HYDRODESULFURIZATION OF THIOPHENE OVER BIMETALLIC ...

HYDRODESULFURIZATION OF THIOPHENE OVER BIMETALLIC ... HYDRODESULFURIZATION OF THIOPHENE OVER BIMETALLIC ...

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64 Hamid A. Al-Megren In summary, a new method has been developed to prepare HDS catalyst and this catalyst has been compared with catalysts prepared by the conventional methods for selective thiophene HDS. This method enables a high dispersion of the molybdenum oxide and sulfide, resulting in higher activity and high yield of olefin in thiophene HDS. ACKNOWLEDGMENT The author would like thank Eng. Saeed Alshihri, Eng. Saud Aldrees, and Mr. Rasheed Al-Rasheed for their help in experimental work in the laboratories of King Abdulaziz City for Science and Technology. The author would also like to thank the Inorganic Chemistry Laboratory (ICL) at the University of Oxford, England, for their assistance in this research. REFERENCES [1] C. Song, X. Ma, “New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization”, Appl. Catal. B: Environ.,41(2003), p. 207. [2] V. Babich and J.A. Moulijn, “Science and Technology of Novel Processes for Deep Desulfurization of Oil Refinery Streams: a Review”, Fuel, 82(2003), p. 607. [3] H. Topsøe, B.S. Clausen, and F.E. Massoth, Catalysis, Science and Technology, vol. 11. Berlin: Springer-Verlag, 1996. [4] R. Prins, H.J. de Beer, and G.A. Somorjai, “Structure and Function of the Catalyst and the Promoter in Co–Mo Hydrodesulfurization Catalysts”, Catal. Rev.-Sci. Eng., 31(1989), p. 1. [5] P.T. Vasudevan and J.L.G. Fierro, “A Review of Deep Hydrodesulfurization Catalysis”, Catal. Rev.-Sci. Eng., 38(1996), p. 161. [6] R. Prins, “Catalytic Hydrodenitrogenation”, Adv. Catal., 46(2001), p. 399. [7] M. Zdrazil, “Recent Advances in Catalysis over Sulphides”, Catal. Today, 3(1988), p. 269. [8] R. Prins, V.H.J. de Beer, and G.A. Somorjai, “Structure and Function of the Catalyst and the Promoter in Co–Mo Hydrodesulfurization Catalysts”, Catal. Rev.-Sci. Eng., 31(1989), p. 1. [9] J.T. Kloprogge, W.J.J. Welters, et al. “Catalytic Activity of Nickel Sulfide Catalysts Supported on Al-Pillared Montmorillonite for Thiophene Hydrodesulfurization”, Appl. Catal. A Gen., 97(1993), p. 77. [10] E. Hayashi. et al. “High Surface Area Smectite Supported Cobalt Oxides as Active Catalysts for Thiophene Hydrodesulfurization”, Chemistry Letters, 5(1997), pp. 433–434. [11] E. Hayashi. et al., “Characterization of High Surface Area Smectite Supported Cobalt Oxides Catalysts for Hydrodesulfurization by Means of TPR, TPS, and ESR”, Appl. Catal. A Gen., 179(1999), p. 203. [12] J.C. Duchet. et al. “Carbon-Supported Sulfide Catalysts”, J. of Catal., 80(1983), p. 386. [13] S. L. Gonzalez-Cortes. et al., “Urea–Organic Matrix Method: an Alternative Approach to Prepare Co–MoS2–Al2O3 HDS Catalyst”, Appl. Catal., A: General, 270(2004), p. 209. [14] S. Damyanova, A. Spojakina, and K. Jiratova, “Effect of Mixed Titania–Alumina Supports on the Phase Composition of NiMo/TiOz–Al2O3 catalysts”, Appl. Catal. A, 125(1995), p. 257. [15] H. Qabazard, F. Abuseedo, A. Stanislaus, M. Andari, and M. Absihalabi, Fuel Sci. Technol. Int., 13(1995), p. 1135. [16] C. Papadopoulou, H. Matralis, A. Lycourghiotis, P. Grange, and B. Delmon, “Florinated Hydrotreatment Catalysts. Acidity and Carbon Deposition on Fluorine-Nickel-Molybdenum/γ-Alumina Catalysts”, J. Chem. Soc.– Faraday Trans., 89(1993), p. 3157. [17] V. Zuzaniuk and R. Prins, “Synthesis and Characterization of Silica-Supported Transition-Metal Phosphides as HDN Catalysts”, J. Catal., 219(2003), p. 85. [18] C. Kwak, J.J. Lee, J.S. Bae, K. Choi, and S.H. Moon, “Hydrodesulfurization of DBT, 4-MDBT, and 4,6-DMDBT on Fluorinated CoMoS/Al2O3 Catalysts”, Appl. Catal. A, 200(2000), p. 233. [19] H. Kim, J.J. Lee, and S.H. Moon, “Hydrodesulfurization of Dibenzothiophene Compounds using Fluorinated NiMo/Al2O3 Catalysts”, Appl. Catal. B, 44(2003), p. 287. [20] W.P. Zhang, M.Y. Sun, and R. Prins, “A High-Resolution MAS NMR Study of the Structure of Fluorinated NiW/γ- Al 2O 3 Hydrotreating Catalysts”, J. Phys. Chem. B, 107(2003), p. 10977. January 2009 The Arabian Journal for Science and Engineering, Volume 34, Number 1A

