Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Patent
1996-10-07
1999-11-16
Richter, Johann
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
558323, 558325, B01J 2300, C07C25300
Patent
active
059857889
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
This invention relates to a process for making (meth)acrylonitriles by ammoxidation of at least one saturated hydrocarbon selected from the group consisting of propane and isobutane, in which the hydrocarbon is contacted with molecular oxygen and ammonia in the vapor phase.
TECHNOLOGICAL BACKGROUND
(Meth)acrylonitriles have been manufactured in large quantities, as the intermediates for a great variety of industrial products represented by synthetic fibers and synthetic resins. As a conventional production process thereof, ammoxidation is generally known, in which olefinic starting materials, i.e., propylene, isobutene, and the like, are contacted with molecular oxygen and ammonia in the vapor phase, in the presence of a catalyst.
Whereas, with the recent rise in olefin price, development of processes for making the various derivatives which have heretofore been manufactured from olefins, using as the starting materials less expensive paraffins, comes to draw attention. As the catalyst systems used for the production of (meth)acrylonitriles from propane or isobutane by "ammoxidation" process, Sb--U oxide catalyst [Japanese Patent Publication (Kokoku) No. 14371/1972], Sb--Sn oxide catalyst (Kokoku No. 28940/1975), V--Sb oxide catalyst [Japanese Laid-open (Kokai) Nos. 33783/1972, 268668/1989, 95439/1990 and 261544/1990], Bi--Mo oxide catalyst (Kokai No. 16887/1973, Kokoku No. 42071/1980, and Kokai No. 157356/1991], V--P oxide catalyst (Kokoku No. 5188/1983), Bi--V oxide catalyst (Kokai No. 295545/1988), etc. are known. Still recently, furthermore, patent applications have been made for V--Sn--Sb--Cu oxide catalyst (Kokai No. 275266/1992), Mo--V--Te--Nb oxide catalyst (Kokai No. 257/1990), Ag--Bi--V--Mo oxide catalyst (Kokai No. 58961/1991), Ga--Bi--Mo or Ta--Bi--Mo oxide catalyst (Kokai No. 58962/1991), Mo--Ta or Mo--Nb oxide catalyst (Kokai No. 213849/1993), etc. Also mixed catalyst systems of a number of above catalyst systems with those having olefin-ammoxidation ability have been proposed (Kokai Nos. 295546/1988, 38051/1989, 17159/1990, 43949/1990, 75347/1990, 111444/1990 and 258065/1990).
Of these processes, those of adding a minor amount of a halide to the reaction systems as a promotor give the nitrites, which are the intended reaction products, at relatively high yield. However, such processes are difficult of industrial practice because of the corrosion problem of the reaction equipments which incurs restrictions on the construction materials of the equipments. On the other hand, the processes not using any promotor give only low yield of nitrites and have not reached an industrially practiceable level.
DISCLOSURE OF THE INVENTION
Accordingly, therefore, the object of the present invention resides in provision of a process which is free of those defects in the conventional processes and which enables production of (meth)acrylonitriles at high yields and with industrial advantages.
We have made concentrative studies on production of (meth)acrylonitriles by ammoxidation process in which at least one saturated hydrocarbon selected from the group consisting of propane and isobutane is contacted with a mixed gas comprising molecular oxygen and ammonia in the vapor phase in the presence of a catalyst, to discover that meth(acrylonitrile) yields higher than those obtainable in conventional processes can be achieved by use of a catalyst composed of a complex oxide containing oxides of three elements of molybdenum, antimony and tungsten as the essential components, which is supported on a refractory inorganic carrier, and completed the present invention.
Thus, according to the invention a process is provided which comprises preparation of (meth)acrylonitriles by catalytically oxidizing propane and/or isobutane in the vapor phase, with molecular oxygen and ammonia in the presence of a catalyst, said process being characterized by use of a catalyst composed of a complex oxide which is expressed by the general formula (I) below: and W, respectively, where, when .alpha. is 1, .beta. is 0.5
Kishimoto Nobuji
Matsueda Taizou
Murray Joseph
Nippon Shokubai Co Ltd
Richter Johann
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