Abstract: A process for recovering substantially dry methyl chloride from a stream of wet methyl chloride by distilling the wet methyl chloride in the presence of at least 10 molar % hydrogen chloride based on the hydrogen chloride, methyl chloride and water being distilled. The distillation is carried out under super atmospheric pressure and a temperature to produce an aqueous hydrochloric acid of less than 36 wt %, and preferably under such super atmospheric pressure and sufficient temperature to produce an azeotropic hydrochloric acid containing a low concentration of hydrogen chloride. Increasing pressures allows increasing temperatures in the bottoms which form azeotropes of lower concentration hydrochloric acid. The resulting overhead of such a distillation, methyl chloride-hydrogen chloride, will contain less than about 400 molar ppm water. When the distillation is carried out in the presence of about 12 to 25 molar % hydrogen chloride, the overhead will contain between about 100 to 400 molar ppm water.

Abstract: A method for producing alkyl halides by reacting the corresponding alkanol with at least 10% molar excess of hydrogen halide at a temperature of at least 50.degree.C. and under sufficient pressure to maintain the reactants dissolved in the liquid water of reaction (but insufficiently high to maintain the alkyl halide reaction product in the aqueous reaction mixture). The heat of reaction causes the alkyl halide to vaporize from the reaction zone along with the excess hydrogen halide. The resulting vapors are delivered to a packed tower where they are contacted with a stream of liquid reflux alkyl halide saturated with the hydrogen halide. The liquid reflux stream is obtained by condensing a portion of the gaseous or vaporous effluent from the tower. The gases or vapors from the reactor are dried by the reflux. In addition to drying the alkyl halide vapors, the tower provides an environment in which the by-product ether of the alkanol hydrochlorination is disassociated into alkyl halide and water.