GB767409A - Improvements in or relating to the production of ketones - Google Patents

Abstract

Olefines containing at least 3 carbon atoms are converted into ketones containing the corresponding number of carbon atoms by reacting the olefines with water wholly or partly in the vapour phase under a pressure of 5 to 1000 atmos. gauge and at 200 DEG to 400 DEG C., in the presence of a solid catalyst comprising at most 10 per cent by weight of a hydrogenating metal from Group IB or VIII of the Periodic Table, supported on a substantially water-insoluble solid hydration catalyst comprising an electronic insulator or semi-conductor material, the terms "insulator" and "semi-conductor" being used in the senses given in the Journal of the Chemical Society, 1950, at page 242 et seq. Preferred hydrogenating metals are platinum and palladium; nickel and copper are also mentioned. The supports for the metal catalysts may be gamma - alumina, alumina - silica, alumina-zirconia, thoria, cadmium and zinc phosphates and the crystalline phosphates of the alkaline earth metals, all of which are best suited for use in the absence of liquid water, and tungsta, molybdena and titania. In general, water : olefine ratios of 1 : 2 to 20 : 1 are employed. Temperatures preferably do not exceed 350 DEG C. In an example, propylene is reacted with water at 270 DEG C. under 250 atmos. gauge pressure using a pelleted catalyst of 5 per cent platinum on tungstic acid yielding acetone together with some isopropanol which is recycled with unchanged propylene. Another catalyst mentioned is 2 per cent Pt on gammaalumina or tungstic acid. Other starting materials mentioned are aliphatic olefines having up to 6 carbon atoms, e.g. butene-1, and cycloaliphatic ketones such as cyclopentene and cyclohexene. Specification 335,551, [Class 2 (iii)], is referred to. According to the Provisional Specification, elevated temperatures and pressures generally may be used.ALSO:Solid catalysts for use in converting olefines into ketones of the same carbon content by reaction with water (see Group IV(b)) comprise at most 10 per cent by weight of a hydrogenating metal from Group I(b) or VIII of the Periodic Table supported on a substantially water-insoluble solid hydration catalyst comprising an electronic insulator or semi-conductor material, the terms "insulator" and "semi-conductor" being used in the senses given in the Journal of the Chemical Society, 1950, at page 242 et seq. Specified hydrogenating metals are platinum, palladium, nickel and copper. The supports for the metals may be gamma-alumina, aluminasilica, alumina-zirconia, thoria, cadmium and zinc phosphates, the crystalline phosphates of the alkaline earth metals, tungsta, molybdena and titania. Specified catalysts are platinum (2 or 5 per cent) on tungstic acid as gamma-alumina. A suitable catalyst may be prepared by impregnating tungstic acid powder with chloroplatinic acid solution, pelleting at 40 or more tons/sq. in. pressure and then igniting in air or hydrogen at 300-400 DEG C. Specification 335,551 [Class 1(i)] is referred to.