Hamid A. Al-Megren [21] V. Schwartz, M.Y. Sun, and R. Prins, “An EXAFS Study of the Influence of Fluorine on the Structure of Sulfided W/Al2O3 and NiW/Al2O3 Catalysts”, J. Phys. Chem. B, 106(2002), p. 2597. [22] M. Nagai, Y. Goto, H. Ishii, and S. Omi, “XPS and TPSR Study of Nitrided Molybdena–Alumina Catalyst for the Hydrodesulfurization of Dibenzothiophene”, Appl. Catal. A, 192(2000), p. 189. [23] P. Da Costa, C. Potvin, J.M. Manoli, J.L. Lemberton, G. Perot, and G. Djega Mariadassou, “New Catalysts for Deep Hydrotreatment of Diesel Fuel Kinetics of 4,6–Dimethyldibenzothiophene Hydrodesulfurization over Alumina Supported Molybdenum Carbide”, J. Mol. Catal. A, 184(2002), p. 323. [24] P. Da Costa, C. Potvin, J.M. Manoli, M. Breysse, and G. Djega-Mariadassou, Catal. Lett., 86(2003), p. 133. [25] H.R. Reinhoudt, M. van Gorsel, A.D. van Langeveld, J.A.R. van Veen, S.T. Sie, and J.A. Moulijn, Hydrotreatment and Hydrocracking of Oil Fractions, 127(1999), p. 211. [26] H. Topsøe, R. Candia, N.Y. Topsøe, and B.S. Clausen, Bull. Soc. Chim. Belg., 93(1984) p. 83. [27] H. Topsøe, B.S. Clausen, N.Y. Topsøe, and E. Pedersen, Ind. Eng. Chem. Fundam., 25(1986) p. 25. [28] H. Farag, D.D. Whitehurst, K. Sakanishi, and I. Mochida, “Carbon versus Alumina as a Support for Co–Mo Catalysts Reactivity Towards HDS of Dibenzothiophenes and Diesel fuel”, Catal. Today, 50(1999), p. 9. [29] A.A. Spozhakina et. al., “Synthesis of Molybdenum/silica and Cobalt–Molybdenum/Silica Catalysts and their Catalytic Activity in the Hydrodesulfurization of Thiophenes”, Appl. Catal., 39(1988), p. 333. [30] R. Cattaneo, T. Shido, R. Prins in: Hydrotreatment and Hydrocracking of Oil Fractions, Amsterdam: Elsevier, 1999, p. 421. [31] M. Breysse, E. Furimsky, S. Kasztelan, M. Lacroix, and G. Perot, “Hydrogen Activation by Transition Metal Sulfides”, Catal. Rev.-Sci. Eng., 44(2002), p.651. [32] F. Bataille et al., “Sulfided Mo and CoMo Supported on Zeolite as Hydrodesulfurization Catalysts: Transformation of Dibenzothiophene and 4,6– Dimethyldibenzothiophene”, Appl. Catal. A, 220(2001), p. 191. [33] P.W. de Bont et al., “Molybdenum-Sulfide Particles Inside NaY Zeolite as a Hydrotreating Catalyst Prepared by Adsorption of Mo(CO) 6”, Appl. Catal. A, 202(2000), p. 99. [34] G. Plazenet, E. Payen, and J. Lynch, “Cobalt-Molybdenum Interaction in Oxidic Precursors of Zeolite-Supported HDS Catalysts”, Phys. Chem. Chem. Phys., 4(2002), p. 3924. [35] J. Vissenberg et al., “The Effect of Support Interaction on the Sulfidability of Al2O3- and TiO2-Supported CoW and NiW Hydrodesulfurization Catalysts”, J. Catal., 198(2001), p. 151. [36] S.K. Maity, M.S. Rana, S.K. Bej, J. Ancheyta-Juarez, G.M. Dhar, and T. Rao, Catal. Lett., 72(2001), p. 115. [37] P. Afanasiev, M. Cattenot, C. Geantet, N. Matsubayashi, K. Sato, and S. Shimada, “(Ni)W/ZrO2 Hydrotreating Catalysts Prepared in Molten Salts”, Appl. Catal. A, 237(2002), p. 227. [38] L. Qu, W. Zhang, P.J. Kooyman, and R. Prins, “MAS NMR, TPR, and TEM Studies of the Interaction of NiMo with Alumina and Silica–Alumina Supports”, J. Catal., 215(2003), p. 7. [39] L.D. Sharma, M. Kumar, J.K. Gupta, M.S. Rana, V.S. Dangwal, and G.M. Dhar, Indian J. Chem. Technol., 8(2001) p. 169. [40] F. Schuth and K. Unger, “Precipitaion and Coprecipitation” in Handbook of Heterogeneous Catalysis, Vol. 1, ed. G. Ertl, H. Knozinger, and J. Weitkamp. Wiley–VCH, 1997, p. 72. [41] M. Che, O. Clause, and Ch. Marcilly, “Impregnation and Ion Exchange”, in Handbook of Heterogeneous Catalysis, Vol. 1, ed. G. Ertl, H. Knozinger, and J. Weitkamp. City: Wıley–VCH, 1997, p. 191. [42] B. H. Davis, in Handbook of Heterogeneous Catalysis, Vol. 1, ed. By G. Ertl, H. Knozinger, and J. Weitkamp. City: Wıley–VCH, 1997, p. 13. [43] E. I. Ko, “Sol-Gel Process”, in Handbook of Heterogeneous Catalysis, Vol. 1, ed. G. Ertl, H. Knozinger, and J. Weitkamp. Wiley–VCH, 1997, p. 86. [44] S.L. Gonzalez-Cortes et. al., “Impact of the Urea–Matrix Combustion Method on the HDS Performance of Ni– MoS2/γ-Al2O3 Catalysts”, J. Mol. Catal. A: Chem, 240(2005), p. 214. [45] S. L. Gonzalez-Cortes, T-C Xiao, and M.L.H. Green, Proceedings of the 9 th International Symposium, Scientific Bases for the Preparation of Heterogeneous Catalysts, Louvain-la-Neuve, Belgium, September 10-14, 2006, p. 817. The Arabian Journal for Science and Engineering, Volume 34, Number 1A January 2009 65

