Patent GB-616260-A (GB)
Title: Improvements in and relating to catalysts for polymerisation and condensation of hydrocarbons
IPC: C07C2/00
Filed: 1945-06-19
Abstract: Polymerization or condensation of olefins to form higher boiling hydrocarbons is effected in the presence as catalyst of a substantially normal crystalline phosphate of iron containing ferric oxide combined with 2-3 molar equivalents of phosphorus pentoxide. Preferably the atomic ratio of oxygen to phosphorus is 3 : 1, as in ferric metaphosphate, containing one phosphorus atom for each valency of iron.  The catalysts are prepared from a compound of iron such as an oxide, sulphide or salt of a volatile acid, and an oxygen-containing phosphorus compound comprising orthophosphoric acid or phosphorus pentoxide, by heating at 250-900 DEG  C., preferably 300-400 DEG  C., in the absence of water, in the requisite proportions.  Reaction is preferably effected in a syrupy medium of phosphorus acid.  The X-ray diffraction patterns of the crystalline phosphates are shown.  In examples, catalysts are prepared by heating 100 per cent H3PO4 to 140-150 DEG  C., adding magnetite, raising the temperature to 165 DEG  C., adding "Celite" (R.T.M.), and finally heating at 300-400 DEG  C., giving products containing Fe2O3 and P2O5 combined in ratios of 1 : 3, 1 : 2.5 or 1 : 2 and, when a copper tray is used, 0.65 per cent CuO. Alternatively, 85 per cent H3PO4 is heated with FeCl3.6H2O, first to about 150 DEG  C. to volatilize hydrogen chloride and water, then to 250, and finally 400 DEG  C., or Fe2O3 and P2O5 are heated in molar ratio o 1 : 3.  The Specification as open to inspection under Sect. 91 comprises also the use of crystalline iron phosphates containing at least one molar equivalent of phosphorus pentoxide combined with ferric oxide.  This subject-matter does not appear in the Specification as accepted.ALSO:Polymerization or condensation of olefins to form higher boiling hydrocarbons is effected in the presence as catalyst of a substantially normal crystalline phosphate of iron containing ferric oxide combined with 2-3 molar equivalents of phosphorus pentoxide.  Preferably, the atomic ratio of oxygen to phosphorus is 3 : 1, as in ferric metaphosphate, containing one phosphorus atom for each valency of iron.  The catalysts are prepared from a compound of iron such as an oxide, sulphide or salt of a volatile acid, and an oxygen-containing phosphorus compound comprising orthophosphoric acid or phosphorus pentoxide, by heating at 250-900 DEG , preferably 300-400 DEG  C., in the absence of water, in the requisite proportions.  Reaction is preferably effected in a syrupy medium of phosphorus acid.  The X-ray diffraction patterns of the crystalline phosphates are shown.  Polymerization, condensation and alkylation of aromatics with olefins are effected with the catalysts at about 200-400 DEG , preferably 250-350 DEG  C. and pressures of, say, 100-1000 p.s.i.  Polymerization of C4 olefins or higher may be effected at 150 DEG  C.  In examples, catalysts are prepared by heating 100 per cent H3PO4 to 140-150 DEG  C., adding magnetite, raising the temperature to 165 DEG  C., adding "Celite" (Registered Trade Mark), and finally heating at 300-400 DEG  C., giving products containing F2O3 and P2O5 combined in ratios of 1 : 3, 1 : 2.5 or 1 : 2 and, when a copper tray is used, 0.65 per cent CuO. Alternatively, 85 per cent H3PO4 is heated with FeCl3.6H2O, first to about 150 DEG C. to volatilize hydrogen chloride and water, then to 250 DEG  and finally 400 DEG  C., or Fe2O3 and P2O5 are heated in molar ratio o 1 : 3.  These catalysts are used to alkylate benzene with ethylene at about 300 DEG  C. and 400 p.s.i. or 247 DEG  C. and 900 p.s.i., with recycling of unreacted ethylene; to alkylate benzene with propylene at about 250 DEG  C. and 400 p.s.i.; naphthalene, admixed with cyclohexane, with ethylene at 300 DEG  C. and 900 p.s.i.; and to polymerize propylene at 250 DEG  C. and 400 p.s.i.  The Specification as open to inspection under Sect. 91 comprises also the use of crystalline iron phosphates containing at least one molar equivalent of phosphorus pentoxide combined with ferric oxide.  This subject-matter does not appear in the Specification as accepted.