed in a Micromeritics ASAP-2010 apparatus employ- Catalyst was activated in situ in 60 mL min
1 of 50%H2/N2 at
ing N2 adsorption and desorption isotherms data at 77 K. The 923 K with a heating rate of 5 K min
1 for 2 h prior to each MDR
aforementioned BET measurement was performed after the test. The flow rate of both reactant (i.e., CH4 and CO2) and N2
samples were degassed in N2 flow at 573 K for 1 h for elimi- diluent gases was accurately regulated by Alicat mass flow
nating residual moisture and volatile impurity. The Rigaku controllers. The input gas pressure was kept constant at 3 bar
Miniflex II system using Cu monochromatic X-ray radiation during experiment whilst the output gas pressure from the
(with wavelength, l of 1.5418 
A) was employed for measuring outlet of reactor was at about 1 atm. After well blending in a
X-ray diffraction (XRD) patterns of both fresh and spent cat- mixer (Swagelok cross), the gaseous mixture was directed to
alysts at 30 kV and 15 mA. Moderately small step size of 0.02 the top of the fixed-bed reactor with a total flow rate of
and scan speed of 1 min
1 were implemented in order to 60 mL min
1. N2 inert gas was used as a top-up to ensure the
obtain a high resolution throughout the scanning within the constant total flow rate of 60 mL min
1 when the flow rates of
range of 2q ¼ 3oe80 . CH4 and CO2 reactants were varied during the study of oper-
The framework and surface morphology of calcined SBA- ating conditions. Gas hourly space velocity (GHSV defined as
Total flow rate
1
1
15 support and fresh 10%Ni/SBA-15 catalyst were studied Catalyst loading [36]) of 24 L gcat h and small mean particle size
using a field-emission scanning electron microscope (FESEM) of 100e140 mm were implemented for each run to assure
in a JEOL JSM-7800F apparatus whilst high-resolution trans- insignificant mass and heat transfer resistances for acquiring
mission electron microscopy (HRTEM, TOPCOM EM-002B, intrinsic catalytic activity. Gaseous products from the bottom
200 kV) were conducted for spent catalyst to examine the of reactor were passed through a cold trap and a drierite
type of carbonaceous deposition on catalyst surface. Speci- adsorbent bed for eliminating H2O by-product before being
mens were dispersed in ethanol and then dropped onto Cu analyzed in an online gas chromatograph (Agilent 6890 Series
microgrid coated with a holey carbon film, followed by the GC system; HP-PLOT Q capillary column with size of
evaporation of the ethanol. 30 m  0.53 mm  40 mm) installed with TCD detector. The
11286 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