Hamid A. Al-Megren<br />

[21] V. Schwartz, M.Y. Sun, and R. Prins, “An EXAFS Study of the Influence of Fluorine on the Structure of Sulfided<br />

W/Al2O3 and NiW/Al2O3 Catalysts”, J. Phys. Chem. B, 106(2002), p. 2597.<br />

[22] M. Nagai, Y. Goto, H. Ishii, and S. Omi, “XPS and TPSR Study of Nitrided Molybdena–Alumina Catalyst for the<br />

Hydrodesulfurization of Dibenzothiophene”, Appl. Catal. A, 192(2000), p. 189.<br />

[23] P. Da Costa, C. Potvin, J.M. Manoli, J.L. Lemberton, G. Perot, and G. Djega Mariadassou, “New Catalysts for<br />

Deep Hydrotreatment of Diesel Fuel Kinetics of 4,6–Dimethyldibenzothiophene Hydrodesulfurization over<br />

Alumina Supported Molybdenum Carbide”, J. Mol. Catal. A, 184(2002), p. 323.<br />

[24] P. Da Costa, C. Potvin, J.M. Manoli, M. Breysse, and G. Djega-Mariadassou, Catal. Lett., 86(2003), p. 133.<br />

[25] H.R. Reinhoudt, M. van Gorsel, A.D. van Langeveld, J.A.R. van Veen, S.T. Sie, and J.A. Moulijn, Hydrotreatment<br />

and Hydrocracking of Oil Fractions, 127(1999), p. 211.<br />

[26] H. Topsøe, R. Candia, N.Y. Topsøe, and B.S. Clausen, Bull. Soc. Chim. Belg., 93(1984) p. 83.<br />

[27] H. Topsøe, B.S. Clausen, N.Y. Topsøe, and E. Pedersen, Ind. Eng. Chem. Fundam., 25(1986) p. 25.<br />

[28] H. Farag, D.D. Whitehurst, K. Sakanishi, and I. Mochida, “Carbon versus Alumina as a Support for Co–Mo<br />

Catalysts Reactivity Towards HDS of Dibenzothiophenes and Diesel fuel”, Catal. Today, 50(1999), p. 9.<br />

