Patent GB-664959-A (GB)
Title: Process for the production of methallyl halides and the methallyl halides so produced
IPC: C07C17/10
Filed: 1949-05-27
Abstract: A methallyl halide is produced by a process comprising halogenating a tertiary butyl halide by reaction with a halogen at a temperature above 300 DEG  C. to form methallyl halide and hydrogen halide, contacting the resulting mixture with isobutylene or a hydrocarbon mixture containing the same, whereby the isobutylene <FORM:0664959/IV (b)/1> combines with the hydrogen halide to form a tertiary butyl halide, removing the tertiary butyl halide from the reaction mixture and recycling it to the halogenation step and recovering the methallyl halide.  Suitable mixtures of hydrocarbons containing isobutylene which may be employed as starting materials include those obtained by a pyrolytic treatment or cracking of natural gas, petroleum, p  petroleum products, coal tar, pitches, peat, shale oil or related carbonaceous materials, though the separation of such mixtures into fractions containing hydrocarbons of approximately the same number of carbon atoms is often advisable, the C4 fraction being used as starting material for the present process.  The C4 fractions containing isobutylene from the products of petroleum cracking may be used.  The fractions used usually contain other hydrocarbons, e.g. 1-butene, n-butane, isobutane, 1 : 3-butadiene, cis-2-butene and trans-2-butene.  Any halogen may be used in the halogenation, but chlorine is preferred, and examples of methallyl halides which may be produced are the chloride, bromide and iodide.  The halogenation is carried out in the vapour phase and vaporization and preheating of the tertiary-butyl halide are advisable before mixing it with the halogen.  An excess of tertiary butyl halide should be maintained. High velocity and turbulent flow are advisable to ensure thorough mixing of the reactants before they enter the reaction chamber, the halogen being admitted as the side stream.  Normal, raised or reduced pressure may be used.  The effluent from the halogenation process, preferably after cooling and substantial condensation by e.g. refrigeration or internal cooling agents, is mixed with the isobutylene or the hydrocarbon mixture containing the same, which may be gaseous but is preferably liquid.  Preferably the hydrogen halide should be in excess.  The isobutylene, or mixture containing it and the reaction products from the halogenation may be separately fed to the hydrohalogenation reaction.  Tertiary butylhalide is produced. The heat of reaction is absorbed by the reactor contents or cooling coils may be provided.  The hydrohalogenation may take place over a wide range of temperature provided the reaction medium is maintained in the liquid phase and sufficient pressure should be employed to ensure that the reaction mixture is substantially liquid.  Catalysts, promotors and inhibitors may be employed but are not normally necessary.  The products of the hydrohalogenation, consisting of methallyl halide, tertiary butyl halide and the residual hydrocarbons if the isobutylene is introduced in admixture with other hydrocarbons, excess hydrogen halide and small amounts of higher halogenated materials are preferably separated by a series of fractionations, the tertiary butyl halide being recycled to the halogenation step.  Batchwise, continuous or semi-continuous operation are envisaged.  Referring to the drawing, tertiary butyl chloride, preferably obtained from a previous operation of the process of the invention is preheated in a furnace, mixed with chlorine from line 2 and passed through conduit 3 to reactor A, constructed, e.g. of mild steel, the reaction products are cooled at scrubber B, compressed at C and further cooled at D and mixed with a stream of the butane-isobutylene mixture from conduit 4 and led to a cooled reactor E.  The products are separated in three successive fractionating towers F, G and H, hydrogen chloride being taken off at F, residual hydrocarbons in G, methallyl chloride and tertiary butyl chloride in H, the latter being recycled to the halogenation step. Residual hydrocarbons removed in G may, after further purification be used in alkylation processes.  Methallyl chloride is obtained using apparatus similar to that described above in examples (1) when tertiary butyl chloride is chlorinated, the cooled products are mixed with liquid isobutylene and the reaction products are fractionated; (2) when a liquid C4 hydrocarbon mixture containing isobutylene is employed instead of isobutylene in a similar process to (1) and in example (3) tertiary butyl bromide and bromine are employed in a process similar to that of example (2) when methallyl bromide is produced.  The tertiary butyl chloride or bromide is recycled to the halogenation step.