Patent GB-952833-A (GB)
Title: Preparation of methyl methacrylate
IPC: C07C69/54
Filed: 1960-03-30
Abstract: Methyl methacrylate is prepared by catalytic dehydrogenation of methyl isobutyrate by a method comprising preparing a catalyst by treating activated alumina, which may have one or more specified additives incorporated therein, at a temperature of at least 400 DEG C. with a quantity of gaseous methyl isobutyrate sufficient to convert the alumina into a form such that when more methyl isobutyrate is contacted therewith at a temperature of at least 400 DEG C. methyl methacrylate is formed, and then contacting gaseous methyl isobutyrate with the catalyst so prepared at a temperature of at least 400 DEG C. The alumina may be gamma, chi, eta, kappa or theta alumina or alpha-alumina hydrate or mixtures thereof. The alumina may comprise one or more of the following substances: silver, lithium, copper, magnesium, calcium, barium, strontium, zinc, cadmium, lead, titanium, zirconium, riobium, antimony, bismuth, chromium, molybdenum, tungsten, manganese, cerium, oxides of those elements and palladium, present in a minor proportion by weight of the total catalyst.  These promoters may be incorporated into the alumina in the form of a salt which is converted during calcination or the dehydrogenation process predominantly into the oxide and maybe in part into the carbonate or metal. The dehydrogenation is preferably effected with the methyl isobutyrate being fed over the catalyst at a sub-atmospheric pressure by use of either reduced pressure or a diluent gas e.g., N2, He, Ar, CO2 or steam with a liquid hourly velocity of 0.05-10 and a contact time of 0.05 to 10 secs. The catalyst may be used in a fixed or fluidised bed and may be regenerated by burning at 500-625 DEG C. Numerous examples are given employing alumina alone or in conjunction with palladium or oxides of various of the above mentioned elements including CaO containing some CaCO3, Bi2O3 and some Bi, and CdO containing some Cd. Another specified catalyst comprises alumina having incorporated therein specified amounts of copper oxide, chromium oxide and an alkaline earth metal oxide.  Specification 952,834 is referred to.ALSO:A dehydrogenation catalyst for use in the conversion of methyl isobutyrate into methyl methacrylate (see Division C2) comprises activated alumina and one or more of the following substances: silver, lithium, copper, magnesium, calcium, barium, strontium, zinc, cadmium, lead, titanium, zirconium, niobium, antimony, bismuth, chromium, molybdenum, tungsten, manganese, cerium, oxides of these elements and palladium, the substances forming a minor proportion by weight, preferably 1 - 15%, of the combined catalyst.  The catalyst requires a pretreatment with the methyl isobutyrate at a temperature of at least 400  DEG C. before being suitable for use in the reaction.  The catalysts are suitably prepared by incorporating in the activated alumina a compound of the desired element which by calcination or during the dehydrogenation process is converted predominantly to the oxide and in part to the metal or carbonate. The alumina may be gamma, chi, eta, kappa, or theta alumina, alpha-alumina monohydrate, or mixtures thereof.  Examples describe gamma alumina or alpha-alumina monohydrate having incorporated therein various molybdenum oxides; MnO2 (ex nitrate); Mn2O3 (ex acetate); MgO and some MgCO3 (ex acetate); CaO (ex nitrate); CaO and some CaCO3 (ex acetate); SrO (ex acetate); BaO and some BaCO3 (ex acetate); TiO2 (ex lactate); ZrO2 (ex acetate); Nb2O5 (ex oxalate); Cr2O3; Pd; CuO (ex nitrate); Ag (ex nitrate); ZnO (ex acetate); CdO and some Cd; PbO (ex acetate); Sb2O4 (ex the sulphide); Bi2O3 (converted to BiO and Bi during the process); Li2O (ex acetate); CeO2 ex nitrate or WO3. Another specified catalyst is activated alumina containing specified amounts of copper oxide, chromium oxide and an alkaline earth metal oxide.  The catalysts may be used in fixed or fluidized beds and may be regenerated by burning at 500-625  DEG C. Specification 952,834 is referred to.