[29] A.A. Spozhakina et. al., “Synthesis of Molybdenum/silica and Cobalt–Molybdenum/Silica Catalysts and their<br />

Catalytic Activity in the Hydrodesulfurization of Thiophenes”, Appl. Catal., 39(1988), p. 333.<br />

[30] R. Cattaneo, T. Shido, R. Prins in: Hydrotreatment and Hydrocracking of Oil Fractions, Amsterdam: Elsevier,<br />

1999, p. 421.<br />

[31] M. Breysse, E. Furimsky, S. Kasztelan, M. Lacroix, and G. Perot, “Hydrogen Activation by Transition Metal<br />

Sulfides”, Catal. Rev.-Sci. Eng., 44(2002), p.651.<br />

[32] F. Bataille et al., “Sulfided Mo and CoMo Supported on Zeolite as Hydrodesulfurization Catalysts: Transformation<br />

of Dibenzothiophene and 4,6– Dimethyldibenzothiophene”, Appl. Catal. A, 220(2001), p. 191.<br />

[33] P.W. de Bont et al., “Molybdenum-Sulfide Particles Inside NaY Zeolite as a Hydrotreating Catalyst Prepared by<br />

Adsorption of Mo(CO) 6”, Appl. Catal. A, 202(2000), p. 99.<br />

[34] G. Plazenet, E. Payen, and J. Lynch, “Cobalt-Molybdenum Interaction in Oxidic Precursors of Zeolite-Supported<br />

HDS Catalysts”, Phys. Chem. Chem. Phys., 4(2002), p. 3924.<br />

[35] J. Vissenberg et al., “The Effect of Support Interaction on the Sulfidability of Al2O3- and TiO2-Supported CoW and<br />

NiW Hydrodesulfurization Catalysts”, J. Catal., 198(2001), p. 151.<br />

[36] S.K. Maity, M.S. Rana, S.K. Bej, J. Ancheyta-Juarez, G.M. Dhar, and T. Rao, Catal. Lett., 72(2001), p. 115.<br />

[37] P. Afanasiev, M. Cattenot, C. Geantet, N. Matsubayashi, K. Sato, and S. Shimada, “(Ni)W/ZrO2 Hydrotreating<br />

Catalysts Prepared in Molten Salts”, Appl. Catal. A, 237(2002), p. 227.<br />

[38] L. Qu, W. Zhang, P.J. Kooyman, and R. Prins, “MAS NMR, TPR, and TEM Studies of the Interaction of NiMo<br />

with Alumina and Silica–Alumina Supports”, J. Catal., 215(2003), p. 7.<br />

[39] L.D. Sharma, M. Kumar, J.K. Gupta, M.S. Rana, V.S. Dangwal, and G.M. Dhar, Indian J. Chem. Technol.,<br />

8(2001) p. 169.<br />

[40] F. Schuth and K. Unger, “Precipitaion and Coprecipitation” in Handbook of Heterogeneous Catalysis, Vol. 1, ed.<br />

G. Ertl, H. Knozinger, and J. Weitkamp. Wiley–VCH, 1997, p. 72.<br />

[41] M. Che, O. Clause, and Ch. Marcilly, “Impregnation and Ion Exchange”, in Handbook of Heterogeneous Catalysis,<br />

Vol. 1, ed. G. Ertl, H. Knozinger, and J. Weitkamp. City: Wıley–VCH, 1997, p. 191.<br />

[42] B. H. Davis, in Handbook of Heterogeneous Catalysis, Vol. 1, ed. By G. Ertl, H. Knozinger, and J. Weitkamp.<br />

City: Wıley–VCH, 1997, p. 13.<br />

[43] E. I. Ko, “Sol-Gel Process”, in Handbook of Heterogeneous Catalysis, Vol. 1, ed. G. Ertl, H. Knozinger, and J.<br />

Weitkamp. Wiley–VCH, 1997, p. 86.<br />

[44] S.L. Gonzalez-Cortes et. al., “Impact of the Urea–Matrix Combustion Method on the HDS Performance of Ni–<br />

MoS2/γ-Al2O3 Catalysts”, J. Mol. Catal. A: Chem, 240(2005), p. 214.<br />

[45] S. L. Gonzalez-Cortes, T-C Xiao, and M.L.H. Green, Proceedings of the 9 th International Symposium, Scientific<br />

Bases for the Preparation of Heterogeneous Catalysts, Louvain-la-Neuve, Belgium, September 10-14, 2006, p. 817.<br />

The Arabian Journal for Science and Engineering, Volume 34, Number 1A January 2009 65

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