United States Patent Office Patented Mar

3,308,151 United States Patent Office Patented Mar. 7, 1967 2 ing that the catalyst is composed either in whole or in 3,308,151. part of these compounds. PROCESS FOR THE OXEDATION OF OLEFN. AMMON A MIXTURES TO UNSATURATED The proportions of antimony and uranium in the cata NITRELES lyst System may vary widely. The Sb:U atomic ratio James L. Callahan, Cuyahoga County, Ohio, and Berthold 5 can range from about 1:50 to about 99:1. However, Gertisser, Essex County, N.J., assignors to The Stand optimum activity appears to be obtained at Sb:U atomic ard Oil Company, Cleveland, Ohio, a corporation of ratios within the range from 1:1 to 25:1. Ohio The catalyst can be employed without support, and No Drawing. Filed Jan. 1, 1965, Ser. No. 462,460 Will display excellent activity. It also can be combined 6 Claims. (C. 260-465.3) O With an inert Support, and preferably at least 10% up to about 90% of the supporting compound by weight of the This invention relates to the oxidation of olefin entire composition is employed in this event. Any known ammonia mixtures to unsaturated nitriles, such as pro Support materials can be used, stable under the reaction pylene-ammonia to acrylonitrile and isobutylene-am conditions to be encountered in the use of the catalyst. monia to methacrylonitrile using oxidation catalyst sys The antimony oxide and uranium oxide can be blended tems consisting essentially of oxides of antimony and together, or can be formed separately and then blended, uranium. or formed separately or together in situ. As starting This application is a continuation-in-part of application materials for the antimony oxide component, for ex Serial No. 201,329, filed June 11, 1962, now abandoned, ample, there can be used any antimony oxide, such as and of application Serial No. 247,331, filed December 26, 20 antimony trioxide, antimony tetroxide and antimony pent 1962, now U.S. Patent No. 3,198,750, patented August Oxide, or mixtures thereof; or a hydrous antimony oxide, 3, 1965. metaantimonic acid, orthoantimonic acid or pyroanti U.S. Patent No. 2,904,580, dated September 15, 1959, monic acid; or a hydrolyzable or decomposable anti describes a catalyst composed of antimony oxide and mony Salt, such as an antimony halide, for example, anti molybdenum oxide, as antimony molybdate, and indi 25 mony trichloride, trifluoride or tribromide; antimony cates its utility in converting propylene to acrylonitrile. pentachloride and antimony pentafluoride, which is hy British Patent 864,666, published April 6, 1961, de drolyzable in water to form the hydrous oxide. Anti scribes a catalyst composed of an antimony oxide alone mony metal can be employed, the hydrous oxide being or in combination with a molybdenum oxide, a tungsten formed by oxidizing the metal with an oxidizing acid oxide, a tellurium oxide, a copper oxide, a titanium oxide, 30 Such as nitric acid. or a cobalt oxide. These catalysts are said to be either The uranium oxide component can be provided in the mixtures of these oxides or oxygen-containing compounds form of uranium oxide or by precipitation in situ from of antimony with the other metal; such as antimony a soluble uranium salt such as the nitrate, acetate, or a ha molybdate or molybdoantimonate. These catalyst sys lide Such as the chloride. Uranium metal can be used as tems are said to be useful in the production of unsatu 35 a starting material, and if antimony metal is also employed, rated aldehydes such as acrolein or methacrolein from the antimony can be converted to the oxide and uranium olefins such as propylene or isobutene and oxygen. to the nitrate simultaneously by oxidation in hot nitric British Patent 876,446, published August 30, 1961, de acid. A slurry of hydrous antimony oxide formed in situ scribes catalysts including antimony, oxygen and tin, and from the metal in nitric acid also can be combined with said to be either mixtures of antimony Oxides with tin 40 a solution of a uranium salt such as uranium nitrate, oxides or oxygen-containing compounds of antimony and which is then precipitated in situ as uranium oxide by tin such as tin antimonate. These catalysts are said to be the addition of ammonium hydroxide. The ammonium useful in the production of unsaturated aliphatic nitriles nitrate and any other soluble salts are removed by filtra such as acrylonitrile from olefins such as propylene, oxy tion of the resutling slurry. gen and ammonia. 