Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
2001-12-21
2004-03-23
McKane, Joseph K. (Department: 1626)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
Reexamination Certificate
active
06710011
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a catalyst for the catalytic ammoxidation of alkanes and olefins, more specifically C
3
to C
5
paraffins or olefins, such as propane or isobutane and propylene or isobutylene, to the corresponding &agr;,&bgr;-unsaturated mononitriles, e.g., acrylonitrile and methacrylonitrile, utilizing the disclosed catalyst. In addition, the catalyst may be used in the ammoxidation of xylenes and methylpyridines to the corresponding mono- and di-nitriles.
The invention is directed also to making the catalyst containing isolated vanadium and antimony species in a matrix formed by the oxides of elements usually used as supports or diluents. The invention is directed also to using the catalyst in a process for catalytic ammoxidation of alkanes and olefins.
2. Description of the Prior Art
Acrylonitrile is industrially prepared from the ammoxidation of propylene over a metal oxide catalyst. Due to the lower cost of propane compared with propylene, much research attention has been directed towards finding a catalyst selective for the formation of acrylonitrile from propane. The majority of such catalysts are based on V-Sb oxides.
U.S. Pat. No. 3,860,534 discloses the use for ammoxidation of propane of catalysts containing only vanadium and antimony in oxidic form. British Patent No. 1,336,136 teaches that catalysts can contain, beside vanadium and antimony, only one other metal, which is disclosed to be tin. U.S. Pat. No. 4,746,641 discloses paraffin ammoxidation catalysts that contain tungsten in addition to vanadium and antimony and, optionally, tin, boron, molybdenum, gallium, iron, cobalt, nickel, chromium, manganese, zinc, selenium, tellurium, arsenic, calcium, strontium, bariun or thallium. U.S. Pat. Nos. 4,784,979 and 4,879,264 disclose processes for making a vanadium-antimony catalyst. U.S. Pat. No. 4,797,381 discloses a V-Sb based catalyst with at least one of tungsten, tin, molybdenum, boron, phosphorus, germanium, copper, silver, niobium, tantallum, titanium, iron, cobalt, nickel, chromium, lead, manganese, zinc, selenium, tellurium, gallium, indium, arsenic, an alkali metal, an alkaline earth metal or a rare earth. U.S. Pat. No. 4,871,706 discloses a vanadium-antimony catalyst with tungsten and phosphorus. U.S. Pat. No. 4,873,215 discloses tungsten and phosphorus in addition to vanadium and antimony without molybdenum in a catalyst supported on silica-alumina or alumina. U.S. Pat. No. 4,888,438 discloses a vanadium-antimony catalyst having tungsten, tin, molybdenum, boron, phosphorus or germanium and, optionally, iron, cobalt, nickel, chromium, lead, manganese, zinc, selenium, tellurium, gallium, indium, arsenic, an alkali metal, thallium, magnesium, calcium, strontium, or barium. U.S. Pat. No. 5,008,427 discloses a process of using a catalyst with titanium, tin, iron, chromium or gallium in addition to vanadium and antimony. U.S. Pat. No. 5,079,207 discloses a catalyst with tellurium or bismuth in addition to vanadium-antimony. U.S. Pat. No. 5,094,989 discloses a catalyst having an atomic ratio of antimony:vanadium is a specific range. U.S. Pat. Nos. 5,214,016 and 5,854,172 disclose a vanadium-antimony-tin catalyst. U.S. Pat. No. 5,332,855 discloses a vanadium-antimony catalyst optionally containing iron, gallium, indium or mixtures thereof. U.S. Pat. No. 5,336,804 discloses a vanadium-antimony-bismuth catalyst optionally containing iron, gallium, indium or mixtures thereof. U.S. Pat. No. 5,498,588 discloses a catalyst with vanadium and antimony with titanium, tin, iron, chromium, gallium, lithium, magnesium, calcium, strontium, barium, cobalt, nickel, zinc, germanium, niobium, zirconium, molybdenum, tungsten, copper, tellurium, tantalum, selenium, bismuth, cerium, indium, arsenic, boron or manganese impregnated with lithium, silver, iron, cobalt, copper, chromium, manganese, (VO)
2+
(PW
12
O
40
)
3−
or (PMo
12
O
40
)
3−
