Patent GB-993194-A (GB)
Title: Hydrogenative cracking of hydrocarbon oils
IPC: B01J23/38
Filed: 1963-04-29
Abstract: In the hydrogenative cracking of a hydrocarbon oil by contacting the oil at an elevated temperature and pressure with hydrogen, the catalyst used comprises at least one metal of Group Ib and at least one metal of the palladium group intimately associated with an acid-acting support comprising from 50% to 90% by weight of silicon and 50% to 10% by weight of alumina.  The alumina may be partially replaced by zirconia, titania borin or magnesia. Specified metals of Group Ib are silver and copper and the palladium group of metals consist of rhodium, ruthenium and palladium. The catalysts may be prepared by (1) impregnating the support in pellet or extrudate form with a solution or solutions of the metals followed by drying and calcining; (2) incorporating the salts into the refractory oxide as the hydrogel is formed by precipitation; (3) contacting the wet hydrogel, which has preferably been freed from alkali metal ions by ammonium hydroxide solution, with a solution of the salts of the metals and (4).  Combinations of methods (1) to (3) e.g. by co-precipitating rhodium with the silica-alumina hydrogel and then adding silver by ion exchange into the hydrogel.  Alternatively rhodium may be added by impregnation of an ion exchanged silver catalyst.  The catalyst preferably contains 0.1% to 20% by weight of the Group Ib metal and 0.01% to 2% by weight of the palladium group metal. The catalyst may also contain 0.1% to 5.0% by weight of fluorine in the hydrogel support.  The hydrocarbon oil may be given a pretreatment to reduce the nitrogen content to less than 30 p.p.m. and hydrogenation takes place at 260 DEG  to 454 DEG  C., 35 to 210 atmospheres gauge pressure, a L.H.S.V. of 0.1 to 10 and a hydrogen to oil mol. ratio in the range 5:1 to 50:1.  The feed may also contain recycle feed.ALSO:A cracking catalyst comprises at least one metal of Group Ib and at least one metal of the palladium group intimately associated with an acid acting support comprising from 50-90% by weight of silica and 50-10% by weight of alumina.  The alumina may be partially replaced by zirconia, titania boria or magnesia. Specified metals of Group Ib are silver and copper and the palladium groups metals are rhodium, ruthenium and palladium.  The catalysts may be prepared by (1) impregnating the support in pellet or extrudate form with a solution or solutions of the metals followed by drying and calcining, (2) incorporating the salts into the refractory oxide as the hydrogel is formed by precipitation, (3) contacting the wet hydrogel, which has preferably been freed from alkali-metal ions by ammonium hydroxide solution, with a solution of the salts of the metals, and (4) combinations of method (1) to (3), e.g. by co-precipitating rhodium with the silica-alumina hydrogel and then adding silver by ion exchange into the hydrogel.  Alternatively, rhodium may be added by impregnation of an ion exchanged silver catalyst.  The catalyst preferably contains by weight 0,-20% of the Group Ib metal and 0,01-2,0% of the palladium group metal.  The catalyst may also contain 0,1-5,0% by weight of fluorine.