flow rate of gaseous effluent from fixed-bed reactor was comparison with other semiconductor oxide supports such as
measured using volumetric (bubble) flowmeter. The sche- Al2O3 [20] and TiO2 [37], the calcined SBA-15 support has a high
matic diagram of experimental set-up for MDR reaction is also specific surface area of about 550 m2 g
1 in line with other
illustrated in Fig. S2 (supplementary data). studies [38,39] as seen in Table 1.
The catalytic performance was assessed using reactant However, there was an unavoidable and significant decline
conversion, Xi (i: CH4 or CO2), product selectivity, Sj (with j in both BET surface area and average pore volume from 550 to
being H2 or CO), yield, Yj, and H2/CO ratio as given in Eqs. 445 m2 g
1 and from 0.49 to 0.40 cm3 g
1, respectively for 10%
(4e10). Ni/SBA-15 catalyst after the addition of NiO on SBA-15 support
surface. This expected drop would indicate the effective
CH4
FCH4
FIn Out
XCH4 ð%Þ ¼  100% (4) diffusion of active metal into the framework of the ordered
FIn
CH4 mesoporous channels of SBA-15 support. The closure of
porous structure due to the clustering of NiO particles on pore
CO2
FCO2
FIn Out
entrances could also cause a decrease in these textural prop-
XCO2 ð%Þ ¼ In
 100% (5)
FCO2 erties (see FESEM image of 10%Ni/SBA-15 catalyst in Fig. 2 (c)).
In addition, the slight expansion of average pore diameter
FOut
H2
from 3.59 to 3.61 nm due to the isomorphous substitution of Si
SH2 ð%Þ ¼  100% (6) atoms in silica frameworks with Ni atoms resulting in
FOut
H2 þ FOut
CO
considerable wall contraction and hence the enlargement of
FOut pores [38,40,41].
SCO ð%Þ ¼ CO
 100% (7)
FOut
H2 þ FOut
CO
X-ray diffraction measurement
FOut The XRD patterns of fresh mesoporous SBA-15 support and 10%
H2
YH2 ð%Þ ¼  100% (8) Ni/SBA-15 catalyst are shown in Fig. 1. The Joint Committee on
2FIn
CH4
Powder Diffraction Standards (JCPDS) database was used for
the interpretation of all X-ray diffractograms [42]. The broad
FOut
YCO ð%Þ ¼ CO
 100% (9) peak detected at 2q of 15.0oe30.0 (cf. Fig. 1) for both support
CH4 þ FCO2
FIn In
and catalyst is attributed to the amorphous SiO2 frameworks of
and the SBA-15 support (JCPDS card No. 29-0085) consistent with
literature [43,44]. Apparently, four discrete diffraction peaks of
FOut
H2 crystalline NiO phase (JCPDS card No. 47-1049) were also
H2 =CO ratio ¼ (10)
FOut
CO noticed at 2q ¼ 37.3 , 43.3 , 63.0 , and 75.5 (belonging to the
with FIn and FOut being the inlet and outlet molar flow rates corresponding (1 0 1), (0 1 2), (2 2 0), and (3 1 1) planes of NiO
(mol s
1), respectively. phase) for the 10%Ni/SBA-15 catalyst. The average crystallite
size (dp) of NiO particles, estimated from Scherrer equation [45]
(see Eq. (11)) as about 27 nm, was significantly larger than
Results and discussion average pore diameter (see Table 1) indicating the agglomera-
tion of NiO crystallites on support surface.
Physicochemical properties of catalyst
0:94l
dp ðnmÞ ¼ (11)
Textural properties B  cosq
Table 1 summarizes the physical properties of both calcined where dp, l, B and q are the average crystallite size, X-ray
SBA-15 support and 10%Ni/SBA-15 catalyst including BET wavelength, the line broadening at half the maximum in-
surface area, average pore volume, and pore diameter. In tensity (FWHM) and Bragg angle in that order.

Table 1 e Summary of physical properties of SBA-15 support and 10%Ni/SBA-15 catalyst.

Catalysts Average BET surface Average pore Average pore Average crystallite
area (m2 g
1) volumea (cm3 g
1) diameter (nm) size, dpb (nm)
Calcined SBA-15 550.05 ± 9.83 0.49 3.59 e
10%Ni/SBA-15c 444.96 ± 6.57 0.40 3.61 27.04
Other studies Reference
Al2O3 174.13 0.38 5.46 [20]
TiO2 8.73 e 22.37 [37]
1%Lae5%Ni/SBA-15 468.00 0.70 7.00 [38]
SBA-15 581.00 1.18 6.90 [39]
a
Calculation is based on Barret-Joyner-Halenda (BJH) desorption method at P/P0 ¼ 0.99.
b
Average crystallite size was computed from XRD pattern using Scherrer equation [45].
c
Ni loading of 10% was verified by EDX measurement of fresh catalyst (see Fig. S3 (a) in supplementary data).
 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4 11287

SiO2 (JCPDS card No. 29-0085)

clustering of NiO particles (blue circles) on support surface
was corroborated with the considerable reduction in BET
(2 0 1) NiO (JCPDS card No. 47-1049)
surface area (cf. Table 1) and the larger average crystallite
(a) size of NiO particles than the average pore diameter of 10%
Ni/SBA-15 catalyst (see Table 1).
Intensity (a.u.)

