RSC Advances
Paper
Prior to TEM observation, the catalysts were rst reduced in
Acknowledgements
ꢁ1
ꢀ
a xed-bed reactor under pure H ow (50 mL min ) at 500 C
2
for 2 h. The samples were prepared by directly suspending the This research was nancially supported by National Natural
powder in ethanol with ultrasonication. A copper microscope Science Funds of China (Grant No. U1203293 and 91434128),
grid covered with perforated carbon was dipped into the the Program of Shanghai Subject Chief Scientist (Grant No.
suspension for observation.
10XD1401500) and the Program of Shanghai Leading Talents
Thermogravimetric analysis (TG) was used to measure the (2013).
amounts of carbon deposited on the spent catalysts and was
performed with a Netzsch Model STA 409 PC instrument under
References
ꢀ
an air ow from room temperature to 800 C at a heating rate of
ꢀ
ꢁ1
10 C min
.
1 K. Hashimoto, N. Kumagai, K. Izumiya, H. Takano,
P. R. Zabinski, A. A. El-Moneim, M. Yamasaki, Z. Kato,
E. Akiyama and H. Habazaki, Arch. Metall. Mater., 2013, 58,
Catalytic performances tests
2
31–239.
J. Kopyscinski, T. J. Schildhauer and S. M. A. Biollaz, Fuel,
010, 89, 1763–1783.
J. J. Gao, Y. L. Wang, Y. Ping, D. C. Hu, G. W. Xu, F. N. Gu and
F. B. Su, RSC Adv., 2012, 2, 2358–2368.
Y. Borodko and G. A. Somorjai, Appl. Catal., A, 1999, 186,
355–362.
S. K. Ryi, S. W. Lee, K. R. Hwang and J. S. Park, Fuel, 2012, 94,
Syngas to methane reaction was conducted in a xed-bed
stainless steel reactor with an inner diameter of 10 mm. Before
the reaction, the catalyst (0.5 g) was reduced by high purity H
with 50 mL min at 500 C for 2 h. Subsequently, the reactor
2
3
4
5
2
2
ꢁ1
ꢀ
ꢀ
was cooled down to 300 C before the gas ow (H
2
1
) was switched
ꢁ
ꢁ1
to syngas (H /CO ¼ 3, GHSV ¼ 15 000 mL g
h
) and the
2
pressure was increased to 0.3 MPa. The outlet gases were
analyzed by an on-line gas chromatograph (Techcomp,
GC7890T). A thermal conductivity detector (TCD) and ame
ionization detector (FID) were used to analyze gaseous products
64–69.
6
7
B. C. Enger and A. Holmen, Catal. Rev., 2012, 54, 437–488.
A. Alihosseinzadeh, B. Nematollahi, M. Rezaei and E. N. Lay,
Int. J. Hydrogen Energy, 2015, 40, 1809–1819.
(CO, CO
2
and CH
4
). The equations used for calculating the CO
yield are shown below:
conversion and CH
4
8
9
Y. Y. Shu, L. E. Murillo, J. P. Bosco, W. Huang, A. I. Frenkel
and J. G. Chen, Appl. Catal., A, 2008, 339, 169–179.
J. R. A. Sietsma, J. D. Meeldijk, M. Versluijs-Helder,
A. Broersma, A. J. van Dillen, P. E. de Jongh and K. P. de
Jong, Chem. Mater., 2008, 20, 2921–2931.
moles of CO reacted
moles of CO supplied
Conversion of CO ð%Þ ¼
ꢂ 100 (1)
4
moles of CH formed
Yield of CH
4
ð%Þ ¼
ꢂ 100
(2)
moles of CO supplied
10 J. Y. Zhang, Z. Xin, X. Meng and M. Tao, Fuel, 2013, 109, 693–
01.
1 M. Tao, X. Meng, Y. Lv, Z. Bian and Z. Xin, Fuel, 2016, 165,
89–297.
7
1
1
2
2 X. Yang, Wendurima, G. Gao, Q. Shi, X. Wang, J. Zhang,
C. Han, J. Wang, H. Lu, J. Liu and M. Tong, Int. J.
Hydrogen Energy, 2014, 39, 3231–3242.
Conclusions
Mesoporous molecular sieve SBA-15 was used as a support of
nickel-based catalysts for CO methanation reaction. The 13 S. Velu and S. Gangwal, Solid State Ionics, 2006, 177, 803–811.
textural properties and catalytic activity of the catalysts 14 F. Bentaleb, M. Che, A.-C. Dubreuil, C. Thomazeau and
prepared by double-solvent and traditional incipient-wetness
impregnation methods were compared. XRD results and TEM 15 Y. Zhang, Y. Liu, G. Yang, Y. Endo and N. Tsubaki, Catal.
images showed that Ni particles were evenly distributed in Ni/ Today, 2009, 142, 85–89.
SBA-15(D), which led to more active sites. Compared with the 16 J. H. Li, Y. Xu, D. Wu and Y. H. Sun, Catal. Today, 2009, 148,
catalyst prepared by traditional impregnation method, the 148–152.
catalyst prepared by double-solvent impregnation method 17 S. F. Chen, J. L. Li, Y. H. Zhang, D. H. Zhang and J. J. Zhu, J.
showed higher CO conversion and CH4 yield for syngas Nat. Gas Chem., 2012, 21, 426–430.
methanation reaction. The 10%Ni/SBA-15(D) catalyst achieved 18 H. Liu, Y. Li, H. Wu, H. Takayama, T. Miyake and D. He,
the best activity with 100% CO conversion and about 99% CH Catal. Commun., 2012, 28, 168–173.
. According to the 19 H. Liu, Y. Li, H. Wu, T. Miyake and D. He, Int. J. Hydrogen
results of TPR analysis, it could be speculated that using double- Energy, 2013, 38, 15200–15209.
solvent impregnation method strengthened the interactions 20 D. Kim, B. S. Kwak, B.-K. Min and M. Kang, Appl. Surf. Sci.,
between NiO and support. Therefore, Ni/SBA-15(D) catalyst 2015, 332, 736–746.
showed better high-temperature-resistant performance than Ni/ 21 S. Hwang, J. Lee, U. G. Hong, J. G. Seo, J. C. Jung, D. J. Koh,
E. Marceau, Catal. Today, 2014, 235, 250–255.
4
ꢀ
ꢁ1 ꢁ1
yield at 400 C, 0.3 MPa and 15 000 mL g
h
SBA-15 catalyst. The results of XRD and TG analysis showed that
catalyst sintering rather than carbon deposition led to the
H. Lim, C. Byun and I. K. Song, J. Ind. Eng. Chem., 2011, 17,
154–157.
catalyst deactivation in the heat-resistant performance and 100 22 G. Prieto, A. Martinez, R. Murciano and M. A. Arribas, Appl.
h stability test. Catal., A, 2009, 367, 146–156.
35882 | RSC Adv., 2016, 6, 35875–35883
This journal is © The Royal Society of Chemistry 2016