Properties Analysis of Spent Catalyst for Fixed-Bed Residue Hydrotreating Unit: Composition of Deposited Elements Along Catalyst Bed

SUN Yudong, YANG Chaohe, LIU Ziyuan

Abstract


Element compositions of spent catalyst from a commercial fixed-bed residue hydrotreating unit of Petro-China were analyzed in order to investigate the reasons for the catalyst deactivation. The spent catalysts were sampled from different axial position of the reactor. Depositions of C, H, S, N, Ni and V on the spent catalysts were studied. No necessary relation was observed for the contents of various deposited elements along the bed at the end of a run. The deposition amount of elements was mainly related to local reaction conditions and catalyst loading states in the fixed-bed. The catalysts with high metal depositions have low contents of coke, high contents of sulfur and high H/C, which indicates that residue hydrotreating is an autocatalytic process. Metal sulfides deposited on catalysts have a hydrogenation activity in residue hydrotreating. The coke on residue hydrotreating catalysts mainly comes from some specific condensed ring structures containing nitrogen existed in asphaltene which is difficult to hydrotreat.

Key words: Spent catalyst; Residue hydrotreating; Deposited elements; Composition


Keywords


Spent catalyst; Residue hydrotreating; Deposited elements; Composition

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References


[1] Xu, C. M., & Yang, C. H. (2009). Petroleum refining Engineering (4th ed.). Beijing: Petroleum Industry Press.

[2] Ferdous, D., Dalai, A. K., & Adjaye, J. (2006). Comparison of Product Selectivity During Hydroprocessing of Bitumen Derived Gas Oil in the Presence of NiMo/Al2O3 Catalyst Containing Boron and Phosphorus. Fuel, 85(9), 1286-1297.

[3] Callejas, M. A., Martinez, M. T., Blasco, T., & Sastre, E. (2001). Coke Characterisation in Aged Residue Hydrotreating Catalysts by Solid-State 13C-NMR Spectroscopy and Temperature-Programmed Oxidation. Appl Catal A, 218(1-2), 181-188.

[4] Sun, Y. D., Yang, C. H., Zhao, H., Shan, H. H., & Shen B. X. (2010). Influence of Asphaltene on the Residue Hydrotreating Reaction. Energy Fuels, 24(9), 5008-5011.

[5] Beuther, H., Larson, O. A., & Perrotta, A. J. (1980). Mechanism of Coke Formation on Catalysts. Stud. Surf. Sci. Catal, (6), 271-282.

[6] Marafi, A., Hauser, H., & Stanislaus, A. (2007). Deactivation Paterns of Mo/Al2O3, Ni-Mo/Al2O3 and Ni-MoP/Al2O3 Catalyst in Atmospheric Hydrodesulphurization. Catal. Today, 125(3-4), 192-202.

[7] Koichi, M., Andre, H., Abdulazem, M., Koide, R., & Anthony, S. (2004). Initial Coke Deposition on Hydrotreating Catalysts. Part1. Changes in Coke Properties as a Function of Time on Stream. Fuel, 83(7-8), 1031-1038.

[8] Chen, S. F., Chen, H., & Yang, C. H. (2002). Characterization of Coked Catalyst for Residual Hydroconversion Process. Acta Petrolei Sinica(Petroleum Processing Section), 18(3), 8-12.

[9] Ternan, M., Furimsky, E., & Parsons, B. I. (1979). Coke Formation on Hydrodesulphurization Catalysts. Fuel Proc. Tech., 2(1), 45-55.

[10] Al-Dalama, K., & Stanislaus, A. (2006). Comparison Between Deactivation Pattern of Catalysts in Fixed-Bed and Ebullating-Bed Residue Hydroprocessing Units. Chemical Engineering Journal, 120(1), 33-42.

[11] Xu, X. K., Zhu, P., & Wong, H. X. (2004). Cause of Coking in Front Reactor of Residue Hydrodesulfurization Unit and the Countermeasures. Petroleum Refinery Engineering, 34(2), 9-13.

[12] Sun Y. D. (2011). Influence of Residue Composition on Hydrotreating Reaction Performance and Properties of Catalyst (Doctoral dissertation). East China University of Science & Technology, China.

[13] Toulhoat, H., Szymanski, R., & Plumail, J.C. (1990). Interrelations Between Initial Pore Structure, Morphology and Distribution of Accumulated Deposits, and Lifetimes of Hydrodemetallisation Catalysts. Catal. Today, 7(4), 531-568.

[14] Smith, B. J., & Wei, J. (1991). Deactivation in Catalytic Hydrodemetallation II. Catalyst Characterization. J. Catal., 132(1), 21-40.

[15] Toulhoat, H., Plumail, J. C., Plumail, J. C., Houpert, C., Szymanski, R., & Muratet, G. (1987). Modelling REM Catalysts Deactivation by Metal Sulfides Deposits: an Original Approach Supported by HERM Investigations and Pilot Tests Results. Acs Div. Pet. Chem. Prepr, 32(2), 463.

[16] Jia, Y. Z., Yang, Q. H., Sun, S. L., Nie, H., & Li, D. D. (2010). Auto-Catalytic Activity of Deposited Vanadium in Residue Hydrodemetallization. Acta Petrolei Sinica (Petroleum Processing Section), 26(4), 635-641.




DOI: http://dx.doi.org/10.3968/j.est.1923847920120401.197

DOI (PDF): http://dx.doi.org/10.3968/pdf

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