(0 1 2)

(1 0 1)
(2 2 0) H2 temperature-programmed reduction
(2 0 1) The reducibility and phase formation during H2 activation
(3 1 1)
(b) were examined by H2-TPR as seen in Fig. 3. The high intensity
peak (P1) centered at low temperature of 644.3 K was attrib-
uted to the reduction of weakly bound NiO particles with high
crystallite size on the SBA-15 support surface to metallic Ni0
phase [38] (see Eq. (12)).
0 10 20 30 40 50 60 70 80
NiO þ H2 /Ni þ H2 O (12)
2 Theta (degree) 0
Gao et al. [46] also reported that Ni phase formed from the
Fig. 1 e XRD diffraction patterns of (a) SBA-15 support, and reduction of large NiO particles softly interacting with support
(b) calcined 10%Ni/SBA-15 catalyst. may freely migrate and agglomerate on support surface at high
reduction and reaction temperature. The small shoulder (P2) at
760.1 K was ascribed to the reduction of smaller NiO particles
Field-emission scanning electron microscope possessing strong metal-support interaction [38] or being
FESEM is a well-known imaging technique for investigating located inside the support channels [43,44,47]. In fact, the
the morphology of heterogeneous catalysts. The surface metal-support interaction in the mesoporous channels was
morphology of both SBA-15 support and 10%Ni/SBA-15 cata- greater than that of surface NiO particles owing to confinement
lyst captured from FESEM measurements is shown in Fig. 2. effect [48]. Additionally, in order to confirm the successful
FESEM micrograph shows that SBA-15 particles had a rela- reduction of NiO to Ni0 particles during H2-TPR measurement,
tively uniform rod-like shape with a diameter of about XRD measurement of 10%Ni/SBA-15 catalyst reduced at 760.1 K
0.55 mm (see Fig. 2 (a)). Additionally, these particles were was carried out at shown in Fig. S4 (supplementary data). The
interlinked to form wheat-like microstructures with ordered Ni0 metallic phase was evidently detected at 2q of 44.7 , 52.1 ,
mesoporous channels. However, the micrograph of 10%Ni/ and 76.6 belonging to the corresponding planes of (1 1 1), (2 0 0),
SBA-15 catalyst (cf. Fig. 2 (b)) shows that the shape of catalyst and (2 2 0) (JCPDS card No. 04-0850). Based on the total amount
particle was bended and particle length was quite shorter of H2 consumed of about 1.54 mmol H2 g
1 cat during H2-TPR, the
than that of SBA-15 support. As seen in Fig. 2 (c), the observed degree of NiO reduction was estimated as 90.1% (see Table 2). In

Fig. 2 e FESEM images of (a) mesoporous SBA-15 support, and fresh 10%Ni/SBA-15 catalyst at (b) £20,000, and (c) £50,000
magnification.
11288 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

100
(a)
P1
80

60
TCD signal (a.u.)

XCH (%)
4
40

P2 20 1023 K
973 K
923 K
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Time-on-stream (h)
0 200 400 600 800 1000 1200
100
Temperature (K) (b)
90
Fig. 3 e H2 temperature-programmed reduction profile of 80
10%Ni/SBA-15 catalyst from 373 to 1173 K with a linear rate 70
of 10 K min¡1 under 50 mL min¡1 flow of 10%H2/Ar mixture
60