. U.S. Pat. Nos. 5,576,469 and 5,693,587 disclose a vanadium-antimony catalyst optionally having tin, titanium, lithium, magnesium, sodium, calcium, strontium, barium, cobalt, iron, chromium, gallium, nickel, zinc, germanium, niobium, zirconium, molybdenum, tungsten, copper, tellurium, tantalum, selenium, bismuth, cerium, indium, arsenic, boron, aluminum, phosphorus or manganese. U.S. Pat. No. 5,994,259 discloses a vanadium-antimony based catalyst in which tin, titanium or iron are optionally present. U.S. Pat. No. 6,072,070 discloses a vanadium-antimony-titanium catalyst containing TiO
2
species. U.S. Pat. No. 6,083,869 discloses a co-precipitated vanadium-antimony-iron catalyst. U.S. Pat. No. 6,156,920 discloses a vanadium-antimony based catalyst which titanium, tin, iron, chromium or gallium must be present and lithium, magnesium, calcium, strontium, barium, cobalt, nickel, zinc, germanium, niobium, zirconium, tungsten, copper, tellurium, tantalum, selenium, bismuth, cerium, indium, arsenic, boron, manganese or molybdenum are optionally present. U.S. Pat. No. 6,162,760 discloses a vanadium-antimony based catalyst in which molybdenum, tungsten, niobium, arsenic, tellurium or selenium must be present and lithium, magnesium, calcium, strontium, barium, cobalt, nickel, zinc, germanium, zirconium, copper, tantalum, bismuth, cerium, indium, boron or manganese are optionally present.
Vanadium-antimony-based oxide catalysts claimed for the use in the process of ammoxidation of alkanes can comprise a single or a number of mixed vanadium, antimony and other oxides, constituting the active phase of the catalyst, or can additionally comprise another inorganic oxide, such as alumina, silica, zirconia, magnesia, titania or niobia, on which the active phase is deposited, e.g., U.S. Pat. No. 4,797,381, or with which the to active phase is mixed, e.g., U.S. Pat. No. 4,871,706, by using various techniques known in the art, such as impregnation or slurry deposition. Oxides used as supports or diluents in the catalyst art are mostly employed to improve catalyst abrasion resistance and/or to reduce its cost and do not substantially affect catalytic behavior of the active phase. The general formula of catalysts in patents do not usually include support material.
None of the above patent documents describe the use of support material as a matrix for isolation of V and Sb species in the catalyst. PCT International Application published under the number WO 00/12208 discloses vanadium antimony oxides (5 mole % of each) dispersed in and distributed by sol-gel method throughout a matrix comprising oxides of silicon, titanium, tantalum and niobium, for using as catalysts for the oxidation of butadiene to furan. There is no mention of the usefulness of these catalysts for ammoxidation reactions. Also, the patent does not disclose or suggest the vanadium antimony oxides implanted into alumina, magnesia, zirconia and hafnia to be useful catalysts. Some indication that alumina can be used as a matrix material comes from the data on propane ammoxidation over vanadium-antimony, vanadium-antimony-aluminum and vanadium-antimony-tungsten-aluminum oxide catalysts recently published by J. Nilsson et. al in
J. Catalysis,
1999, 186, 442. The present invention discloses that the incorporation of oxides vanadium and antimony into an inert oxide matrix, such as alumina, zirconia, magnesia and others, improves catalytic behavior in propane ammoxidation in terms of both stability and selectivity of catalyst activity.
SUMMARY OF THE INVENTION
The present invention provides mixed metal oxide catalysts containing vanadium and antimony for the ammoxidation of paraffins to unsaturated mononitriles, in particular the amoxidation of propane and isobutane to acrylonitrile and methacrylonitrile, respectively.
The present invention provides a method for preparing mixed metal oxide catalysts containing isolated vanadium and antimony species in an inert matrix.
The present invention provides an ammoxidation process for making unsaturated mononitriles from lower paraffins, in particular for the producing acrylonitrile and
Araujo Armando
Bethke Kathleen A.
Khodakov Andrei
Kulkarni Neeta K.
Mamedov Edouard A.
McKane Joseph K.
Saeed Kamal
Saudi Basic Industries Corporatioin
Wheelington Jim
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