Catalyst based on oxides of Fe, Co, Bi and Mo

Details Catalyst based on oxides of Fe, Co, Bi and Mo Catalyst based on oxides of Fe, Co, Bi and Mo

1996-03-22

1998-09-15

Green, Anthony

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acids and salts thereof

502202, 502207, 502302, 502303, 502304, 502305, 502306, 502307, 502308, 502310, 502311, 502312, 502313, 502314, 502315, 502316, 502317, 502318, 502319, 502320, 502321, 502322, 502323, 502324, 502325, 502326, 502327, 502328, 502329, 502330, 502331, 502332, 502335, 502336, 502337, 502338, 502340, 502341, 502342, 502343, 502344, 502345, 502346, 502349, 502352, 502353, 502354, 502355, 562418, 562518, 562519, 562520, 562521, 562522, 562523, 562524, 562525, 562526, 684699, 68470, 68471, C07C 516, B01J 2100, B

Patent

active

058081437

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to catalysts of the formula I F.sub.j O.sub.y !.sub.q I, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury, other than oxygen in I, and p and q are numbers whose ratio p/g is in the range from 0.001 to 0.099.
The present invention also relates to a process for the preparation of these catalysts, to the use of these catalysts for the ammonoxidation, oxidation or dehydrogenation of ethylenically unsaturated compounds, and to a process for the ammonoxidation, oxidation or oxidative dehydrogenation of othylenically unsaturated compounds in the presence of the novel catalysts.
EP-A 000 835 describes catalysts having the composition E'.sub.d' F'.sub.e' N'.sub.f' O'.sub.y' !.sub.p', Si, Ge, Pb, Th and/or U. elements other than oxygen, and q' and p' are numbers whose ratio q'/p' is in the range from 0.1 to 10. F'.sub.e' N'.sub.f' O'.sub.y' ! is referred to as the guest phase.
Regarding the preparation of these catalysts, EP-A 000 835 recommends the other constituents, and then mixing it with oxides or water-soluble salts of the elements of the guest phase and, after drying, calcining the mixture.
EP-A 000 835 furthermore discloses to employ the catalytic compositions mentioned therein as catalysts for gas-phase-catalytic oxidation of organic compounds. However, the compositions disclosed in EP-A 000 835 have the disadvantages that they do not have entirely satisfactory activity and selectivity when used in the gas-phase-catalytic oxidation of organic compounds.
DE-C 33 38 380 discloses catalytically active compositions of the formula II Y.sup.3.sub.g" Y.sup.4.sub.h" O.sub.x" (II), niobium,


______________________________________ where a"/b" is b" is from 0.5 to 4 from 0.1 to 4, ______________________________________ other than oxygen in II, compound in an aqueous medium, drying the aqueous mixture, calcining the resultant composition at from 600.degree. to 900.degree. C. and subsequently powdering the product in such a way that the particle size is less than 152 .mu.m, and treating the resultant powder with an aqueous solution of the sources of the other constituents of the composition II, and evaporating, shaping and calcining the resultant mixture.
DE-C 33 38 380 also discloses that the compositions II are suitable as catalysts for the gas-phase-catalytic preparation of unsaturated aldehydes by oxidation.
However, the compositions II disclosed in DE-C 33 38 380 have the disadvantage that they do not have entirely satisfactory activity and selectivity in the ammonoxidation of propene to acrylonitrile.
It is an object of the present invention to provide catalysts which do not have said disadvantages.
We have found that this object is achieved by the catalysts defined at the outset.
Suitable elements in the novel catalysts are: cerium, chromium, cadmium, molybdenum, bismuth and/or mercury,
Preferred catalysts are those which contain at least one of the elements bismuth, molybdenum and/or tungsten and iron having a stoichiometric coefficient which is not zero and is preferably .gtoreq.0.01.
Furthermore, the novel catalysts I prove to be more advantageous the higher the percentage of the various chemically different components having a mean particle size (measured using a Sympatec laser diffraction instrument) in the range from 10 nm to less than 1 .mu.m, preferably in the range from 10 nm to 800 nm, particularly preferably from 10 nm to 600 nm.
In particular, particles of the key phase and/or of the guest phase of the catalyst preferably have a mean particle size in the range from 10 nm to less than 1 .mu.m, particularly preferably in the range from 10 nm to 800 nm, very particularly preferably from 10 nm to 600 nm.
The key phase A.sub.a B.sub.b O.sub.x here preferably has the stoichiometry
The novel compositions are obtainable by the following steps: O.sub.x, Fe.sub.e Co.sub.f E.sub.i F.sub.j O.sub.y or water-soluble salts of elements of the guest phase or a mixture of at least one water-soluble salt of these elements and at least one calcined phase of o

REFERENCES:
patent: 3746657 (1973-07-01), Miller et al.
patent: 4388223 (1983-06-01), Ferlazzo et al.
patent: 4537874 (1985-08-01), Sato et al.

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