XCO (%)
(Amount of H2 consumption of 1.54 mmol H2 g¡1 cat).
50
2

40
addition, the greater intensity of peak 1 than that of peak 2 30
would suggest that the amount of metallic Ni0 phase on sup-
20 1023 K
port surface was superior to the number of Ni0 particles within 973 K
10
the channel of porous support. 923 K
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Catalytic performance for methane dry reforming reaction
Time-on-stream (h)
Effect of reaction temperature
Fig. 4 e Effect of reaction temperature on (a) CH4, and (b)
The influence of reaction temperature was studied at stoi-
CO2 conversions over 10%Ni/SBA-15 catalyst at
chiometric feed ratio (PCH4 ¼PCO2 ¼20 kPa and PN2 ¼61 kPa) and
PCH4 ¼PCO2 ¼20 kPa and PN2 ¼61 kPa.
varying reaction temperature of 923e1023 K. As seen in Fig. 4,
CH4 and CO2 conversions increased significantly about 83.4%
and 59.0%, respectively with growing reaction temperature
from 923 to 1023 K rationally due to the endothermic property supplementary data) [49e51]. In fact, the percentage of car-
of MDR reaction (with positive DH0 values ranging from 258.98 bon content on catalyst surface estimated from TPO mea-
to 260.12 kJ mol
1 at temperature from 923 to 1023 K) in line surement of spent catalysts after MDR reaction (see Fig. S8 in
with other studies [34]. Additionally, both CO2 and CH4 con- supplementary data) reduced from 21.0% to 0.7% (see Table 3)
versions were steady within 4 h on-stream at 973 and 1023 K with increasing reaction temperature from 923 to 1023 K.
whilst a decline of about 21.4% and 35.6% for the corre- From the above reasons (the presence of thermodynamically
sponding XCO2 and XCH4 was observed at 923 K. The unstable preferred reverse Boudouard reaction and hence the elimi-
catalytic activity at low reaction temperature of 923 K was nation of carbon deposition on catalyst surface), both CO2 and
probably due to the closure of active sites by deposited carbon CH4 conversions were more stable at high reaction tempera-
from methane decomposition reaction (cf. Eq. (3)). However, ture of 973 and 1023 K than 923 K.
the carbonaceous deposit was simultaneously eliminated
1

CO2 þ C%2CO DG0 ¼ 170:34
0:18T kJ mol (13)
from catalyst surface by CO2 reactant via the reverse Bou-
douard reaction (cf. Eq. (13)), thermodynamically favored at Apart from TPO measurements, CHNS elemental analysis
high reaction temperature of 973e1023 K (see Fig. S5 in and EDX measurement for selected spent 10%Ni/SBA-15

Table 2 e Summary of H2 consumption during H2-TPR measurement for 10%Ni/SBA-15 catalyst.

Peak temperature (K) Actual H2 Theoretical H2 Degree of
consumed (mmol H2 g
1
cat) consumed (mmol H2 g
1
cat) reductiona (%)
Peak P1 (644.3 K) 1.16 1.71 67.84
Peak P2 (760.1 K) 0.38 22.22
Total 1.54 90.06
a Actual H2 consumed
Degree of reduction ¼ Theoretical H2 consumed  100%.
 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4 11289

Table 3 e Summary for percentage of carbon deposition on spent 10%Ni/SBA-15 catalysts after MDR at PCO2 ¼PCH4 ¼20 kPa,
PN2 ¼61 kPa and temperature of 923e1023 K for 4 h on-stream.
Reaction Temperature-programmed SEM-EDX measurement CHNS elemental analysis
temperature (K) oxidation (TPO) measurement
Weight loss (%) Carbon content (%) Carbon content (%)
923 21.0 e e
973 5.3 e e
1023 0.7 0.3a 0.2
a
Detailed elemental composition of spent catalyst was shown in Fig. S3 (b) (supplementary data).

