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United States Patent (19) 11 Patent Number: 5,976,482 Sasaki Et Al

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United States Patent (19) 11 Patent Number: 5,976,482 Sasaki Et Al USOO5976482A United States Patent (19) 11 Patent Number: 5,976,482 Sasaki et al. (45) Date of Patent: Nov. 2, 1999 54 PROCESS FOR PRODUCTION OF PRUSSIC 5,094,990 3/1992 Sasaki et al.. ACID 5,158,787 10/1992 Sasaki et al.. 75 Inventors: Yutaka Sasaki; Hiroshi Utsumi; FOREIGN PATENT DOCUMENTS Kazuo Morishita; Kenichi Miyaki, all O 340 909 11/1989 European Pat. Off.. of Yokohama, Japan O 404 529 A1 12/1990 European Pat. Off.. 0.641771 A1 3/1995 European Pat. Off.. 73 Assignee: Mitsubishi Rayon Co., Ltd., Tokyo, 0 750942 A2 1/1997 European Pat. Off.. Japan 51-10200 1/1976 Japan. 106226 of OOOO U.S.S.R. 21 Appl. No.: 09/038,947 Primary Examiner Wayne Langel 22 Filed: Mar 12, 1998 Attorney, Agent, or Firm- Pillsbury Madison & Sutro LLP 51) Int. Cl. ............................. C01C3/02; B01J 27/198 (57) ABSTRACT 52) U.S. Cl. ............................................. 423/376; 502/209 A proceSS for producing prussic acid by Subjecting methanol 58 Field of Search .............................. 502/209; 423/376 to a gas-phase contact reaction with molecular oxygen and ammonia in the presence of a catalyst, wherein Said catalyst 56) References Cited is an oxide composition containing iron, antimony, phos U.S. PATENT DOCUMENTS phorus and Vanadium with a content of Vanadium content being at least 0.6 in terms of atomic ratio relative to iron 3,911,089 10/1975 Shiraishi et al.. content taken as 10, and a mixed raw material gas for the 4,457.905 7/1984 Ebner. gas-phase contact reaction contains Oxygen at an OXygen 4,461,752 7/1984 Sasaki et al.. to-methanol molar ratio of less than 1.6. 4,511,548 4/1985 Attig et al.. 4,946,819 8/1990 Sasaki et al.. 4,981,830 1/1991 Sasaki et al.. 3 Claims, No Drawings 5,976,482 1 2 PROCESS FOR PRODUCTION OF PRUSSIC SUMMARY OF THE INVENTION ACID In order to achieve the above object, the present inventors made an extensive Study on the improvement of the oxide BACKGROUND OF THE INVENTION catalyst containing iron, copper, antimony and phosphorus, 1. Field of the Invention described in U.S. Pat. No. 5,158,787 and the catalyst con The present invention relates to a process for producing taining iron, antimony and phosphorus as essential compo prussic acid. More particularly, the present invention relates nents and iron antimonate as a crystal phase, described in to a process for producing prussic acid by Subjecting metha U.S. Pat. No. 5,094,990. As a result, the present inventors nol to ammoxidation in a gas-phase contact reaction. found out that an oxide catalyst obtained from a combination 2. Description of the Related Art of iron, antimony, phosphorus and Vanadium can well utilize oxygen in a catalytic reaction of methanol, oxygen and Prussic acid is produced by decomposition of formamide, ammonia for production of prussic acid and can prevent a reaction of methane with ammonia, ammoxidation of reduction in prussic acid yield even at a low oxygen-to methane, etc. A large portion of the prussic acid consumed methanol molar ratio and that the catalyst, when the content is a by-product formed when propylene is Subjected to 15 of Vanadium component therein is at a certain level or ammoxidation to produce acrylonitrile. higher, can have a significantly improved redox Stability and Prussic acid has been increasingly used as raw material has very high resistance to deterioration. The present inven for acetone cyanohydrin, adiponitrile, chelating agent Such tion has been completed based on the above finding. as EDTA and the like, and also used for gold recovery. The The present invention relates to a proceSS for producing gap between its Supply and demand has been becoming prussic acid by Subjecting methanol to a gas-phase contact more obvious. reaction with molecular oxygen and ammonia in the pres In view of the above situation, the present invention have ence of a catalyst, wherein the catalyst used is an oxide been completed in order to develop a novel process for composition containing iron, antimony, phosphorus and producing pruSSic acid by ammoxidation of methanol, which 25 vanadium with the content of vanadium being 0.6 in terms has excellent industrial applicability. of atomic ratio relative to the iron content taken as 10, and For production of prussic acid by ammoxidation of the mixed raw material gas fed into the reaction System methanol, various catalysts are known Such as molybdenum contains oxygen at an oxygen-to-methanol molar ratio of oxide, described in U.R.S.S. Patent No. 106226; an oxide less than 1.6. containing molybdenum, bismuth and other elements, described in U.S. Pat. No. 3,911,089; an oxide