| 摘要 |
Ethylenically unsaturated hydrocarbon chlorides containing 2 to 4 carbon atoms are produced by reacting a saturated aliphatic hydrocarbon containing 2 to 4 carbon atoms and/or an incompletely chlorinated derivative thereof, an oxygen-containing gas and a chlorinating agent which is chlorine and/or hydrogen chloride in the presence of a catalyst comprising cupric chloride-zinc chloride-potassium chloride on a carrier or support, there being employed 0.4 to 2.4 mols. of oxygen per mol of chlorinating agent and also a mol. ratio of chlorinating agent to hydrocarbon and/or chlorohydrocarbon of 0.3 to 2.0 for chlorine and 0.6 to 4.0 for hydrogen chloride. Several carriers are specified. The catalyst may be used in the form of a fixed or fluidized bed, the preferred temperature range being 325-700 DEG C. In examples, ethane is converted to vinyl chloride. The reaction product of Example 2 additionally contains dichloro-, trichloro- and tetrachloroethylene, dichloromethane, chloroform, carbon tetrachloride, methyl chloride and ethyl chloride. The conversion of propane to allyl chloride is also specified.ALSO:A chlorination catalyst comprises cupric chloride-zinc chloride-potassium chloride on a carrier or support. Specified carriers are silica, alumina, Fuller's earth, kieselguhr, pumice and a calcined diatomaceous earth. The cupric chloride is preferably present in an amount between 8% and 25% by weight of the impregnated carrier. The molar ratio of cupric chloride: potassium chloride: zinc chloride is preferably 0,8-1,5:1:0,8-1,5, more preferably 1:1:1. The catalyst may be prepared by contacting the carrier particles with aqueous solutions of the chloride salts. In Example I a calcined diatomaceous earth is treated with an aqueous solution containing cupric chloride, potassium chloride, zinc chloride and concentrated hydrochloric acid.
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