catalyst obtained from MDR at PCH4 ¼PCO2 ¼20 kPa, PN2 ¼61 kPa evident as PCO2 was increased in agreement with both exper-
and 1023 K were also conducted to validate the presence of imental [32] and thermodynamic studies [52]. The significant
deposited carbon. As seen in Table 3, the carbon content of decline of XCO2 with growing PCO2 was owing to the surplus CO2
about 0.2% and 0.3% was obtained from CHNS and EDX mea- presence and insufficient amount of CH4 acting as limiting
surements, respectively. The effect of reaction temperature reactant for converting CO2-rich feed composition [34,52]. In
on product yield is also shown in Fig. S6 (supplementary data). addition, the drop in XCO2 with rising PCO2 could be due to the
Both H2 and CO yields increased significantly with rising re- oxidation of active Ni0 metallic site to NiO in excess CO2
action temperature from 923 to 1023 K further confirming the environment (see Eq. (16)).
improvement of MDR activity with growing temperature.
Ni þ CO2 /NiO þ CO (16)
Effect of CO2 partial pressure
The role of CO2 partial pressure on MDR reaction was inves-
100
tigated by changing PCO2 within the range of 20e60 kPa while (a)
PCH4 was kept constant at 20 kPa for all reaction temperature.
90
Fig. 5 depicts the influence of CO2 partial pressure on both CH4
and CO2 conversions over 10%Ni/SBA-15 catalyst at
80
923e1023 K. Regardless of CO2 partial pressure, CH4 conver-
XCH (%)

sion improved significantly with increasing reaction temper-

70
4

ature within 923e1023 K (see Fig. 5 (a)). Interestingly, the initial

improvement in XCH4 with rising PCO2 was observed for all
temperature probably due to the enhancement of concomi- 60

tant reverse Boudouard reaction with CO2-rich reactant for

1023 K
the simultaneous gasification of carbonaceous deposition on 50
973 K
catalyst surface. Indeed, Foo et al. [11] postulated a 2-step 923 K
mechanism for MDR reaction involving CO2 gasification of 40
deposited carbon formed by CH4 dehydrogenation as seen in 20 30 40 50 60

Eq. (14). PCO (kPa)

2

H2 þCO2
CH4 ƒƒƒƒƒ!Cx H1
x ƒƒƒƒƒ!CO þ H2 (14)
100
where CxH1-x is carbonaceous deposit and x is 1. As sug- (b)
gested by Donazzi et al. [31], the rise in CH4 conversion with 90
increasing PCO2 was also attributed to the involvement of CH4
steam reforming due to the rising formation of intermediate 80
H2O by-product by reverse water-gas shift reaction, RWGS (see
XCO (%)

Eq. (15)) in CO2-excess environment.

70
2

0
1

CO2 þ H2 %CO þ H2 O DG ¼ 34:51
0:03T kJ mol (15)
60
However, a drop in CH4 conversion beyond the maximum
at PCO2 of 30e50 kPa depending on reaction temperature was 50 1023 K
973 K
observed as seen in Fig. 5 (a). Xu et al. [32] also observed the 923 K
optimal XCH4 at CO2/CH4 feed ratio of 1.3 for MDR over NieCo 40
bimetallic catalyst and suggested that the balance between 20 30 40 50 60
the rate of carbon deposition from CH4 decomposition and PCO (kPa)
2
carbon removal via CO2 gasification affected the relationship
of XCH4 vs. PCO2 . Fig. 5 e Effect of CO2 partial pressure on (a) CH4, and (b) CO2
As seen in Fig. 5 (b), irrespective of CO2 partial pressure, conversions over 10%Ni/SBA-15 catalyst at temperature
CO2 conversion increased with reaction temperature of range of 923e1023 K, PCH4 ¼20 kPa and PN2 ¼101.325 e PCO2
923e1023 K. However, a substantial reduction in XCO2 was e PCH4 (kPa).
11290 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

1

The effect of CO2 partial pressure on gaseous product C þ CO2 %2CO DG0 ¼ 170:34
0:18T kJ mol (17)
selectivity, and H2/CO ratio is shown in Fig. 6. Irrespective of
Indeed, the ratio of H2/CO was always lesser than stoi-
reaction temperature, and CO2 partial pressure, CO selectivity
chiometric ratio of unity (cf. Fig. 6 (c)) for all reaction tem-
was always higher than H2 selectivity (see Fig. 6 (a), and (b)).
perature and CO2 partial pressure further confirming the
This trend was attributed to the parallel occurrence of RWGS
presence of these side reactions (see Eqs. (15) and (17)) during
reaction (cf. Eq. (15)) converting H2 to CO and/or CO2 gasifi-
MDR reaction. Interestingly, increasing PCO2 resulted in a
cation reaction (see Eq. (17)).
reduction of H2 selectivity, and H2/CO ratio but improved CO
55 selectivity as seen in Fig. 6. This observation could be due to
(a)
the enhancement of both RWGS (cf. Eq. (15)) and CO2 gasifi-
cation (cf. Eq. (17)) reactions in CO2-rich environment. How-
50
ever, as seen in Fig. 6 (c), H2/CO ratio improved with rising
reaction temperature from 923 to 1023 K. It would suggest that
45 although RWGS and reverse Boudouard reactions are ther-
SH (%)

