Patent GB-1240858-A (GB)
Title: Process for the preparation of ketones and/or aldehydes from olefins
IPC: B01J23/84
Filed: 1968-10-04
Abstract: 1,240,858. Catalysts and preparation thereof. STAMICARBON N.V. 4 Oct., 1968 [7 Oct., 1967; 10 Feb., 1968], No. 47309/68. Heading B1E. [Also in Division C2] A catalyst composition comprises particulate support material which carries at least one oxide of titanium, tin or iron and at least oxide of vanadium, molybdenum or tungsten, the oxide or oxides of titanium, tin or iron being homogeneously distributed over the support material in the form of particles at least a predominant proportion of which have a diameter of not more than 50 Angstroms. The catalyst composition may be prepared by a process which comprises forming a mixture of particulate support material and a solution containing ions of titanium and/or tin and/or iron, agitating the mixture to form a suspension of the support material and making available hydroxyl ions in the suspension by an in situ generation of hydroxyl ion at such a low and controlled rate that a precipitate of material containing titanium and/or tin and/or iron is formed on the support material and not in the body of the solution, adding at least one oxide or salt of vanadium, molybdenum or tungsten to the suspension whereby material containing vanadium and/or molybdenum and/or tungsten is deposited on the support material, separating the loaded support material from the suspension and drying and calcining the separated support material. The hydroxyl ions may be made available in the suspension by the provision therein of a compound which reacts with water to provide hydroxyl ions, for example urea, sodium nitrile or hexamethyllenediamine. Silica-stannic oxide-molybdenum trioxide catalyst compositions in which the stannic acid is homogeneously distributed over the silica in the form of particles having an average diameter of 10 Angstroms are prepared by suspending silica (a commerciallyavailable highly-porous silica obtained from silica tetrachloride by flame hydrolysis) in a solution containing stannic ions derived from stannic chloride pentahydrate, adding urea to the resulting suspension, boiling the suspension with stirring until the pH thereof reaches a value of 7, cooling the suspension, adding molybdenum trioxide to the cooled suspension with stirring, filtering the resulting suspension, washing the resulting solid with water and calcining the washed solid at a temperature of 450‹C or 550‹C, the calcined material may be subjected to steam at a temperature of 450‹C. Such compositions analyze, by weight, 75.4% SiO 2 , 4.2% SnO 2 , 20.4% MoO 3  or 77.3% SiO 2 , 7.4% SnO 2 , 15.3% MoO 3 ; compositions similarly prepared contain 18.0 or 43.8% by weight stannic acid. Comparative catalyst compositions disclosed are (i) a mixture of stannic oxide and molybdenum trioxide, (ii) particulate stannic oxide loaded with molybdic acid, and (iii) silica-stannic oxidemolybdenum trioxide prepared by suspending silica in a solution containing stannic ions derived from stannic chloride pentahydrate, adjusting the pH of the resulting suspension to a value of 7 by addition thereto of ammonia, adding molybdenum trioxide to the suspension, filtering, the resulting suspension and calcining the resulting solid at a temperature of 450‹C to provide a composition in which the stannic oxide is in the form of conglomerates having a size greater than 100 Angstroms. The catalyst composition may be used as catalyst in the oxidation of an olefin, for example propylene or a butene, by oxygen in the presence of steam to provide, inter alia, a ketone, for example acetone or butanone.