| 摘要 |
Olefines are oxidised directly to unsaturated aldehydes and ketones and in the presence of ammonia to unsaturated nitriles by use of a bismuth oxide-molybdenum oxide combination catalyst such that the atomic ratio Bi = Mo is above 1:3, promoted with a B2O3, Bi2O3 mixture. The catalyst may be supported and additional catalyst constituents include Mn and P. Specified olefines are propylene, butene-1, butene-2, isobutylene, pentene-1, pentene-2,3, methyl-butene-1, 2-methyl-butene-2, hexene-1, hexene-2, 4-methyl-pentene-1, 3,3-dimethyl-butene-1, 4-methylpentene-2, octene-1, cyclopentene, cyclohexene and 3-methyl-cyclohexene. Reaction may be effected in gaseous phase at elevated temperature, at atmospheric pressure or above in a fluidised or fixed catalyst bed under batchwise or continuous conditions. Examples are given. Specifications 821,999, 867,438, 932,046 and U.S.A. Specification 2,991,320 are referred to.ALSO:Olefines are dehydrogenated to diolefines in the presence of a bismuth oxide-molybdenum oxide combination catalyst such that the atomic ratio Bi : Mo is above 1 : 3 promoted with a B2O3-Bi2O3 mixture. Reactants and product mentioned are n-butenes to butadiene, tert amylenes to isoprene, n-amylenes to piperylene and hexenes and heptenes to their more unsaturated counterparts. Dehydrogenation may be effected in gaseous phase in the presence of air, pure oxygen or hydrogen peroxide and in the presence of diluents such as steam, CO2 and saturated hydrocarbons. Steam is preferred in amounts of 0.1-2 mols. per mol. of olefin and oxygen is added in amounts of 0.3-2 mols per mol., preferably below 12% of the total. Dehydrogenation is effected at 340-600 DEG C., up to 300 p.s.i.g. with a total GHSV of 50-5000.ALSO:Oxidation catalystic compositions comprise a mixture of bismuth and molybdenum oxides such that the atomic ratio Bi:Mo is above 1:3 promoted by a mixture of oxides of boron and bismuth such that the second mixture contains 0,5 to about 1% B and 5-10% Bi. Additionally the catalyst may contain P and/or Mu. The catalysts may be supported on "Alundum" (Registered Trade Mark), SiC, Al2O3/SiO2, Al2O3 or TiO2. Numerous examples are given which include reference to heteropolyacids compounded of the above elements. |