modynamically favored at high reaction temperature, CH4

2

40 dehydrogenation reaction may be prevalent in comparison

with other side reactions and hence increasing H2/CO ratio.

35 1023 K
973 K
Effect of CH4 partial pressure
923 K The influence of PCH4 on catalytic activity was studied at fixed
30 PCO2 ¼20 kPa and varying PCH4 of 20e60 kPa and PN2 of 61e21 kPa
20 30 40 50 60
as seen in Fig. 7. Although both CH4 and CO2 conversions
PCO (kPa) improved with reaction temperature regardless of PCH4 , the
2

decreasing reactant conversions with rising PCH4 was a result

70
(b) of increasing formation rate of deposited carbon via CH4
cracking [32]. Methane decomposition would be prevalent and
65
facilitated by CH4-excess environment [33]. Thus, the rise in
CH4 decomposition rate led to an imbalance between carbon
60
formation and carbon gasification rates, and hence increasing
SCO (%)

carbon deposit. Ayodele et al. [33] suggested the change in

55
reaction mechanism favoring carbon formation induced the
drop in CH4 conversion with rising CH4 partial pressure.
50
In order to assess the stability of 10%Ni/SBA-15 catalyst in
CH4-rich feedstock, the effect of PCH4 on CH4 conversion with
45 1023 K
973 K time-on-stream is shown in Fig. S7 (supplementary data).
923 K SBA-15 supported Ni catalyst appeared to be stable within 4 h
40 on-stream at PCH4 of 20e40 kPa whilst a decline in CH4 con-
20 30 40 50 60
version was evidenced at PCH4 greater than 50 kPa due to car-
PCO (kPa) bon formation from CH4 decomposition in excess CH4
2

environment [33].

1.0
(c)
Characterization of used catalysts

0.9
X-ray diffraction measurement of spent catalyst
The crystalline phases of representative spent catalyst after
0.8
H2/CO ratio

MDR reaction were also examined by XRD measurement.

Fig. S9 (see in supplementary data) shows the comparison
0.7
between XRD patterns of fresh and spent 10%Ni/SBA-15
catalyst from MDR reaction at stoichiometric feed ratio (CH4/
0.6
CO2 ratio of 1:1) and 1023 K. As seen in the diffractogram of
1023 K spent 10%Ni/SBA-15 catalyst, the first broad peak ranging
0.5 973 K
923 K from 15.0oe30.0 with highest intensity at 2q ¼ 26.6 was
0.4 attributed to overlapped peaks between SiO2 and graphitic
20 30 40 50 60 carbon phases [39]. Additionally, the characteristic peaks
PCO (kPa) observed at 2q of 44.5 , and 52.0 were assigned to metallic Ni0
2
phase (JCPDS card No. 04-0850) [53].
Fig. 6 e Effect of CO2 partial pressure on (a) H2 selectivity, (b) Interestingly, the typical peaks for NiO phase (JCPDS card
CO selectivity, and (c) H2/CO ratio over 10%Ni/SBA-15 No. 47-1049) were not detected for spent catalyst indicating
catalyst at temperature range of 923e1023 K, PCH4 ¼20 kPa that the active Ni0 metallic phase was not re-oxidized to
and PN2 ¼101.325 e PCO2 e PCH4 (kPa). inactive metal oxide phase even in the presence of oxidizing
 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4 11291

