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Hydrocracking of n-decane over zeolite-supported metal sulfide catalysts. 1. CaY-supported transition metal sulfides

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1156 Znd. Eng. Chem. Res. 1995,34, 1156-1165 Hydrocracking of n-Decane over Zeolite-Supported Metal Sulfide Catalysts. 1. Cay-Supported Transition Metal Sulfides Wim J. J. Welters, Onno H. van der Waerden, Henny W. ZandbergenJ Vincent H. J. de Beer,* and Rutger A. van Santen Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands The hydrocracking properties of various Cay-supported metal (Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Ir, and Pt) sulfide catalysts (prepared by impregnation) are examined by studying the hydroconversion of n-decane. All catalysts show cracking conversions which are significantly higher than that of the Cay support. There are large differences in catalytic behavior dependent on the metal sulfide present on the zeolite support. The amounts of S present on the catalyst are analyzed to determine the degree of sulfidation of the metal sulfide, while high resolution electron microscopy is used to characterize the distribution of the metal sulfide phase over the zeolite support. The observed differences in activity can be explained by the differences in intrinsic activity of the metal sulfide phase and the differences in distribution of this phase over the zeolite particle (internal or external sulfide deposition). Introduction Hydrocracking is a typical example of bifunctional catalysis, in which both the hydrogenatiorddehydroge- nation and the cracking function play a crucial role. Weitkamp et al. (Schulz and Weitkamp, 1972; Weit- kamp, 1982) and Jacobs et al. (Martens et al., 1986a,b; Jacobs and Martens, 1991) have extensively studied the hydrocracking reaction to unravel the mechanism, in particular for the hydrocracking of higher paraffins over noble metal on zeolite catalysts. The reaction starts with the dehydrogenation of the paraffins over the metallic (or metal sulfide) function producing olefins. These form carbenium ions at the acid sites and then undergo the usual acid

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