Patent GB-981697-A (GB)
Title: Production of hydrocarbons
IPC: C07C1/30
Filed: 1962-05-15
Abstract: In a process for preparing olefins (see Division C5), a halogen substituted paraffin is passed with an olefinically unsaturated hydrocarbon over a halogenated catalyst under conditions such that constituent parts of the halogen substituted paraffin undergo addition across the olefinic bond.  Specified olefinic feedstocks are ethylene, propylene, n or iso butenes and halogen substituted paraffins used include chloroform, carbon tetrachloride trichloropropane, and tertiary butyl chloride.  The process is carried out at - 30 DEG  to + 350 DEG  C. preferably in the gaseous or liquid phase in presence of nitrogen as an inert carrier gas and at sub-normal and superatmospheric pressures.  In the example, ethylene is bubbled into tertiary butyl chloride while refluxing for two hours in presence of a chlorinated-alumina catalyst to produce (CH3)3 CCH2CH2Cl.  Specifications 953,187 and 981,691 are referred to.  Reference has been directed by the Comptroller to Specification 921,796.ALSO:Olefins are prepared by passing a halogen-substituted paraffin with an olefinically unsaturated hydrocabon over a first halogenated catalyst under conditions such that constituent parts of the halogen-substituted paraffin undergo addition across the olefinic bond of said olefinically unsaturated compound, and thereafter passing the product or a fraction thereof over a second halogenated catalyst under conditions such that dehydrohalogenation takes place, whereby a homologue of the feedstock olefinically unsaturated compound is formed, said first and second halogenated catalysts being the same or different and each being obtained by contacting a halogenatable inorganic oxide with a compound containing the group =C(Ha)(Ha1), wherein Ha and Ha1 are halogen atoms which may be the same or different.  The halogenatable inorganic oxides are preferably refractory oxides of Group III, IV, V and VIII elements and the halogen containing compounds specified have the general formula (X)(Y)CCl2, wherein X and Y may be the same or different and are H, Cl, Br, F or SCl and together may be O or S; specified examples are carbon tetrachloride, chloroform and methylene chloride.  Specified refractory oxides are alumina, borin, silica, titania, zirconia or ferric oxide.  Specified olefinic feedstocks are ethylene, propylene, n or iso butenes and halogen-substituted paraffins used include chloroform, carbon tetrachloride, trichloropropane and tertiary butyl chloride.  The process is carried out at -30 DEG  to +350 DEG  C., preferably in the gaseous or liquid phase in the presence of nitrogen as an inert carrier gas and at sub, normal or super atmospheric pressures. The catalyst material used has a surface area of 250 sq. metres per gram and is pretreated before halogenation with an alkali metal compound or alkaline earth metal compound so that 0.01 to 10% by weight of the alkaline earth compound is retained.  The halogenation of the pretreated catalyst is described in Specification 953,187 and 981,691, the uptake of halogen being 1 to 15% by weight based on the weight of the oxide.  In the example, ethylene is bubbled into tertiary butyl chloride in which chlorinated-alumina catalyst is suspended and the reaction mixture refluxed for two hours.  The product is passed in a nitrogen stream over the chlorinated-alumina catalyst at 316 DEG  C. and the reaction product contained 15 to 20% by weight of C6 olefins.  Reference has been directed by the Comptroller to Specification 921,796.