GB904084A - Production of chlorinated hydrocarbons - Google Patents

Abstract

Chlorinated hydrocarbons are prepared by establishing in a reaction zone or bed containing metal halide oxychlorination catalyst impregnated on a carrier or support in the form of particles, introducing chlorine and/or hydrogen chloride together with an aliphatic C1-4 hydrocarbon and/or partially chlorinated derivative thereof into the lower part of said bed, introducing an oxygen-containing gas into the bed at a level above the level of introduction of the aforesaid reactants; withdrawing products of the resulting reaction from the upper portion of the bed; and maintaining the rate of flow of chlorine and/or hydrogen chloride, oxygen, and hydrocarbon and/or chlorohydrocarbon sufficiently high to suspend the catalyst particles above the level of oxygen introduction. The catalyst particles may be completely fluidised. Up to 25% of the oxygen may be introduced into the bed with the organic reactant and chlorinating agent; the remaining oxygen is fed as indicated above, using one or more feed points. Reaction temperatures are generally 570 - 930 DEG F. The reaction zone may be cooled. Suitable metal halide catalysts are chlorides of Cu, Fe and Cr, alone or in combination with alkali metal or alkaline earth metal chlorides; a preferred catalyst is a copper chloride-zinc chloride-calcium chloride catalyst. Suitable carriers are silica, alumina, fuller's earth, kieselguhr, and pumice. The catalyst particles may be diluted with sand. Examples react ethylene to obtain C2Cl4 and C2HCl3 as the main products, together with CHCl3, C2H2Cl2, C2H3Cl, C2Cl6, C2HCl5, C2H2Cl4 and C2H4Cl2; and CH2Cl.CH2Cl to obtain perchloroethylene, together with C2HCl3 and C2HCl5. Other specified starting materials are methane, ethane, propane, ethylene, and tetrachloroethane.