Patent GB-1348137-A (GB)
Title: Hydrocracking catalyst
IPC: B01J29/16
Filed: 1970-12-23
Abstract: 1348137 Hydrocracking catalysts SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ NV 23 Dec 1970 [29 Dec 1969] 61040/70 Heading B1E [Also in Division C5] Hydrocracking catalysts consists of (a) crystalline aluminasilicate zeolite having a silica:alumina moler ratio of from 2:1 to 10:1 and an alkali metal content (calculated as oxide) of less than 2, preferably of from 0.04 to 1.0, weight per cent, (b) nickel and/or a compound thereof in an amount (calculated as metal) constituting from 15 to 30, preferably from 19 to 22, weight per cent of the catalyst, (c) at least one Group IIB metal and/or a compound thereof in an amount (calculated as metal) constituting from 0.05 to 6, preferably from 0.2 to 4, weight per cent of the catalyst and, optionally, (d) halogen, for example fluorine in an amount constituting up to 10 weight per cent of the catalyst. The zeolite may be natural or synthetic, for example selected from faujasite, mordenite and zeolites X, Y and L, and may have been subjected to cation exchange with ammonium ions (and thereafter calcined to provide hydrogenform zeolite) or with ions selected from silver, magnesium, calcium, zinc, aluminium and rare earth metal ions. The Group VIB metal may be selected from chromium, molybdenum and tungsten. The nickel and Group VIB metal may be present in the form of metals, oxides or sulphides or bound to the zeolite. The catalyst may be prepared by a procedure wherein the nickel and Group VIB metal are composited, either separately or simultaneously, with the zeolite by ion exchange and/or by impregnation, with the proviso that, for incorporation of nickel by ion exchange, incorporation of nickel is effected either prior to or simultaneously with incorporation of Group VIB metal, the resulting material being dried, for example at a temperature of from 100 to 200‹C, and calcined, for example at a temperature of from 400 to 650‹C in an oxygencontaining environment such as air. Catalyst deactivated by use may be regenerated by heating at a temperature not above 800‹C, preferably not above 525‹C, in gas having a low content of oxygen, for example diluted air; regenerated catalyst preferably is sulphided before re-use. As exemplified, catalyst comprising nickel and either fluorine but no tungsten (comparison catalyst A) or tungsten but no fluorine (catalysts B and C) or both tungsten and fluorine (comparison catalyst D) on aluminium-form zeolite Y is prepared by a procedure wherein sodium-form zeolite Y is contacted with aluminium nitrate solution, dried at 120‹C, contacted with a solution containing nickel acetate and, as required, ammonium metatungstate and/or ammonium fluoride, dried at 120‹C, pelleted, calcined at 550‹C and sulphided at 200-540‹C using a mixture of hydrogen sulphide and hydrogen; catalyst comprising nickel and either tungsten but no fluorine (catalysts E and H) or both tungsten and fluorine (comparison catalyst F) on hydrogen-form zeolite Y is prepared by a procedure wherein ultra-stable zeolite Y is contacted with ammonium nitrate solution, filtered, dried at 120‹C, calcined at 550‹C, contacted with a solution containing nickel acetate, ammonium metatungstate and, if required, ammonium fluoride, dried at 120‹C, pelleted and calcined at 550‹C; and catalyst comprising palladium on hydrogen-form zeolite Y (comparison catalyst G) is prepared by a procedure wherein ultra-stable zeolite Y is contacted with a solution containing ammonium nitrate and palladium chloride, dried at 120‹C, pelleted and calcined successively at 200‹C, 350‹C and 550‹C. Reference is made to Specification 1,189,934 and also to U.S.A. Specifications 3,130,007 and 3,405,055.