Patent GB-1189930-A (GB)
Title: Process for the Preparation of a Catalyst Suitable for the Conversion of Hydrocarbons
Inventor: CLEMENT CLAUDE
IPC: C10G47/16
Filed: 1968-12-03
Abstract: 1,189,930. Catalyst composition for hydrocarbon conversion processes. SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N.V. 3 Dec., 1968 [5 Dec., 1967], 'No. 57368/68. Heading B1E. [Also in Division C5] A catalyst composition for use in hydrocarbon conversion processes is prepared by a process which includes the steps of: (a) forming a catalyst support by mixing mordenite in the hydrogen form with a cracking catalyst comprising silica and alumina or with a precursor for such cracking catalyst, (b) impregnating the catalyst support with a solution comprising a compound of fluorine, (c) drying the fluorine-impregnated catalyst support, for example at a temperature of between 20‹C and 200‹C., preferably of between 110‹C and 130‹C., (d) forming a catalyst precursor by treating the dried fluorine-impregnated catalyst support with a solution which comprises at least one compound of at least one of the metals of Groups IIB, IIIA, VIA, VIIA and VIII of the Periodic Table of Elements according to Mendeleoff, (e) drying the catalyst precursor, for example at a temperature of between 100‹C and 200‹C, preferably of between 110‹C and 130‹, and (f) calcining the dried catalyst precursor, for example at a temperature of between 550‹C and 750‹C. Prior to mixing with the cracking catalyst or precursor therefor, the mordenite is converted to the hydrogen form, if not already in such form, by treatment to replace the sodium ions thereof by hydrogen ions or by ions which readily will convert to hydrogen ions, for example ammonium ions. To effect such ion exchange, the mordenite may be treated with an acid, for example phosphoric acid, sulphuric acid, nitric acid or hydrochloric acid, or with an ammonium compound, i.e. a compound (organic or mineral) or mixture capable of forming ammonium ions, examples of such compounds being given in the Specification, the mordenite may be treated, in succession and in either order, both with an acid and with an ammonium compound. If desired, such treatment or treatments may be repeated; the or each treatment may be followed by drying or calcining. Alternatively, the mordenite may be treated with another substance containing exchangeable hydrogen ions, for example a carboxy polyester or an ion exchange material. The mordenite may be natural mordenite but preferably is synthetic mordenite. The mordenite and cracking catalyst are mixed preferably at a temperature of between 20‹C and 300‹C and preferably in the presence of water, for example a volume of water which is at least equal to the total pore volume of the mordenite and cracking catalyst. The catalyst support preferably contains 5 to 50 weight per cent mordenite and from 95 to 50 weight per cent cracking catalyst; the cracking catalyst preferably contains from 50 to 90 weight per cent silica and from 50 to 10 weight per cent alumina. The precursor for the cracking catalyst may be a hydrogel of hydrated silica and alumina, the catalyst support being formed by preparing a mixture of mordenite and hydrogel and drying the mixture to convert the hydrogel to the cracking catalyst; the mixture of mordenite and hydrogel may be prepared by precipitating the hydrogel in the presence of mordenite, excess water thereafter being removed from the mixture. The solution comprising a compound of fluorine may be an aqueous solution of hydrogen fluoride, for example a solution comprising from 1 to 10 weight per cent hydrogen fluoride, or an aqueous solution of acid ammonium bifluoride (HF.NH 4 F). Impregnation of the catalyst support preferably in such as to deposit from 1 to 10 weight per cent fluorine thereon. Treatment of the impregnated catalyst support with the solution which comprises at least one compound of at least one of the aforesaid metals preferably in such as to deposit from 1 to 5 weight per cent, based on the dry catalyst composition, of metal(s) on the catalyst support; the treatment may be either an impregnation treatment or an ion exchange treatment which is effected at a temperature preferably of between 10‹C and 100‹C, for example at ambient temperature, and which may be followed by washing to remove excess solution. As exemplified, the metal deposited is nickel and the solution is an aqueous solution comprising either nickel nitrate and ammonium hydroxide or nickel nitrate alone. The catalyst composition may be used, for example in the form of extruded 3 mm x 3 mm tablets, in the hydrogenative cracking of at least one hydrocarbon in the presence of hydrogen and at elevated temperature and elevated pressure.