| 摘要 |
1381620 1,2,2,3-Tetrachloropropane and 1,1,2,3-tetrachloropropene MONSANTO CO 15 Dec 1972 [27 Dec 1971] 31416/74 Heading C2C The invention comprises a process for the production of 1,2,2,3-tetraohloropropane and 1,1,2,3 - tetrachloropropene which comprises feeding a stream comprising 1,2,3-trichloropropane to a liquid-phase chlorinator, chlorinating the feed stream so that from 20 to 60% by weight of the chlorinator effluent remains as unreacted 1,2,3-trichloropropane, passing the chlorinator effluent to a fractionating column, fractionating said chlorinator effluent into a 1,2,3-trichloropropane fraction, a 1,2,2,3-tetrachloropropane fraction, a 1,1,2,3-tetrachloropropane fraction, a 1,1,1,2,3- and 1,1,2,2,3-pentachloropropanes fraction, and a 1,1,2,3,3-pentachloropropane and heavy ends fractions, recycling the 1,2,3-trichloropropane fraction to the chlorinator, removing the 1,2,2,3-tetrachloropropane fraction, passing the 1,1,2,3-tetrachloropropane fraction from the fractionating column to a caustic dehydrochlorinator, dehydrochlorinating the 1,1,2,3-tetrachloropropane, passing the dehydrochlorinator effluent which comprises mixed 1,1,3-, 1,2,3- and 2,3,3-trichloropropenes to a second liquid-phase chlorinator, adding chlorine to the carbon/carbon double bond of the trichloropropenes contained in the dehydrochlorinator effluent, passing the second chlorinator effluent which comprises 1,1,1,2,3- and 1,1,2,2,3-pentachloropropane to a second caustic dehydrochlorinator, passing the 1,1,1,2,3- and 1,1,2,2,3-pentachloropropanes fraction from the fractionating column to the second caustic dehydrochlorinator, dehydrochlorinating the second chlorinator effluent and the 1,1,1,2,3- and 1,1,2,2,3-pentachloropropanes fraction from the fractionating column, passing the second dehydrochlorinator effluent which comprises mixed 1,1,2,3- and 2,3,3,3-tetrachloropropenes to an isomerizer packed with siliceous granules having a polar surface, and isomerizing 2,3,3,3- tetrachloropropene to 1,1,2,3-tetrachloropropene by heating the second dehydrochlorinator effluent in contact with the siliceous granules at 150‹ to 200‹ C. for 0À4 to 2 hours. The chlorinations are preferably conducted in the presence of actinic light in the presence of a free-radical forming catalyst such as azobisisobutyronitrile. Preferably 30 to 50% of the feed is chlorinated. The isomerization catalyst is advantageously clay granules, e.g. attapulgite. |
