Oxidative halogenation of C1 hydrocarbons to halogenated C1 hydrocarbons and integrated processes related thereto

A process of oxidatively monohalogenating methane to form methyl chloride or methyl bromide, the process comprising contacting methane with hydrogen chloride or hydrogen bromide, and oxygen in the presence of a catalyst at a temperature greater than about 300° C. and less than about 500° C. such that methyl chloride or methyl bromide is formed, the catalyst comprising a rare earth halide or rare earth oxyhalide compound that is essentially free of iron and copper, with the proviso that when cerium is present in the catalyst, then at least one rare earth element is also present in the catalyst.

A process of preparing methyl alcohol comprising (a) contacting methane with a source of halogen, and optionally, a source of oxygen in the presence of a catalyst under oxidative monohalogenation process conditions sufficient to prepare methyl halide, the catalyst comprising a rare earth halide or rare earth oxyhalide essentially free of iron and copper, with the proviso that when the catalyst contains cerium, the catalyst also contains at least one other rare earth element;

• and thereafter (b) contacting the methyl halide thus prepared with water in the presence of a hydrolysis catalyst under conditions sufficient to prepare methyl alcohol and co-product hydrogen halide;
• and optionally (c) recycling the co-product hydrogen halide to the oxidative halogenation process step (a).

A process of condensing methyl halide to form light olefins and/or gasolines comprising (a) contacting methane with a source of halogen, and optionally, a source of oxygen in the presence of a catalyst under oxidative halogenation process conditions sufficient to prepare methyl halide and, optionally, dihalomethane, the catalyst comprising a rare earth halide or rare earth oxyhalide being essentially free of iron and copper, with the proviso that when the catalyst contains cerium, the catalyst also contains at least one other rare earth element;

• and thereafter (b) contacting the methyl halide and, optionally, dihalomethane thus prepared with a condensation catalyst under conditions sufficient to prepare at least one light olefin, at least one C5+ gasoline, or a combination thereof;
• and (c) optionally recycling the co-product hydrogen halide to the oxidative halogenation step (a).

A process of preparing vinyl halide monomer comprising (a) contacting methane with a first source of halogen, and optionally, a first source of oxygen in the presence of a first oxidative halogenation catalyst under process conditions sufficient to prepare methyl halide and, optionally, dihalomethane, the catalyst comprising a rare earth halide or rare earth oxyhalide being essentially free of iron and copper, with the proviso that when the catalyst contains cerium, the catalyst also contains at least one other rare earth element;

• (b) contacting the methyl halide and, optionally, dihalomethane thus prepared with a condensation catalyst under condensation conditions sufficient to prepare ethylene and co-product hydrogen halide;
• (c) contacting ethylene with a second source of halogen, and optionally, a second source of oxygen in the presence of a second oxidative halogenation catalyst under oxidative halogenation process conditions, and optional thermal cracking conditions, sufficient to prepare vinyl halide monomer;
• and optionally (d) recycling the co-product hydrogen halide to process steps (a) and/or (c).

The process of claim 56 wherein the mixture of methyl halide and vinyl halide are separated;

• vinyl halide is collected as a product;
• and the methyl halide is recycled to step (b) to produce ethylene.

A process of preparing acetic acid comprising (a) contacting methane with a source of halogen and, optionally, a source of oxygen in the presence of a an oxidative halogenation catalyst under oxidative halogenation process conditions sufficient to prepare methyl halide, (b) contacting the methyl halide thus produced with a source of carbonyl in the presence of a carbonylation catalyst under carbonylation process conditions sufficient to prepared acetyl halide;

• and thereafter (c) hydrolyzing the acetyl halide thus produced to yield acetic acid.

The process of claim 58 wherein the oxidative halogenation catalyst is a rare earth halide or rare earth oxyhalide, being essentially free of copper and iron, and with the proviso that when cerium is present in the catalyst, at least one other rare earth element is also present in the catalyst.