Reactivity of Olefins and Thiophenes in Hydrodesulfurization of FCC Gasoline

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Abstract:

The reactivity of olefins and S-compounds and their distributions in different catalyst-bed lengths were experimentally evaluated with a FCC gasoline in a high-pressure fixed-bed continuous flow pilot unit over the CoMoS/γ-Al2O3 catalyst. The evaluation results demonstrated that the increased steric hindrances around the double bond (C=C) and that to the thiophene molecules could suppress the hydrogenation of olefins and hydrodesulfurization (HDS) of S-compounds, respectively. Meanwhile, the reaction temperatures could influence the acidic property of the CoMoS active phase confirmed by FT-IR analysis, and thus induced the different reactions. It was found that the isomerization of terminal olefins to internal olefins was promoted by the Brønsted acid sites (-SH) at low temperatures, as well as the skeletal isomerization by the strong Lewis acid sites occurred to a minor extent at high temperatures. Besides, the distributions of olefins and S-compounds in different catalyst-bed lengths showed that the removal of S-compounds reached 80% of its maximum conversion at the first 40% of the reactor length, however, the saturation of olefins increased linearly as the reactor length increased. Therefore, a new catalyst-loading method was developed, i.e., the upper 40% of the reactor length filling with catalyst of high HDS activity and the bottom 60% with catalyst of low olefin saturation activity, respectively. The evaluation results showed that the graded catalyst loading process showed higher selectivity in HDS of FCC gasoline.

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Advanced Materials Research (Volumes 881-883)

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271-278

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January 2014

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© 2014 Trans Tech Publications Ltd. All Rights Reserved

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[1] T.G. Kaufmann, A. Kaldor, G.F. Stuntz, M.C. Kerby, L.L. Ansell, Catalysis science and technology for cleaner transportation fuels, Catal. Today 62 (2000) 77-90.

DOI: 10.1016/s0920-5861(00)00410-7

Google Scholar

[2] M. Toba, Y. Miki, T. Matsui, M. Harada, Y. Yoshimura, Reactivity of olefins in the hydrodesulfurization of FCC gasoline over CoMo sulfide catalyst, Appl. Catal. B 70 (2007) 542-547.

DOI: 10.1016/j.apcatb.2005.12.026

Google Scholar

[3] S. Hatanaka, M. Yamada, O. Sadakane, Hydrodesulfurization of Catalytic Cracked Gasoline. 3. Selective Catalytic Cracked Gasoline Hydrodesulfurization on the Co-Mo/γ-Al2O3 Catalyst Modified by Coking Pretreatment, Ind. Eng. Chem. Res. 37 (1998).

DOI: 10.1021/ie970735l

Google Scholar

[4] S. Hatanaka, M. Yamada, Hydrodesulfurization of Catalytic Cracked Gasoline. 1. Inhibiting Effects of Olefins on HDS of Alkyl(benzo)thiophenes Contained in Catalytic Cracked Gasoline, Ind. Eng. Chem. Res. 36 (1997) 1519-1523.

DOI: 10.1021/ie9603777

Google Scholar

[5] S. Brunet, D. Mey, G. Pérot, C. Bouchy, F. Diehl, On the hydrodesulfurization of FCC gasoline: a review, Appl. Catal. A 278 (2005) 143-172.

DOI: 10.1016/j.apcata.2004.10.012

Google Scholar

[6] L.E. Kallinikos, A. Jess, N.G. Papayannakos, Kinetic study and H2S effect on refractory DBTs desulfurization in a heavy gasoil, J. Catal. 269 (2010) 169-178.

DOI: 10.1016/j.jcat.2009.11.005

Google Scholar

[7] B. Liu, Y. Chai, Y. Wang, T. Zhang, Y. Liu, C. Liu, A simple technique for preparation of presulfided eggshell MoS2/Al2O3 catalysts and kinetics approach for highly selective hydrodesulfurization of FCC gasoline, Appl. Catal. A 388 (2010) 248-255.

DOI: 10.1016/j.apcata.2010.08.059

Google Scholar

[8] M. Toba, Y. Miki, Y. Kanda, T. Matsui, M. Harada, Y. Yoshimura, Selective hydrodesulfurization of FCC gasoline over CoMo/Al2O3 sulfide catalyst, Catal. Today 104 (2005) 64-69.

DOI: 10.1016/j.cattod.2005.03.027

Google Scholar

[9] P. Ghosh, A.T. Andrews, R.J. Quann, T.R. Halbert, Detailed Kinetic Model for the Hydrodesulfurization of FCC Naphtha, Energy Fuels 23 (2009) 5743-5759.

DOI: 10.1021/ef900632v

Google Scholar

[10] T. Mochizuki, H. Itou, M. Toba, Y. Miki, Y. Yoshimura, Effects of Acidic Properties on the Catalytic Performance of CoMo Sulfide Catalysts in Selective Hydrodesulfurization of Gasoline Fractions, Energy Fuels 22 (2008) 1456-1462.

DOI: 10.1021/ef700644e

Google Scholar

[11] G. Berhault, M. Lacroix, M. Breysse, F. Maugé, J. -C. Lavalley, H. Nie, L. Qu, Characterization of Acidic Sites of Silica-Supported Transition Metal Sulfides by Pyridine and 2, 6 Dimethylpyridine Adsorption: Relation to Activity in CH3SH Condensation, J. Catal. 178 (1998).

DOI: 10.1006/jcat.1998.2196

Google Scholar

[12] J.V. Lauritsen, J. Kibsgaard, G.H. Olesen, P.G. Moses, B. Hinnemann, S. Helveg, J.K. Nørskov, B.S. Clausen, H. Topsøe, E. Lægsgaard, F. Besenbacher, Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts, J. Catal. 249 (2007).

DOI: 10.1016/j.jcat.2007.04.013

Google Scholar

[13] N. Dos Santos, H. Dulot, N. Marchal, M. Vrinat, New insight on competitive reactions during deep HDS of FCC gasoline, Appl. Catal. A 352 (2009) 114-123.

DOI: 10.1016/j.apcata.2008.09.035

Google Scholar

[14] A. Daudin, S. Brunet, G. Perot, P. Raybaud, C. Bouchy, Transformation of a model FCC gasoline olefin over transition monometallic sulfide catalysts, J. Catal. 248 (2007) 111-119.

DOI: 10.1016/j.jcat.2007.03.009

Google Scholar

[15] A. Travert, H. Naskamura, R.A.V. Santen, S. Cristol, J.F. Paul, E. Payen, Hydrogen Activation on Mo-Based Sulfide Catalysts, a Periodic DFT Study, J. Am. Chem. Soc 124 (2002) 7084.

DOI: 10.1021/ja011634o

Google Scholar

[16] D. Mey, S. Brunet, C. Canaff, F. Maugé, C. Bouchy, F. Diehl, HDS of a model FCC gasoline over a sulfided CoMo/Al2O3 catalyst: Effect of the addition of potassium, J. Catal. 227 (2004) 436-447.

DOI: 10.1016/j.jcat.2004.07.013

Google Scholar