Patent GB-1079106-A (GB)
Title: Synthetic crystalline zeolites
IPC: C01B39/02
Filed: 1964-10-02
Abstract: Synthetic crystalline, alkali metal alumino silicate zeolites having 1 to 20% of water-insoluble inorganic oxides held within their crystal structures (see Division C1) are used, after cation exchange with metal or hydrogen-containing cations, as catalysts in hydrocarbon conversion processes, e.g. in catalytic cracking, hydrocracking.  The inorganic oxides may be oxides of rare earth metals and of elements in Groups II and IV of the Periodic Table, e.g. magnesium, calcium, silicon, beryllium, cerium, lanthanum, zinc, aluminium, boron, lithium. The exchange metal cation may be a metal from Groups I to VIII or a rare earth metal and is preferably magnesium, calcium.  The ion exchanged zeolites can be impregnated with a hydrogenating metal, e.g. palladium, platinum, rhodium, or molybdenum, chromium, vanadium, cobalt, nickel, copper, silver, manganese. The catalysts may be embedded in an amorphous material such as silica gel, or cogel of silica and at least one other metal oxide wherein the metal is selected from Groups 11a, IIIa, IVb, e.g. alumina, titania, magnesia. The catalysts may be used in fluidized and moving bed processes.  In Example 10, a sodium alumino-silicate zeolite containing magnesium oxide is base exchanged with magnesium sulphate to reduce the sodium content and is admixed with a silica hydrogel and pelleted to form a cracking catalyst in a fixed bed catalytic cracking process.  In Example 11, sodium alumino-silicate zeolite containing magnesium oxide is base exchanged with ammonium chloride to reduce the sodium content, impregnated with an ammoniacal palladium chloride complex solution, heat treated and pelleted and used as a catalyst in hydrocracking a cycle oil.ALSO:A process for preparing a synthetic crystalline alumino silicate zeolite product comprises crystallizing the zeolite from an aqueous reaction mixture of a solution or sol of alkali metal oxides, silica and alumina, in which reaction mixture there is included a substantially water-insoluble inorganic oxide, said oxide being included in the reaction mixture at any time before the time that crystallization of the zeolite is initiated in the form of discrete oxide particles sufficiently finely divided to be held within the crystal structure of the resulting zeolite and in amount of from 1 to 20% by weight, and recovering the crystalline alumino silicate zeolite containing the substantially water insoluble inorganic oxide held within its crystal structure.  The zeolite may have the faujasite, mordenite or "Zeolite A" structure. The inorganic oxides may be oxides of rare earth metals, and oxides of elements in Groups II and IV of the Periodic Table, e.g. magnesium, calcium, silicon, beryllium, cerium, lanthanum, zinc, aluminium, boron, lithium.  Combinations of metal oxides can be used.  The zeolites may be crystallized at 180 DEG  to 250 DEG  F. and the product crystals, after separation from the mother liquor and washing, may be activated by heating to, say, 300 DEG  to 450 DEG  C.  The products may be cation-exchanged with metal or hydrogen-containing cations to reduce their alkali metal oxide content to less than 10% and used as catalytic materials in hydrocarbon conversion processes, e.g. in catalytic cracking, hydrocracking, and used in gas drying.  The exchange metal cation can be a metal from Groups I to VIII and rare earth metals and is preferably magnesium or calcium.  The ion-exchanged zeolites can be impregnated with a hydrogenating metal, e.g. palladium, platinum, rhodium or with molybdenum, chromium, vanadium, cobalt, nickel, copper, silver or manganese. The zeolitic catalysts may be used in the above described form or embedded in an amorphous material such as silica gel, or cogel of silica and at least one other metal oxide wherein the metal is selected from Groups IIa, IIIa, IVb, e.g. alumina, titania, magnesia.  The composite materials may be used in fluidized and moving bed operations.ALSO:Synthetic crystalline, alkali metal alumino silicate zeolites having 1 to 20% of water insoluble inorganic oxides held within their crystal structures (see Division C1) are used, after cation exchange with metal or hydrogen-containing cations, as catalysts in hydrocarbon conversion processes e.g. in catalytic cracking, hydrocracking.  The inorganic oxides may be oxides of rare earth metals and of elements in Grougs II and IV of the Periodic Table e.g. magnesium, calcium, silicon, beryllium, cerium, lanthanum, zinc, aluminium, boron, lithium.  The exchange metal cation may be a metal from Groups I to VIII or a rare earth metal and is preferably magnesium, calcium.  The ion exchanged zeolites can be impregnated with a hydrogenating metal e.g. palladium, platinum, rhodium, or molybdenum, chromium, vanadium, cobalt, nickel, copper, silver, manganese.  The catalysts may be embedded in an amorphous material such as silica gel, or cogel of silica and at least one other metal oxide wherein the metal is selected from Groups IIA, IIIA, IVB e.g. alumina, titania, magnesia. The catalysts may be used in fluidized and moving bed processes.  In Example 10, a sodium alumino-silicate zeolite containing magnesium oxide is base exchanged with magnesium sulphate to reduce the sodium content and is admixed with a silica hydrogel and pelleted to form a cracking catalyst in a fixed bed catalytic cracking process.  In Example 11 sodium alumino-silicate zeolite containing magnesium oxide is base exchanged with ammonium chloride to reduce the sodium content, impregnated with an ammonical palladium chloride complex solution, heat treated and pelleted and used as a catalyst in hydrocracking a cycle oil.