45 It will be apparent from the above that uranium tri bromide, uranium tetrabromide, uranium trichloride, The catalyst uranium tetrachloride, uranium pentachloride, uranium hexafluoride, uranium tetraiodide, uranyl nitrate, uranyl In accordance with the invention, an oxidation catalyst Sulfate, uranyl chloride, uranyl bromide, uranium trioxide, is provided consisting essentially of oxides of antimony 50 and uranium peroxide can be employed as the source of and uranium. This catalyst is useful not only in the oxi the uranium oxide component. dation of olefins to oxygenated hydrocarbons such as un The catalytic activity of the system is enhanced by heat saturated aldehydes and acids, for example, acrolein and ing at an elevated temperature. Preferably, the catalyst methacrolein, and acrylic and methacrylic acid, and the mixture is dried and heated at a temperature of from oxidation of olefin-ammonia mixtures to unsaturated ni 55 about 500 to about 1150 F., preferably at about 700 to triles such as acrylonitrile, and methacrylonitrile, but 900 F., for from two to twenty-four hours. If activity also in the catalytic oxidative dehydrogenation of olefins then is not sufficient, the catalyst can be further heated to diolefins. at a temperature above about the 1000 F. but below a The nature of the chemical compounds which com temperature deleterious to the catalyst at which it is melted pose the catalyst of the invention is not known. The cata 60 or decomposed, preferably from about 1400 F. to about lyst may be a mixture of antimony oxide or oxides and 1900 F. for from one to forty-eight hours, in the pres uranium oxide or oxides. It is also possible that the anti ence of air or oxygen. Usually this limit is not reached mony and uranium are combined with the oxygen to form before 2000 F., and in some cases this temperature can an antimonate or uranate. X-ray examination of the be exceeded. catalyst system has indicated the presence of a struc 65 In general, the higher the activation temperature, the turally common phase of the antimony type, composed less time required to effect activation. The sufficiency of of antimony oxide, and some form of uranium oxide. activation at any given set of conditions is ascertained Antimony tetroxide has been identified as present. For by a spot test of a sample of the material for catalytic the purposes of description of the invention, this catalyst activity. Activation is best carried out in an open cham system will be referred to as a mixture of antimony and ber, permitting circulation of air or oxygen, so that any uranium oxides, but this is not to be construed as mean oxygen consumed can be replaced. 3,308,151 3 4. The antimony oxide-uranium oxide catalyst composi reaction vessel improves the selectivity of the reaction and tion of the invention can be defined by the following em yield of nitrile. However, reactions not including water pirical formula: in the feed are not to be excluded from this invention, in Sbal JOc asmuch as water is formed in the course of the reaction. In general, the molar ratio of added water to olefin, where a is 1 to 99, b is 50 to 1, and c is a number taken to when water is added, is at least about 0.25:1. Ratios on satisfy the average valences of antimony and uranium in the order of 1:1 to 3:1 are particularly desirable, but the oxidation states in which they exist in the catalyst as higher ratios may be employed, i.e., up to about 10:1. defined by the empirical formula above. Thus, the Sb The reaction is carried out at a temperature within the valence may range from 3 to 5 and the U valence from range of from about 550 to about 1100 F. The pre 4 to 6. 10 ferred temperature range is from about 800 to 1000 F. This catalyst system is useful in the oxidation of olefins The pressure at which reaction is conducted is also to oxygenated compounds, such as aldehydes and acids, in an important variable, and the reaction should be carried the presence of oxygen, and in the oxidation of olefins out at about atmospheric or slightly above atmospheric to unsaturated nitriles in the presence of oxygen and (2 to 3 atmospheres) pressure. In general, high pres ammonia. Nitriles and oxygenated compounds such as sures, i.e., about 250 p.s.i.g., are not suitable, since aldehydes and acids can be produced simultaneously using higher pressures tend to favor the formation of undesir process conditions within the overlapping ranges for these able by-products. reactions, as set forth in detail below. The relative pro The apparent contact time is not critical, and contact portions of each that are obtainable will depend on the 20 times in the range of from 0.1 to about 50 seconds may catalyst and on the olefin. The same catalyst may pro be employed. The optimum contact time will, of course, duce predominantly the nitrile with propylene and pre vary, depending upon the olefin, being treated, but in dominantly the aldehyde and/or acid with isobutylene.

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