agents, i.e., CO2, and H2O during MDR reaction. The stability presence of these carbons was also verified by Raman
of Ni phase was most likely due to the continuous formation analysis (see Fig. 9). Abatzoglou and Fauteux-Lefebvre re-
of H2 and CO products with reducing property suppressing ported that filamentous carbon formed by the diffusion of C
the re-oxidation of active metal. Additionally, the unreduced through Ni crystals did not result in the severe deterioration
NiO particles on catalyst surface during H2 pretreatment of active Ni metal whilst graphite generated from CH4
prior to MDR reaction could contribute to oxidation resis- cracking encapsulated catalyst particles and hence wors-
tance. The resistance of active Ni0 particles to oxidation could ening reactant conversion [56]. Interestingly, as seen in
also contribute to the explanation of catalytic stability within Fig. 8 (b) and (c), carbonaceous deposition was formed
4 h on-stream for MDR reaction. The average crystallite size mainly on the surface of mesoporous SBA-15 support and
of Ni0 particles on spent catalyst estimated from Scherrer support surface was not fully covered by deposited carbon.
equation was about 11.80 nm inferior to that of NiO particles Hence, the catalytic activity of SBA-15 supported Ni catalyst
on fresh catalyst (27.04 nm). This observation would further was stable within 4 h on-stream. In addition, negligible
confirm the successful removal of oxygen atoms via reduc- graphite phase associated with Ni nanoparticles located
tion of NiO particles to metallic Ni0 phase during H2- inside the mesoporous channels of SBA-15 support was
pretreatment. observed in compared with agglomerated Ni particles with
lager size on support surface (see Fig. 8 (b)). This observation
HRTEM measurement of spent catalyst could be rationally due to the confinement effect which
Fig. 8 shows the HRTEM images at different scales of stabilized Ni nanoclusters resided within the mesoporous
representative spent catalyst after MDR reaction. Appar- channels and prevented them from migrating to the outer
ently, carbon nanofilament (CNF) and graphic carbon (red surface of support and aggregating to greater particles [48].
circles) encapsulating Ni particles were observed for spent Chen et al. also reported that small-sized Ni crystals had a
10%Ni/SBA-15 catalyst as seen in Fig. 8 (a)-(d) [54,55]. The high saturation concentration of carbonaceous species
resulting in a low driving force for carbon diffusion and thus
a lesser carbon formation rate [57].
100
(a)
Raman spectroscopy measurement
80 Fig. 9 displays the Raman spectrum of a representative spent
10%Ni/SBA-15 catalyst. The Raman spectrum of fresh catalyst
was also captured for comparison purpose. As seen in Fig. 9
60
XCH (%)

(a), the typical Raman shifts detected at 483.01 and

1004.66 cm
1 were attributed to the presence of NiO phase due
4

40 to the oscillation of NieO bond [58] in line with the results of

X-ray diffractogram (see Fig. 1). However, these characteristic
peaks were not identified for the Raman spectrum of spent
20 1023 K
973 K
10%Ni/SBA-15 catalyst (cf. Fig. 9 (b)) further confirming the
923 K oxidation resistance of active metallic Ni0 phase to CO2 reac-
0 tant and H2O by-product during MDR reaction for 4 h reaction
20 30 40 50 60 time and hence maintaining catalytic activity. Both filamen-
PCH (kPa) tous and graphic carbons were also detected on the surface of
4

spent 10%Ni/SBA-15 catalyst due to the presence of D- and G-

100 bands. In fact, as seen in Fig. 9 (b), the D-band (the breathing
(b) mode of k-point phonons of A1g symmetry) located at
1338.3 cm
1 was assigned to the vibrations of sp3-bonded
80 carbon atoms with swinging bonds in plane boundaries of
amorphous or filamentous carbons whilst the peak at
1571.6 cm
1 belonged to the tangential G-band associated
XCO (%)

