Patent GB-808456-A (GB)
Title: Process and catalyst for polymerization of polymerizable hydrocarbons
IPC: C08F4/22
Filed: 1956-11-30
Abstract: A catalyst for polymerizing olefines consists of chromium oxide and oxide of phosphorus associated with silica, zirconia, alumina, or thoria as a support.  At least a part of the chromium is present in hexavalent state.  The preferred form of catalyst is made by impregnating a silica/alumina complex consisting mainly of silica, with a solution containing chromic acid and ortho-phosphoric acid. Alternatively the ammonium or hydrazine salts of these acids can be used.  The product is then dried and heated at 900 DEG  to 1100 DEG F. preferably in a current of air or oxygen, but nitrogen may be used.  The silica/alumina may be activated before impregnation by treating with steam and air at 1200 DEG  C., whereby the product is of low surface area and of high pore size.  The catalyst contains 0.1 to 10 per cent of chromium and 0.1 to 4 atoms of phosphorus per chromium atom. Polymerization may be effected in a fixed or fluidized bed of the catalyst at a temperature of 150 DEG  to 450 DEG  F. and under a pressure of 500 p.s.i. or higher, the higher temperature up to 700 DEG  F. favouring production of solid polymer (see Group IV (a)). Preferably the starting material is fed in counter-current to a slowly gravitating bed of the catalyst, with a temperature gradient rising to the middle of the column and falling at the entry and exit. The catalyst is regenerated by washing with solvent and heating with an inert gas and air to burn off carbon deposits.  Specifications 790,195, 790,196 and 804,641 are referred to.ALSO:Olefines are polymerized in the presence of a catalyst consisting of chromium oxide and an oxide of phosphorus associated with silica, zirconia, alumina, or thoria as a support.  At least part of the chromium is present in hexavalent state.  The preferred form of catalyst (see Group III) is made by impregnating a silica/alumina complex containing mainly silica, with a solution containing chromic acid and orthophosphoric acid; the product is then dried and heated at 900 DEG to 1100 DEG  F. preferably in a current of air or oxygen, but nitrogen may be used.  Polymerization may be effected in a fixed or a fluidized bed of the catalyst under pressures up to about 500 p.s.i. and at a temperature of 150 DEG  to 450 DEG  F. or higher, the higher temperature up to 700 DEG  F. favouring production of solid polymers. Preferably the starting material is fed in counter-current with a slowly gravitating bed of the catalyst, with a temperature gradient rising towards the middle of the column and falling towards the entry and exit.  Temperature of the reaction is controlled by regulating the temperature of the feed both of reactant and catalyst.  By this means fresh reactant meets used catalyst, and after reaching the zone of maximum temperature the polymer is treated with more active catalyst but at a lower temperature, thus avoiding excessive reaction, and producing a heavier polymer.  Olefines treated are preferably 1-olefines not exceeding 8 C atoms, and no branching nearer the double bond than 4-position, except in the case of conjugated diolefines where alkyl and Cl radicals may be in 3-position. Ethylene, butadiene and isoprene are specified, and also mixtures of olefines, e.g. ethylene/1-butene, and propylene/pentene. Diluents may be used, e.g. specified paraffins and cyclo-paraffins, the heavier paraffins being preferred. Aromatics are less desirable. The polymers may be fractionated by the use of distillation and/or solvents and give products which may be used either as films, e.g. for wrapping foods, drugs and chemicals, or for coating paper. Specifications 790,195, 790,196 and 804,641 are referred to.