Patent GB-559080-A (GB)
Title: Process for halogenation of unsaturated aliphatic or alicyclic compounds
IPC: C07C17/02
Filed: 1942-06-08
Abstract: 559,080. Catalytic agents; alumina. SHELL DEVELOPMENT CO. June 8, 1942, No. 7784. Convention date, June 9, 1941. [Classes 1 (i) and 1 (iii)] [Also in Group IV] Finely-divided chloride or bromide of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, molybdenum, tungsten or uranium having a valency greater than the minimum is reacted, in the form of a suspension, with the vapour of an unsaturated aliphatic or cycloaliphatic compound, whereby the latter is chlorinated or brominated. The process may be made continuous by separating the halogenating agent, regenerating it by bringing it into contact with a mixture of hydrogen halide and oxygen and returning it to the reaction zone. The metal halides may be supported upon carriers such as asbestos, pumice, clay, alumina or aluminium silicates. Activated aluminas comprising gamma alumina and α-alumina monohydrate prepared from the aluminium hydrate precipitated from aqueous sodium aluminate may also be used as a carrier. In the Figure butylene is introduced together with a diluent into a mixer 12, which receives finely-divided cupric chloride through line 13. The resulting mixture is then passed to the reactor 18, the gases and/or solids being first raised to the necessary temperature. The products are separated in the cyclone separators 26, 27, the gases, comprising dichlorbutane, leaving by line 32, and the reduced halide by lines 29, 30. The halide, after leaving a container 31 is mixed with oxygen and hydrogen chloride in a mixer 37 and passes to a reactivator 40. The treated halide passes to a cooler 42, and then to separators 44, 48. The gases pass out through line 50 and the regenerated halide is collected in container 46. and supplies the mixer 12. When necessary, further oxidation of the halide may be effected by passing it through line 53, and mixer 55 to the reactivator 40. Apparatus is also shown which is suitable for intermittent operation. It comprises a heated vertical tube having a funnelshaped hopper at the top provided with a filter or cyclone separate at its mouth. The unsaturated compound and the heated halide pass into the bottom of the tube, the gases and vapours entering at sufficient velocity to maintain the halide in suspension. Periodically, halogenation is stopped and the halide is oxidized by passing a stream of hydrogenhalide and oxygen through the tube. It is however possible to pass continuously a mixture of unsaturated compounds, hydrogenhalide and oxygen into contact with the halide to effect simultaneous halogenation and regeneration. In examples, butylene is chlorinated by means of an activated alumina impregnated with cupric chloride, and in some of the examples with sodium chloride. The process is conducted in four stages: (1) oxidation with steam, air and hydrogen chloride; (2) flushing with air and steam to remove hydrogenchloride; (3) chlorination of the butylene; (4) recovery of products using steam. The starting materials mentioned include: ethylene, pentene, 1-methylbutene-2, hexene-1, 3:3-dimethylbutene-1, 4- methyl pentene-2, octene-1, cyclopentene, 3- methylcyclohexene, butadiene-1:3, hexadiene, acetylene, propayne, hexyne, vinylhalides, allylhalides, 2-halogen propylene, isocrotyl halide, methallylhalides, monohalogenatedacetylene, proparzylhalide, 1: 1-dihalogenethylene, 3-halogencyclohexene, and 3 - halogenpentadiene - 1 : 4. Bromine, iodine and fluorine derivatives are mentioned.