Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China

Abstract

The development and application of ex-situ presulfurization (EPRES) technology for hydrotreating catalysts has been reviewed in the present article. The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components, shorten the start-up period, and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit. This catalyst has been proved to be versatile for different types of hydrogenation reactions. Different types of active site models are also discussed for better understanding the nature of presulfurized catalysts.

Keywords

ex-situ presulfurization / in situ presulfurization / hydrotreating catalyst / hydrotreating catalyst / sulfur utilization ratio

References

[1] Wilson J H, Berrebi G. Sulficat^®: off-site presulfiding of hydroprocessing catalyst from Eurecat.Studies in Surface Science and Catalysis, 1988, 38: 393-398

[2] De Wind M, Heinerman J J L, Lee S L, Plantenga F L, Johnson C C, Woodward D C. Air quality and economics spur use of presulfided catalysts.Oil & Gas Journal, 1992, 90: 49-53

[3] Blashka S, Bond G, Ward D. New presulfurized catalyst reduces exotherm potential in hydrocrackers.Oil & Gas Journal, 1998, 96: 36-40

[4] Berrebi G. Process of presulfurizing catalysts for hydrocarbons treatment.US Patent, 4530917,1985

[5] Dufresne P, Labruyere F. Ex-situ presulfuration in the presence of hydrocarbon molecule. US Patent, 6417134,2002

[6] Seamans J D, Welch J G, Gasser N G. Method of presulfiding a hydrotreating catalyst. US Patent, 4943547,1990

[7] Seamans J D, Adams C T, Dominguez W B, Chen A A. Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst.US Patent, 5215954,1993

[8] Neuman D J, Semper G K, Creager T. Method of presulfiding and passivating a hydrocarbon conversion catalyst. US Patent, 5958816, 1999

[9] Berrebi G. Process for presulfurizing with phosphorous and/or halogen additive.US Patent, 4983559,1991

[10] Wang Y X. Ex-situ presulfurization technology for hydrotreating catalyst.Petroleum Refinery Engineering,2000, 30: 57-58 (in Chinese)

[11] Seamans J D, Adams C T, Dominguez W B, Chen A A. Method of presulfurizing a hydrotreating: hydrocracking or tail gas treating catalyst. US Patent, 5688736, 1997

[12] Gao Y, Fang X. Study on hydrogenation catalyst with ex-situ presulfurization technology.Petroleum Processing and Petrochemicals, 2005, 36(7): 1-4 (in Chinese)

[13] Gao Y, Fang X, Wang G, Cao F, Li C. Pilot plant test of ex-situ presulfurization hydrotreating catalyst.Petroleum Refinery Engineering, 2005, 35(4): 34-35 (in Chinese)

[14] Gao Y, Wang A, Fang X, Hu Y. Development and application of EPRES ex-situ presulfiding technology.Industrial Catalysis, 2007, 15(2): 33-35

[15] Gao Y, Fang X, Cheng Z. A comparative study on the ex-situ and in-situ presulfurization of hydrotreating catalysts.Catalysis Today, 2010, 158(3-4): 496-503

[16] Schuit G C A, Gates B C. Chemistry and engineering of catalytic hydrodesulfurization.AIChE Journal, 1973, 19(3): 417-438

[17] Wivel C, Clausen B S, Candia R, Mørup S, Topsøe H. Mössbauer emission studies of calcined Co-Mo/Al₂O₃ catalysts: catalytic significance of Co precursors.Journal of Catalysis, 1984, 87(2): 497-513

[18] Sakashita Y, Yoneda T. Orientation of MoS₂ clusters supported on two kinds of γ-Al₂O₃ single crystal surfaces with different indices.Journal of Catalysis, 1999, 185(2): 487-495

[19] 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

[20] Grange P, Vanhaeren X. Hydrotreating catalysts: an old story with new challenges.Catalysis Today, 1997, 36(4): 375-391

[21] Eijsbouts S. On the flexibility of the active phase in hydrotreating catalyst.pplied Catalysis A: General, 1997, 158(1-2): 53-92

[22] Lauritsen J V, Helveg S, Lægsgaard E, Stensgaard I, Clausen B S, Topsøe H, Besenbacher F. Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts.Journal of Catalysis, 2001, 197(1): 1-5

[23] Raybaud P, Hafner J, Kresse G, Kasztelan S, Toulhoat H. Ab initio study of the H₂-H₂S/MoS₂ gas-solid interface: the nature of the catalytically active sites.Journal of Catalysis, 2000, 189(1): 129-146

Acknowledgements

We are grateful for the help of the colleagues in the present study: Minghua Guan, Jifeng Wang, Gang Wang, Fenglan Cao, Chonghui Li, Guang Chen, Liming Xu, Fengxiang Ling, Xiwen Zhang, Jihua Liu, Yang Li, Zhen Wang, Guangwei Cao, Xingwei Qi, Shunxin Li, Lijing Jiang, Zhaoming Han, Huimin Qi, Zhongying Zhang, and Bingbing Guo.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg