United States Patent [19] [11] Patent Number: 4,980,327 Wolfe [45] Date of Patent: Dec

United States Patent [19] [11] Patent Number: 4,980,327 Wolfe [45] Date of Patent: Dec. 25, 1990 [54] REDUCED AND STABILIZED 4,096,093 6/1978 HYDROGENATION CATALYSTS 4,161,483 7/1979 4,166,805 9/1979 [75] Inventor: David C. Wolfe, Louisville, Ky. 4,309,511 I/ 1982 [ 73 1 A sslgnee-. _ U "1.tedc 3 tal Y5 tsIn “2 L mm“. .11 e’ K y- 4,808,5624,471,068 2/19899/1984 Kubersky et al. ................ .. 502/151 [21] Appl' No’: 489’44'2 Primary Examiner-Patrick P. Garvin [22] Filed; Man 6, 1990 Assistant Examiner-E. D. Irzinski Attorney, Agent, or Firm-Herbert P. Price [51] Int. Cl.5 ...................... .. B01J 31/34; B01J 31/28; BOIJ 31/02 [57] ABSTRACT U.S. Cl. .................................... .. Transition metal on an Stable carrier hydrogena _ 502/167; 502/173 tion catalysts are stabilized with a coating of a fatty [58] Field of Search ................ .. 502/62, 165, 167, 173 amine and an alkane wherein the fatty amine_a1kane [56] References Cited coating has a melting point of about 130° C. to about . 180° F. U.S. PATENT DOCUMENTS 4,041,225 8/1977 Pullurat ............................. .. 502/167 16 Claims, No Drawings 4,980,327 1 _ 2 about 10 to about 22 carbon atoms. The blend of fatty REDUCED AND STABILIZED HYDROGENATION amine and alkane has a melting point between about CATALYSTS 130° F. and about 180° F. BACKGROUND OF THE INVENTION 5 DESCRIPTION OF THE INVENTION The ?eld of art to which this invention pertains is The hydrogenation catalyst of this invention are reduced and stabilized hydrogenation catalysts. used, primarily, in the manufacture of fatty amines, i.e., Finely divided reduced nickel catalysts have been alkyl amines wherein each alkyl group contains about used as hydrogenation catalysts for a large number of 12 to about 22 carbon atoms. An example of such years. The preparation of such catalysts on diatoma 10 amines is saturated tallow amine. The amines are de ceous earth or Kieselguhr is described, for example, in rived fromvfatty nitriles which in turn are derived from “Reactions of Hydrogen with Organic Compounds fatty acids. In the reaction scheme, natural fats and oils, over Copper-Chromium Oxide and Nickel Catalysts” e.g., tallow, are reacted to form fatty acids which are by Homer Adkins, University of Wisconsin Press treated with ammonia to form fatty acid amides which (1937). Catalysts of this type are very sensitive to air in are then converted to nitriles. An example of such a their activity to the point of being pyrophoric and, reaction scheme is found in U.S. Pat. No. 3,299,117. The therefore, must be stabilized against the action of air in fatty nitriles are then hydrogenated to amines using the order to be utilized commercially. catalysts of this invention. U.S. Pat. No. 4,808,562 discloses processes for stabi Reduced transition metal catalysts are sensitive to the lizing ?nely divided pyrophoric catalysts by impregnat action of air to the point of being pyrophoric. In order ing them with solid fats, solid paraf?n, fatty amines or to protect such catalysts from air and to preserve their similar products. reactivity, they are encapsulated, according to this in Nickel catalysts dispersed in fat are described in U.S. vention, with a fatty amine which amine is also the Pat. No. 2,609,346. desired product of the fatty nitrile hydrogenation reac According to U.S. Pat. No. 2,865,865, Raney nickel tion. This encapsulation stabilizes the catalyst against catalysts are mixed with a fatty alcohol to form a solid the action of air. However, during storage, it has been suspension of the catalyst in the fatty alcohol. found that an ‘in situ reaction takes place between the U.K. Patent No. 2,052,296 describes a process for amine coating and the reduced transition metal resulting stabilizing Raney metal catalysts. For example, a water in the formation of, for example, higher order amines, wet Raney nickel catalyst is rendered oleophilic by a amides and imides whereby free ammonia is released to surface active agent followed by dispersing the oleo the environment, and subsequent loss in the activity of philic particles in molten wax, fat, or organic polymer the catalyst occurs. The addition of the alkane to the and then solidifying the mixture. Examples of surface amine coating results in a catalyst which retains its active agents, which are used in the amounts of i to 1 percent by weight based on the weight of catalyst and activity and from which there is no evolution of ammo water, include the organic acid salts of long chain ma. amines, such as tallow amine, soy bean oil amine and the The transition metals used in the catalysts of this like. invention include iron, cobalt, nickel, copper, zinc, The use of nickel catalysts in the hydrogenation of molybdenum, and tin either alone or in various combi nitriles to amines is well known and is described in such 40 nations. The preferred metals are iron, cobalt, and publications as “Reactions of Hydrogen with Organic nickel with nickel being most preferred. Compounds” referred to hereinabove as well as U.S. The carriers useful in this invention are any of the Pat. Nos. 3,293,298, 3,163,676 and Japanese Patent No. well known inert materials which are used to support ?nely divided-metals. Example of such carriers are 6464/55. ' 45 diatomaceous earth (Kieselguhr), pumice, activated SUMMARY OF INVENTION clay, natural and synthetic aluminas and silicas, and This invention is directed to hydrogenation catalysts. combinations of any of the above. The invention pertains to a reduced and stabilized hy The transition metal on inert carrier catalysts have drogenation catalyst. been known for a considerable number of years and can The catalyst of this invention is a particulate transi be prepared by impregnating a porous support, e.g., tion metal on a suitable carrier hydrogenation catalyst diatomaceous earth, with an aqueous solution of the stabilized with a fatty amine and an alkane. The catalyst metal salt, precipitating the metal as the oxide, hydrox contains (A) about 20 to about 50 weight percent transi ide, or carbonate with a base, drying the mass, and tion metal on a suitable carrier encapsulated with (B) reducing the oxide to the metal with hydrogen. The about 50 to about 80 weight percent fatty amine and the 55 preparation of such metal catalysts is described in U.S. alkane, said weight percents being based on the weight Pat. No. 3,235,515 which is hereby incorporated by of (A) and (B). Preferably, the catalyst contains about reference. 30 to about 50 weight percent of (A) and about 50 to The transition metal-inert carrier catalysts contain about 70 weight percent of (B). (A) contains about 25 to about 50 to about 70 weight percent metal/metal oxide about 35 weight percent reduced transition metal, about 60 and about 30 to about 50 weight percent carrier. About 25 to about 35 weight percent transition metal oxide 40 to about 60 weight percent of the metal/ metal oxide and about 30 to about 50 weight percent suitable carrier, is reduced to the metal. The catalysts can also contain a said weight percents being based on the weight of (A). small amount of promoters, such as aluminum, magne (B) contains about 85 to about 95 weight percent fatty sium, zirconium, or titanium. Generally, such promot amine and about 5 to about 15 weight percent alkane, 65 ers will'be used in the amount of 0 to about 5 weight said weight percents being based on the weight of (B). percent based on the weight of the catalysts. The fatty groups of the fatty amine are alkyl groups The fatty amines which are used as coatings or as containing 12 to 22 carbon atoms. The alkane contains encapsulants for the metal-carrier catalysts are primary 4,980,327 3 4 and secondary amines which have about 12 to about 22 Forty minutes after purging with hydrogen had be carbon atoms in each alkyl group. Examples of such gun, analysis of a sample shows that conversion of ni amines are lauryl amine, dilauryl'amine, myristyl amine, trile to amine is 33.9 percent with the amount of second dimyristyl amine, palmyl amine, dipalmyl amine, stearyl ary amine being 15.2 percent. After 80 minutes, the amine, distearyl amine, archidyl amine, diarchidyl conversion from nitrile to amine is 67.4 percent with the amine, behenyl amine and dibehenyl amine. The pre amount of secondary amine being 31.7 percent. After ferred amines are those containing 16 to 18 carbon 120 minutes, the conversion from nitrile to amine is 86.4 atoms in each fatty group. The most preferred amines percent, and the amount of secondary amine is 50.7 are secondary amines containing 18 carbon atoms in percent. each fatty group. Exemplary of such preferred amines is EXAMPLE 3 di(saturated tallow) amine. The alkanes useful in this invention are the ten to Using the same procedure described in Example 1, a twenty two carbon atom alkanes, i.e., dodecane, tetra nickel/nickel oxide catalyst on diatomaceous earth is decane, hexadecane, octadecane, eicosane and doco encapsulated with di(saturated tallow) amine and hexa sane. The preferred alkanes are hexadecane and octa decane. The catalyst contains 71.6 parts of di(saturated decane. Mixtures of the alkanes can be used. tallow) amine, 8 parts of hexadecane 13.5 parts of nick The coating or encapsulating composition, i.e., the el/nickel oxide, and 6.9 parts of diatomaceous earth.

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