Investigation of the catalytic performance and coke formation of nanocrystalline Ni/SrO-Al2O3 catalyst in dry reforming of methane

Document Type : Research Paper


Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan


In this study, nickel catalysts supported on mesoporous nanocrystalline gamma alumina promoted by various strontium contents were prepared by the impregnation method and employed in dry reforming of methane (DRM). The prepared catalysts were characterized using N2 adsorption (BET), temperature-programmed reduction and oxidation (TPR,) and oxidation (TPDTPO), X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques. TPR analysis revealed that the increases in Sr content enhanced the reducibility of the catalysts. The obtained results indicated that increasing Sr content increased both the methane and carbon dioxide conversions. In addition, the CO2 conversion was higher than the CH4 conversion due to the occurrence of the reverse water gas shift reaction. Among the studied catalysts, Ni/10% Sr-Al2O3 exhibited the highest catalytic activity and the lowest carbon formation. This catalyst showed high stability without any decrease in methane conversion up to 12 h of reaction. The results of this study could be employed in developing an industrial catalyst for the dry reforming reaction.


Main Subjects

[1] Goff. S. P.,  Wang S. I., “Syngas Production by Reforming”, J. Chem. Eng. Prog., 1987, 83: 8.
[2] Jeong H., Kim K. I., Kim D., Song I. K., “Effect of promoters in the methane reforming with carbon dioxide to synthesis gas over Ni/HY catalysts”, J. Molecular Catalysis A: Chemical, 2006, 246: 43.
 [3] Nematollahi B., Rezaei M., Khajenoori M., “Combined dry reforming and partial oxidation of methane to synthesis gas on noble metal catalysts”. int. J. hydrogen energy, 2011,28: 2969.
 [4] Potdar H.S., Roh H.S., Jun K.W., Ji M., Liu Z.W. “Carbon dioxide reforming of methane over co-precipitated Ni-Ce-ZrO2 catalysts. Catalysis letters”, 2002, 84: 95.
 [5] Meshkani F., Rezaei M., “Nanocrystalline MgO supported nickel-based bimetallic catalysts for carbon dioxide reforming of methane”, int. J. hydrogen energy, 2010, 35: 10295.
 [6] Alves H.J., Junior C.B., Niklevicz R.R., Frigo E.P., Frigo M.S., Coimbra-Araujo C.H., “Overview of hydrogen production technologies from biogas and the applications in fuel cells”, int. J. hydrogen energy, 2013, 38: 5215.
 [7] Wang S., Lu G.Q., Millar G.J., “Carbon dioxide reforming of methane to produce synthesis gas over metal-supported catalysts: state of the art”, Energy & Fuels, 1996, 10: 896.
 [8] Alipour Z., Rezaei M., Meshkani F., “Effect of alkaline earth promoters (MgO, CaO, and BaO) on the activity and coke formation of Ni catalysts supported on nanocrystalline Al2O3 in dry reforming of methane”, J. Industrial and Engineering Chemistry, 2014, 20: 2858.
 [9] Shekhawat II D., Spivey J. J., Berry D. A. editors, Fuel cells: technologies for fuel processing, Elsevier, 2011.
 [10] Alipour Z., Rezaei M., Meshkani F., " Effect of K2O on the catalytic performance of Ni catalysts supported on nanocrystalline Al2O3 in CO2 reforming of methane", Irainian journal of hydrogen & fuel cell,  2015, 2: 215-226.
 [11] Zhang J., Ph.D. Thesis, University of Saskatchewan, 2009.
 [12] Sutthiumporn K. and Kawi S., “Promotional effect of alkaline earth over Ni–La2O3 catalyst for CO2 reforming of CH4: role of surface oxygen species on H2 production and carbon suppression” Int. J. Hydrogen Energy, 2011, 36: 14435.
[13] San José-Alonso D., Illán-Gómez M.J., Román-Martínez M.C., " K and Sr promoted Co alumina supported catalysts for the CO2 reforming of methane", Catalysis Today , 2011, 176 : 187–190.
 [14] Jing Q., Lou H., Fei J., Hou Z., Zheng X., “Syngas production from reforming of methane with CO2 and O2 over Ni/SrO–SiO2 catalysts in a fluidized bed reactor”, Int. J. hydrogen energy, 2004, 29: 1245.
 [15] Leofanti G., Padovan M., Tozzola G., Venturelli B., “Surface area and pore texture of catalysts”, J. Catalysis Today, 1998, 41: 207.
 [16] Cai X., Dong X., Lin W., “Effect of CeO2 on the catalytic performance of Ni/Al2O3 for autothermal reforming of methane”, J. Natural Gas Chemistry, 2008, 17: 98.
 [17] Valentina R., Ph.D. Thesis, J. Alma Mater Digital-Università di Bologna 2007.
 [18] Meshkani F., Rezaei M.,  Andache M., “Investigation of the catalytic performance of Ni/MgO catalysts in partial oxidation, dry reforming and combined reforming of methane”, J. Industrial and Engineering Chemistry, 2014, 20: 1251.
 [19] Kang K.M., Kim H.W., Shim I.W., Kwak H.Y., 2011, “Catalytic test of supported Ni catalysts with core/shell structure for dry reforming of methane”, J. Fuel Processing Technology, 92: 1236.
 [20] Ranjbar A., Rezaei M., “Preparation of nickel catalysts supported on CaO.2Al2O3 for methane reforming with carbon dioxide”, int. J. hydrogen energy, 2012, 37: 6356.
 [21] Joo O.S., Jung K.D., Han S.H., “Modification of H-ZSM-5 and gamma-alumina with formaldehyde and its application to the synthesis of dimethyl ether from syn-gas”, J. Bulletin-Korean Chemical Society, 2002, 23: 1103.
 [22] Cesteros Y., Fernandez R., Estellé J., Salagre P., Medina F., Sueiras J.E., Fierro J.L.G., “Characterization and catalytic properties of several LaNi and SrNi solids”, J. Applied Catalysis A: General, 1997, 152: 249.
 [23] Fei J., Hou Z., Zheng X. and Yashima T., “Doped Ni catalysts for methane reforming with CO2”, J. Catalysis letters, 2004, 98: 241.
 [24] Lertwittayanon K., Atong D., Aungkavattana P., Wasanapiarnpong T., Wada S., Sricharoenchaikul V., “Effect of CaO–ZrO2 addition to Ni supported on γ-Al2O3 by sequential impregnation in steam methane reforming” int. J. hydrogen energy, 2010, 35: 12277.
[25] Hou Z., Yokota O., Tanaka T., Yashima T., “Investigation of CH4 reforming with CO2 on meso-porous Al2O3-supported Ni catalyst”, J. Catalysis Letters, 2003, 89: 121.