Patent GB-981094-A (GB)
Title: Hydrocarbon colversion process and catalyst
IPC: C10G35/095
Filed: 1960-12-19
Abstract: A zeolitic metal alumino-silicate molecular sieve catalyst having at least 40% of the aluminium oxide tetrahedra satisfied by polyvalent metal cations, e.g. Mg, Ca, Sr, Zn, Mn, Ce, or Al, a crystalline structure, a SiO2 to Al2O3 molar ratio greater than 3, has at least 0.05, preferably 0.2 to 0.6 weight per cent of a metal of Group VIII of the Periodic Table, preferably platinum or palladium dispersed in elemental form either within or on and within the molecular sieve. The catalyst may be prepared by impregnating the zeolite exchanged with polyvalent metal cations to the requisite degree, with an aqueous solution of a suitable Group VIII metal compound followed by drying and thermal or chemical decomposition of the metal compound, by cation exchange using an aqueous solution of a suitable metal salt followed by chemical reduction of the cation; or by cation exchange using an aqueous solution of a metal compound in which the metal is in the cationic state with co-ordination complexing agents followed by thermal or chemical decomposition of the cationic complex. Decomposition of the metal compound may be effected by heating preferably to above 400 DEG  C.  When the metal is iron, cobalt or nickel it is preferred to conduct this operation in a reducing atmosphere such as is provided by hydrogen, methane or carbon monoxide.  The zeolite may be activated by heating slowly in air at 300-600 DEG  C. and then cooling.  The zeolite should then be heated slowly to 500 DEG  C. from room temperature in a stream of hydrogen at atmospheric pressure. The resulting zeolite is used as a hydrocarbon conversion catalyst. The preferred zeolites are zeolite "Y" (see Specification 909,266) and zeolite "L" (see Specification 909,264).  The degree of polyvalent cation substitution may be 75% or more and further alkali metal cations may be removed by ion exchange with ammonium or alkyl substituted ammonium cations which may then be driven off during reactivation treatment to provide active additional sites in the structure, this process being designated decationization (see Specification 980,502). According to a typical example, a sodium zeolite Y after slurrying in water and filtering was contacted with a calcium chloride solution to effect calcium exchange and thereafter washed, dried and contacted with a solution of tetrammineplatinum chloride.  The zeolite was then filtered, washed and dried, granulated and finally tableted before activating by heating in air at 350 or 510 DEG  C. Specifications 777,233, 788,588 and 972,831 also are referred to.  Reference has been directed by the Comptroller to Specifications 937,748, 937,749 and 937,750.ALSO:Reforming and isomerization of paraffinic hydrocarbons is effected in the presence of a zeolitic molecular sieve (see Division C1) in which at least 40% of the aluminium oxide tetrahedra are satisfied by the presence of polyvalent metal cations for example Mg, Ca, Sr, Zn, Mn, Ce or Al, and which has a crystalline structure, a silicon dioxide to alumina trioxide ratio greater than 3 and bears either on and within or within its pores at least 0.05 weight per cent of a metal of Group VIII of the Periodic Table in elemental form, preferably platinum or palladium.  The zeolites specified zeolite "Y" (see Specification 909,266) and zeolite "L" (see Specification 909,264).  The hydrocarbon conversion is effected under conditions which include a space velocity of 1-10 grams of feed per gram catalyst per hour and a hydrogen to hydrocarbon molar ratio of from 0.5-1 to 10-1. Temperatures of 300-425 DEG  C. are preferably employed.  Pressures should be from 7.8-69 atmospheres absolute. Specifications 777,233, 788,588, 972,831 and 980,502 also are referred to.  Reference has been directed by the Comptroller to Specifications 937,748, 937,749 and 937,750.ALSO:A zeolitic metal alumino silicate molecular sieve catalyst having at least 40% of the aluminium oxide tetrahedra satisfied by polyvalent metal cations, e.g. Mg, Ca, Sr, Zn, Mn, Ce, or Al, a crystalline structure, a SiO2 to Al2O3 molar ratio greater than 3, has at least 0,05, preferably 0,2-0,6 weight per cent of a metal or Group VIII of the Periodic Table, preferably platinum or palladium dispersed in elemental form either within or on and within the molecular sieve.  The catalyst may be prepared by impregnating the zeolite exchanged to the requisite degree with polyvalent metal cations, with an aqueous solution of a suitable Group VII metal compound followed by drying and thermal or chemical decomposition of the metal compound; by cation exchange using an aqueous solution of a suitable metal salt followed by chemical reduction of the cation; or by cation exchange using an aqueous solution of a metal compound in which the metal is in the cationic state with co-ordination complexing agents followed by thermal or chemical decomposition of the cationic complex.  Decomposition of the metal compound may be effected by heating preferably to above 400  DEG C.  When the metal is iron, cobalt or nickel, it is preferred to conduct this operation in a reducing atmosphere such as is provided by hydrogen, methane or carbon monoxide.  The zeolite may be activated by heating slowly in air at 300-600  DEG C. and then cooling.  The zeolite should then be heated slowly to 500  DEG C. from room temperature in a stream of hydrogen at atmospheric pressure.  The resulting zeolite is used as a hydrocarbon conversion catalyst.  The said zeolites are zeolite "Y" (see Specification 909,266) and zeolite "L" (see Specification 909,264).  The degree of polyvalent cation substitution may be 75% or more and further alkali metal cations may be removed by ion exchange with ammonium or alkyl substituted ammonium cations which may then be driven off during reactivation treatment to provide active additional sites in the structure, this process being designated decationization (see Specification 980,502).  According to a typical example, a sodium zeolite Y after slurrying in water and filtering was contacted with a calcium chloride solution to effect calcium exchange and thereafter washed, dried and contacted with a solution of tetrammineplatinum chloride.  The zeolite was then filtered, washed and dried, granulated and finally tableted before activating by heating in air at 350 or 510  DEG C.  Specifications 777,233, 788,588 and 972,831 also are referred to.  Reference has been directed by the Comptroller to Specifications 937,748, 937,749 and 937,750.