containing PREFERRED EMBODIMENTS OF THE antimony and at least one element Selected from the group INVENTION consisting of iron, cobalt, nickel, manganese, Zinc and Catalyst uranium, described in JP-A-51-10200; an oxide catalyst The catalyst used in the present proceSS contains, as containing manganese and phosphorus, described in U.S. essential components, not only iron, antimony and phospho Pat. No. 4,457.905; an antimony phosphate, described in 35 rus but also a particular amount of Vanadium, and thereby U.S. Pat. No. 4,511,548; and so forth. has improved activity and other properties and can give a In order to improve the iron and antimony-based oxide high prussic acid productivity. The content of Vanadium in catalyst described in JP-A-51-10200, the present inventors the catalyst is at least 0.6, preferably 0.6-3 in terms of proposed an oxide catalyst containing iron, copper and 40 atomic ratio to the iron content taken as 10. antimony, in U.S. Pat. No. 4,461,752; an oxide catalyst The present catalyst, when specifically shown, is an oxide containing iron, copper, antimony and phosphorus, in U.S. composition represented by the following empirical for Pat. No. 5,158,787; and a catalyst containing iron, antimony mula: and phosphorus as essential components and iron anti monate as a crystal phase, in U.S. Pat. No. 5,094,990. The 45 present inventors further proposed improved processes for wherein X is at least one element Selected from the group catalyst production, in U.S. Pat. No. 4,946,819, U.S. Pat. consisting of Mg., Zn, La, Ce, Al, Cr, Mn, Co, Ni, Bi, U and No. 4,981,830, etc. Theses processes showed progresses in Sn (preferably at least one element Selected from the group various respects, but Still had points to be improved for consisting of Zn, Al, Mn, Co and Ni); Y is at least one industrial application. 50 element Selected from the group consisting of B and Te; Z That is, in producing prussic acid by ammoxidation of is at least one element Selected from the group consisting of methanol, the above-mentioned catalysts require a high Li, Na, K, Rb, CS, Ca and Ba; and a, b, c, d, e, f, g, h, ii, oxygen-to-methanol ratio in a mixed raw material gas in k and l are atomic ratios, and when a is 10, b=12-30 order to avoid a reduction in prussic acid yield or a reduction (preferably 15–27), c=1-30 (preferably 3-20, more prefer in catalytic activity with time. Consequently, when pruSSic 55 ably 5-15, and b/c21.5), d=0.6-3 (preferably 0.8-2.8, more acid is produced industrially with the catalysts, the reaction preferably 1-2.5), e=0-0.3, f=0-5, preferably 0.5-4, g=0-3, must be conducted at a low methanol concentration, which h=0-6, i=0-5, j=0-3, k=a number corresponding to the results in a lower productivity. oxides formed by the elements Fe, Sb, P. V. Mo, Cu, W, X, The present invention has been completed in order to (1) Y and Z, and l=0-200. alleviate the above-mentioned problems of the prior art and 60 In the present catalyst containing iron, antimony, phos (2) provide an economical process for producing prussic phorus and Vanadium as essential components, it is not clear acid, which uses a catalyst having significantly improved what compound these components form in the catalyst to redox Stability, which enables an efficient reaction at a low exhibit improved activity and other properties. It is oxygen-to-methanol ratio of mixed raw material gas, and presumed, however, that the components are closely related which gives prussic acid as intended product at a high yield, 65 to each other to exhibit improved activity and other at a high Selectivity and Stably with the lapse of reaction properties, in View of the fact that, when the composition of time. the catalyst deviates from the range of the above empirical 5,976,482 3 4 formula, the Selectivity of prussic acid formation decreases ammonium dihydrogen phosphate, ammonium or the properties of the catalyst are deteriorated, making it hydrogenphosphate, ammonium phosphate, etc. difficult to achieve the intended object of the present inven AS the raw material for the Vanadium component, there tion. It is preferred that iron antimonate is contained as a can be used Vanadium pentoxide, ammonium metavanadate, crystal phase in the catalyst. The Vanadium component is Vanadyl oxalate, Vanadyl Sulfate, etc. presumed to form a Solid Solution with iron antimonate. The AS the raw material for the copper component, there can presence of iron antimonate is effective for the improvement be used cuprous oxide, cupric oxide, copper nitrate, etc. of prussic acid yield, the prevention of reduction in yield AS the raw material for the molybdenum component, during long-term operation, and the optimization of catalyst there can be used molybdenum trioxide, molybdic acid, properties.
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