Effect of a promoter on the methanation activity of a Mo-based sulfur-resistant catalyst

Abstract

The effect of adding Co, Ni or La on the methanation activity of a Mo-based sulfur-resistant catalyst was investigated. As promoters, Co, Ni and La all improved the methanation activity of a 15% MoO₃/Al₂O₃ catalyst but to different extents. Similar improvements were also found when Co, Ni or La was added to a 15% MoO₃/25%-CeO₂-Al₂O₃ catalyst. The promotion effects of Co and Ni were better than that of La. However, the catalytic methanation activity deteriorated the most with time for the Ni-promoted catalyst. The used catalysts were analyzed by nitrogen adsorption measurement, X-ray diffraction and X-ray photoelectron spectroscopy.

Keywords

sulfur-resistant / methanation / promoter

References

[1] Adachi M, Contescu C, Schwarz J A. Catalyst preparation variables that affect the creation of active sites for HDS on Co/Mo/Al₂O₃ catalytic materials. Journal of Catalysis, 1996, 162(1): 66–75

[2] Pecoraro T A, Chianelli R R. Hydrodesulfurization catalysis by transition metal sulfides. Journal of Catalysis, 1981, 67(2): 430–445

[3] Ho T C. Hydrodenitrogenation catalysis. Catalysis Reviews. Science and Engineering, 1988, 30(1): 117–160

[4] Zou J, Schrader G L. Multicomponent thin film molybdate catalysts for the selective oxidation of 1,3-butadiene. Journal of Catalysis, 1996, 161(2): 667–686

[5] Brito J L, Barbosa A L, Albornoz A, Severino F, Laine J. Nickel molybdate as precursor of HDS catalysts: effect of phase composition. Catalysis Letters, 1994, 26(3-4): 329–337

[6] Brito J L, Barbosa A L. Effect of phase composition of the oxidic precursor on the HDS activity of the sulfided molybdates of Fe(II), Co(II), and Ni(II). Journal of Catalysis, 1997, 171(2): 467–475

[7] Travert A, Dujardin C, Maugé F, Veilly E, Cristol S, Paul J F, Payen E. CO adsorption on CoMo and NiMo sulfide catalysts: a combined IR and DFT study. Journal of Physical Chemistry B, 2006, 110(3): 1261–1270

[8] Prins R, de Beer V H J, Somorjai G A. Structure and function of the catalyst and the promoter in Co-Mo hydrodesulfurization catalysts. Catalysis Reviews. Science and Engineering, 1989, 31(1-2): 1–41

[9] Byskov L S, Nørskov J K, Clausen B S, Topsøe H. DFT calculations of unpromoted and promoted MoS₂-based hydrodesulfurization catalysts. Journal of Catalysis, 1999, 187(1): 109–122

[10] Sorescu D C, Sholl D S, Cugini A V. Density functional theory studies of the interaction of H, S, Ni-H, and Ni-S complexes with the MoS₂ basal plane. Journal of Physical Chemistry B, 2004, 108(1): 239–249

[11] Topsøe H, Clausen B S, Candia R, Wivel C, Mørup S. In situ Mössbauer emission spectroscopy studies of unsupported and supported sulfided Co-Mo hydrodesulfurization catalysts: evidence for and nature of a Co-Mo-S phase. Journal of Catalysis, 1981, 68(2): 433–452

[12] Wivel C, Candia R, Clausen B S, Mørup S, Topsøe H. On the catalytic significance of a Co-Mo-S phase in Co-Mo/Al₂O₃ hydrodesulfurization catalysts: combined in situ Mössbauer emission spectroscopy and activity studies. Journal of Catalysis, 1981, 68(2): 453–463

[13] Niemann W, Calusen B S, Topsøe H. X-ray absorption studies of the Ni environment in Ni-Mo-S. Catalysis Letters, 1990, 4(4-6): 355–363

[14] Startsev A N. The mechanism of HDS catalysis. Catalysis Reviews. Science and Engineering, 1995, 37(3): 353–423

[15] Rodriguez J A. Interaction of hydrogen and thiophene with Ni/MoS₂ and Zn/MoS₂ surfaces: a molecular orbital study. Journal of Physical Chemistry B, 1997, 101(38): 7524–7534

[16] Byskov L S, Hammer B, Nørskov J K, Clausen B S, Topsøe H. Sulfur bonding in MoS₂ and Co-Mo-S structures. Catalysis Letters, 1997, 47(3-4): 177–182

[17] Rodriguez J A, Dvorak J, Jirsak T, Li S Y, Hrbek J, Capitano A T, Gabelnick A M, Gland J L. Chemistry of thiophene, pyridine, and cyclohexylamine on Ni/MoS_x and Ni/S/Mo(110) surfaces: role of nickel in hydrodesulfurization and hydrodenitrogenation processes. Journal of Physical Chemistry B, 1999, 103(39): 8310–8318

[18] Yamashita K, Barreto L. Energyplexes for the 21st century: coal gasification for co-producing hydrogen, electricity and liquid fuels. Energy, 2005, 30(13): 2453–2473

[19] Williams R H. Toward zero emissions from coal in China. Energy for Sustainable Development, 2001, 5(4): 39–65

[20] Gao Y L, Fang X C, Cheng Z M. Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China. Frontiers of Chemical Science and Engineering, 2011, 5(3): 287–296

[21] Hou P Y, Wise H. Kinetic studies with a sulfur-tolerant methanation catalyst. Journal of Catalysis, 1985, 93(2): 409–416

[22] Fu Y L, Tang X B, Huang Z G, Fan C Z, Ji M R, Wu J X. Valency and adsorption characteristics of a sulphided MoO₃/γ-A1₂O₃ methanation catalyst. Applied Catalysis, 1989, 55(1): 11–20

[23] Wang M W, Luo L T, Li F Y, Wang J J. Effect of La₂O₃ on methanation of CO and CO₂ over Ni-Mo/γ-Al₂O₃ catalyst. Journal of Rare Earths, 2000, 18(1): 22–26

[24] Wang B W, Ding G Z, Shang Y G, Lv J, Wang H Y, Wang E D, Li Z H, Ma X B, Qin S D, Sun Q. Effects of MoO₃ loading and calcination temperature on the activity of the sulphur-resistant methanation catalyst MoO₃/γ-Al₂O₃. Applied Catalysis A, General, 2012, 431-432(1): 144–150

[25] Liu X Y, Liu J Z, Geng F F, Li Z K, Li P, Gong W L. Synthesis and properties of PdO/CeO₂-Al₂O₃ catalysts for methane combustion. Frontiers of Chemical Science and Engineering, 2012, 6(1): 34–37

[26] Kumar M, Aberuagba F, Gupta J K, Rawat K S, Sharma L D, Dhar G M. Temperature-programmed reduction and acidic properties of molybdenum supported on MgO-Al₂O₃ and their correlation with catalytic activity. Journal of Molecular Catalysis A Chemical, 2004, 213(2): 217–223

[27] Trovarelli A. Catalytic properties of ceria and CeO₂-containing materials. Catalysis Reviews, 1996, 38(4): 439–520

[28] Wang B W, Shang Y G, Ding G Z, Lv J, Wang H Y, Wang E D, Li Z H, Ma X B, Qin S D, Sun Q. Effect of the ceria-alumina composite support on the Mo-based catalyst’s sulfur-resistant activity for the synthetic natural gas process. Reaction Kinetics. Mechanisms and Catalysis, 2012, 106(2): 495–506

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag Berlin Heidelberg