The Effect of Coking on Kinetics of HDS Reaction under Steady and Transient States

Document Type : Research Article

Authors

Department of Chemical Engineering, Faculty of Engineering, University of Tehran, P. O. Box 11365-4563, Tehran, I.R. IRAN

Abstract

A study was made of the coking of a commercial fresh sulfide Ni-Mo/Al2O3 catalyst in a fixed-bed reactor. The catalyst was coked using different coke precursors in the gas oil under accelerated conditions at temperatures of 400 to 450°C to yield different deactivated catalysts containing 2-20 wt% C. Two cases were studied; crushed catalyst without diffusional resistance and extruded pellets with diffusional resistance. Physical properties and catalytic activities of the coked catalysts were measured using the thiophene sulfur removal in the gas oil.It is concluded that coking occurs by selective deactivation on hydrotreating catalyst and the experimental results of the catalyst activity under different operating conditions, obey a power law as a function of the coke cantent. In the pellet catalyst showed a lower rate of coking and deactivation in comparison to the catalyst without diffusional resistance. It is inferred that high level of coke content ( higher than 12 wt% C) affects the tortusity factor of the catalyst,considerably.In the study of transient deactivation, initial activity of the catalyst  was derived by a time variable function, then this equation was used in  dynamic model of hydrodesulfurization reaction in a packed bed reactor to determine  the activity change of the catalyst in the reactor during actual operational conditions. 

Keywords

Main Subjects


[1] Leglise J., Finot, L., Van Gestel, J. N. M. and Duchet, J. C., “Conversion of Model Sulfur Compounds to Characterize Hydrodesulfurization Co-Mo/Al2O3 Catalyst, in B. Delmon, G. F. Froment and P. Grange (eds.)” Hydrotreating and Hydrocracking of Oil Fractions, Elsevier, 127, 51 (1999).
[2] Muegge B. and Massoth, F. E., “Comparison of Hydrotreating Catalyst Deactivation by Coking With Vaccum Gas Oil vs. Anthracene, in C. H. Bartholomew and Butt, J. B., (eds.), “Catalyt Deactivation”, Elsevier, 68,297 (1991).
[3] Richardson, S. M., Nagaishi, H.  and Gray, M.R., “Initial Coke Deposition on Ni-Mo/g-Al2O3 Bitumene Hydroprocessing Catalyst”, Ind. Eng. Chem. Res., 35, 3940 (1996).
[4] Froment, G. F., “Coke Formation in Catalytic Process; Kinetics and Catalyst Deactivation”, in C. H. Bartholomew and G. A. Fuentes (eds.) “Catalyst Deactivation”, Elsevier, 126 ,53(1997).
[5] Gorra, F., Scribano, G., Christens, P., Andersen, K. V. and Casaro, O. G., “ New Catalyst Improved Presulfiding  Results in 4+ Year Hydrotreatment”, Oil & Gas J., 23 Aug., 39 (1993).
[6] Lulic P., Zrncevic, S., Meider, H. and Sevdic, D., “The Relation Between the Quality of Catalyst and Feedstock in Hydrotreating Process”, in D. L. Trimm, S. Akashah, M. Absi-Halabi, and A. Bishara (eds.), “Catalysts in Petroleum Refining”, Elsevier, 451(1989).
[7] Furimsky, E. and Massoth, F. E., “Deactivation of Hydroprocessing Catalysts”, Cat. Today, 52, 381(1992).
[8] Smith, J. M., “Chemical Engineering Kinetics”, McGraw-Hill, New York,265 (1981).
[9] Krishna, A. K., Diffusional Influences on Catalyst Deactivation, Catal. Rev. Sci. Eng., 32 (4),279 (1991).
[10] Takalsuka, T., Wada, Y. and Inone, S., “A Catalyst Deactivation Model For Residual Oil HDS and Application to Deep  HDS of Diesel Fuel”, Ame. Chem. Soc., 414 (1996).
[11] Fogler, H. S., “Elements of Chemical Reaction Engineering”, Prentice- Hall, p. 738 (1992).
[12] Fatemi, Sh., Abolhamd, G., Moosavian, M.A. and Mortazavi, Y., "The Empirical model of HDS reaction from gas oil by Ni-Mo/Al2O3 Catalysts", The Fifth National Congress of Chemical Eng., Shiraz, April, 24-27 (2000).
[13] Petersen, E. E., “The Fouling  of Catalysts; Experimental Observation and Modeling” in E.E.   Petersen and A. T. Bell (eds.), “ Catalyst Deactivation” Marcel Dekker,(1987).
[14] Fatemi Sh., Abolhamd, G., Moosavian, M.A. and Mortazavi, Y., “Investigation and Comparison of Ni-Mo/Al2O3 Catalysts Activity in Hydrode-sulfurization Reaction of Thiophene in Gas Oil”, J. Faculty Eng., 35 (2), 169 (2001).[15] Fatemi, Sh., “Determination of Deactivating Parameters of HDS Catalysts and Their Effects on Kinetic Model at Steady and Transitional State”,  Ph. D. Dissertation , Dep. of Chemical Eng., Faculty of Eng., University of Tehran, (2001).