Abstract: Saturated, lower aliphatic acids and esters are oxydehydrogenated to the corresponding unsaturated acids and esters by use of a catalyst of the empirical formula:Mo.sub.12 P.sub.0.1-3 Bi.sub.0.01-2 M.sub.0.1-3 Cu.sub.0.01-2 V.sub.0.01-3 X.sub.a M'.sub.b O.sub.c (I)whereM is at least one of K, Rb and Cs;X is at least one of Ba, Zn, Ga, Cd, Ti, when a>0;M' is at least one of Ca, Mg, Ta, Zr, Ce, Ni, Co, Cr, Fe and Tl when b>0;a is a number of 0 to about 2;b is a number of 0 to about 2; andc is a number that satisfies the valence requirements of the other elements present.
Type:
Grant
Filed:
September 5, 1980
Date of Patent:
December 22, 1981
Assignee:
Standard Oil Company
Inventors:
Wilfrid G. Shaw, James E. Rinz, Christos Paparizos
Abstract: Isobutyric acid or a functional equivalent, e.g., a lower alkyl ester is oxidatively dehydrogenated to effect the vapor phase conversion thereof to the corresponding .alpha.,.beta.-ethylenically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of calcined phosphates of iron containing tellurium as a modifier or dopant component.
Abstract: Isobutyric acid or a functional equivalent, e.g., a lower alkyl ester is oxidatively dehydrogenated to effect the vapor phase conversion thereof to the corresponding .alpha.,.beta.-ethylenically unsaturated derivative by contact with a heterogeneous catalyst in the presence of molecular oxygen. The catalyst is composed of calcined phosphates of iron containing silver as a modifier or dopant component.
Abstract: In a process wherein ethylene or propylene is carbonylated with carbon monoxide to form carboxylic acid esters in the presence of a catalyst complex of one mole of BF.sub.3 and one mole of alcohol, the invention concerns a technique wherein the catalyst is recovered from the reaction product and recycled. The carbonylation is carried out until approximately one-half of the alcohol is consumed, to form a reaction mass containing the BF.sub.3, the alcohol, and the carboxylic acid ester in a 2:1:1 molar ratio. In the first step, the one mole of the free BF.sub.3 is vaporized from the reaction mass. The remaining admixture is a 1:1:1 mixture of the three aforesaid compounds. To this mixture additional alcohol is added and the mixture is subjected to distillation. A carboxylic acid ester/alcohol azeotrope and residual alcohol are removed by the distillation, to leave a residue containing a 1:2 BF.sub.3 /alcohol complex. This complex is combined with an additional mole of BF.sub.
Abstract: Propylene and ethylene may be carbonylated to form carboxylic acid esters or carboxylic acids in the presence of a catalyst complex containing 1 mole of BF.sub.3 and 1 mole of a second complexing component. The carboxylic acid product or acid portion of the ester product has one more carbon atom than the olefin reacted. High yields of these products are obtained. In the case of the formation of the ester, the second complexing component is an alcohol, while in the case of the preparation of carboxylic acid, the second complexing component is water. Methyl isobutyrate and methyl propionate formed by the carbonylation of propylene and ethylene, respectively, in the presence of a BF.sub.3.CH.sub.3 OH catalyst may be dehydrogenated to prepare methyl methacrylate and methyl acrylate, respectively. Similarly, the isobutyric acid and propionic acid formed from propylene and ethylene, respectively, in the presence of BF.sub.3.H.sub.
Abstract: Certain C.sub.4 to C.sub.9 saturated acids, esters and aldehydes are oxidatively dehydrogenated catalytically and exothermically to the corresponding .alpha.,.beta.-unsaturated acids, esters and/or aldehydes with certain calcined catalysts containing the elements Mo and V.
Abstract: A catalyst containing alkali metal, chromium, iron, lead, phosphorus and oxygen, and a process for the preparation of unsaturated lower aliphatic acids and esters of such acids by catalytic oxidative dehydrogenation of the corresponding saturated acids and esters using the catalyst.
Abstract: The invention concerns dehydrogenation of carboxylic acids, lactones, esters, nitriles, the carbon skeleton of the feed material being characterized as containing mono-unsaturation or alternatively functional groups such as hydroxyl which convert under process conditions to unsaturation, the dehydrogenation reaction being conducted in the presence of a contact catalyst comprising a carbonaceous layer effective for the dehydrogenation of mono-unsaturated reactants to di-unsaturated products. Another aspect of the invention involves production of the mono-unsaturated reactants. In particular, the invention provides a route to sorbic acid, for example by dehydrogenation of hexenoic acids or esters thereof.