60 with the stretching vibration of sp2-bonded carbon (C]C)

2

atoms (E2g symmetry) indicative of the existence of ordered

carbon structure, viz., graphite [59e61]. Additionally, the high
40 intensity band detected at 2688.2 cm
1 was attributed to G'-
1023 K band, the overtone of D-band [62].
973 K
923 K As seen in Fig. 9 (b), there was no observable peak within
20 the range of 100e350 cm
1 for the radial breathing mode (RBM
20 30 40 50 60 band) typical for the presence of single-walled carbon nano-
PCH (kPa) tubes (SWCNTs) [63,64]. This would suggest that the detected
4
filamentous carbon on catalyst surface possessed a multi-wall
Fig. 7 e Effect of CH4 partial pressure on (a) CH4, and (b) CO2 structure. Additionally, the small band identified at low
conversions over 10%Ni/SBA-15 catalyst at temperature Raman shift of 410.7 cm
1 was originated from the phonon
range of 923e1023 K, PCO2 ¼20 kPa and PN2 ¼101.325 e PCO2 density of states, and RBM-like mode owing to the presence of
e PCH4 (kPa). defects [65].
11292 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4

Fig. 8 e HRTEM images of spent 10%Ni/SBA-15 catalyst after MDR reaction at PCO2 ¼PCH4 ¼ 20 kPa, PN2 ¼61 kPa and T ¼ 1023 K
at different magnifications ((a) 200 nm, (b) 100 nm, (c) 50 nm and (d) 5 nm scale bars).

G-band
SBA-15 support and 10%Ni/SBA-15 catalyst possessed high
1571.6 cm-1 BET surface area of 550.05 and 444.96 m2 g
1, respectively.
D-band FESEM image shows a relatively uniform rod-like shape of
1338.3 cm-1 G'-band SBA-15 support with a diameter of about 0.55 mm. In addition,
2688.2 cm-1 XRD and Raman measurements detected the formation of NiO
Intensity (a.u.)

phase on catalyst surface with dimension size of 27 nm. The

(b) reduction of NiO to metallic Ni0 phase was also identified by
410.7 cm-1 nonisothermal H2-TPR measurement (with degree of reduc-
tion of 90.1%) at different reduction temperature dependent
NiO on the degree of metal-support interaction and the location of
NiO particles on the surface or inside the channels of meso-
NiO porous SBA-15 support. Generally, catalytic performance was
(a)
unchanged for 4 h on-stream at 973e1023 K. However, a
decrease in both XCO2 and XCH4 of about 21.4% and 35.6%,
400 800 1200 1600 2000 2400 2800 3200
respectively was experienced at 923 K because of carbona-
-1
Raman shift (cm ) ceous deposition from CH4 decomposition reaction. The
optimal PCO2 in terms of CH4 conversion was observed at
Fig. 9 e Raman spectra of (a) fresh, and (b) spent 10%Ni/ 30e50 kPa depending on reaction temperature. Nevertheless,
SBA-15 catalysts after MDR reaction at PCO2 ¼PCH4 ¼20 kPa, increasing PCO2 resulted in a negative effect on CO2 conver-
PN2 ¼61 kPa and T ¼ 1023 K. sion. Interestingly, regardless of CO2 partial pressure and re-
action temperature, CO selectivity was always superior to H2
selectivity owing to the co-existence of RWGS reaction con-
Conclusions verting H2 to CO and/or CO2 gasification. Additionally, the
increase in CH4 partial pressure from 20 to 60 kPa yielded a
The effect of operating parameters on MDR reaction was significant decline in both XCO2 and XCH4 probably due to rising
investigated in a fixed-bed reactor using Ni/SBA-15 catalyst CH4 decomposition rate in CH4-excess reactant. 10%Ni/SBA-15
prepared by incipient wetness impregnation method. Both catalyst was resistant to re-oxidation up to 4 h during MDR
 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 4 2 ( 2 0 1 7 ) 1 1 2 8 3 e1 1 2 9 4 11293

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