United States Patent [191 [1 1] 4,409,404 Pretzer Et Al

United States Patent [191 [1 1] 4,409,404 Pretzer et al. [45] * Oct. 11, 1983 [54] PROCESS FOR PRODUCING ETHANOL [56] References Cited USING SAID NOVEL CATALYST SYSTEM U.S. PATENT DOCUMENTS [75] Inventors: ' Wayne R. Pretzer; Thaddeus P. 3,248,432 4/1966 Riley et al. ........................ .. 568/902 3,285,948 ll/l966 Butter . .. 568/902 ‘ Kobylinski, both of Gibsonia; John E. 3,448,157 6/1969 Slaugh et a1. Bozik, Pittsburgh, all of Pa. , .. 568/909 3,631,111 12/1971 >Tucci ............ .. 568/909 4,133,966 l/1979 Pretzer et al. 568/902 [73] Assignee: Gulf Research & Development 4,139,924 12/ 1980 Pretzer et al'. .. 568/902 Company, Pittsburgh, Pa. 4,239,925 12/19801 Pretzer et al. .................... .. 568/902 OTHER PUBLICATIONS [*1 Notice: The portion of the term of this patent subsequent to Jan. 9, 1996 has been Wender et al., “Science”, vol. 113 (1951), pp. 206-207. disclaimed. Primary Examiner-J. E. Evans Attorney, Agent, or Firm—Deane E.’ Keith; Forrest D. [21] Appl. No.: 352,807 Stine; Joseph J. Carducci [s7] ' ABSTRACT ‘ [22] Filed: Feb. 26, 1982 A novel process for selectively , producing ethanol which comprises introducing into a reaction zone (1) methanol, (2) hydrogen, (3) carbon monoxide, (4) a Related U.S. Application Data cobalt carbonyl, a hydrido cobalt carbonyl or a cobalt [63] Continuation-impart of Ser. No. 220,427, Dec. 29, containing material convertible to a cobalt carbonyl or 1980, Pat. No. 4,346,020, which is a continuation-in a hydrido cobalt carbonyl, (5) a tertiary organo Group part of Ser. No. 42,563, May 25, 1979, abandoned, VA compound of the Periodic Table, (6) an iodine which is a continuation-in-part of Ser. No. 939,258, compound and (7) a ruthenium compound; and then Sep. 5, 1978, abandoned. subjecting the contents of said reaction zone to an ele vated temperature and an elevated pressure for a time [51] Int. Cl.3 ..................... .. C07C 29/00; C07C 27/00 suf?cient to convert methanol to ethanol. [52] U.S. Cl. ........................................... .. 568/902 [58] Field of Search ....................................... .. 568/902 32 Claims, No Drawings 4,409,404 1 L 2 complicates the separation and recovery of desired PROCESS FOR PRODUCING ETHANOL USING products, but results in reduced yieldlof ethanol and SAID NOVEL CATALYST SYSTEM erosion of reactants in the production of undesirable by-products. This application is a continuation~in-part application The reaction of methanol with hydrogen and carbon of our US. patent application Ser. No. 220,427 for monoxide to produce ethanol is appreciated and dis NOVEL CATALYST SYSTEM AND PROCESS closed by'the prior art. However, in general, most FOR PRODUCING ETHANOL USING SAID known processes produce an undesirable, large mixture NOVEL CATALYST SYSTEM, ?led Dec. 29, 1980, of alcohols, aldehydes, ketones and carboxylic acids in now US. Pat. No. 4,346,020 which, in turn, was a con addition to the desired alcohol. tinuation-in-part application of our US. patent applica For example, US. Pat. No. 3,285,948, entitled HA tion Ser. No. 42,563, ?led May 25,1979 now abandoned LIDES OF RUTHENIUM ANDOSMIUM IN CON for PROCESS FOR PRODUCING ETHANOL, JUNCTION WITH COBALT AND IODINE IN which, in turn, was a continuation-in-part application of THE - PRODUCTION OF ETHANOL FROM , our US. patent application Ser. No. 939,258, ?led Sept. 15 METHANOL, issued to Butter on Nov. 15, 1966, 5, 1978 now abandoned for CRITICAL I/Co RATIOS teaches a method for producing alcohols in which any IN A METHANOLCARBONYLATION PROCESS‘ source of cobalt soluble in the reaction medium which FOR THE SELECTIVE PRODUCTION OF ETHA will yield ‘a cobalt carbonyl or hydrogen. cobalt car NOL. bonyl under the reaction conditions can be used. In 20, addition, an iodine promoter is employed, for example BACKGROUND OF THE INVENTION 1;, or alkali metal iodides. A secondary promoter is also 1. Field of the Invention employed, i.e., ruthenium halide or osmium halide. This invention is directed to the use of a novel cata I-Iigh selectivity is described as better when the second lyst system comprising (1) a cobalt carbonyl, a hydrido ary promoter is used in combination with the primary cobalt carbonyl or a cobalt-containing material convert promoter and other reactants. - ible to a cobalt carbonyl or a hydrido cobalt carbonyl, ‘US. Pat. No. 4,013,700, entitled CATALYTIC (2)_ a tertiary organo Group VA compound of the Peri PROCESS FOR POLYHYDRIC ALCOHOLS AND odic Table, (3) an iodine compound and (4) a ruthenium DERIVATIVES, issued to Cawse on Mar. 22, 1977, compound in anovel process for selectively producing discloses a process for the preparation of polyhydric ethanol which ‘comprises introducing into a reaction alcohols, their ether and ester derivatives, and oligo zone (1) methanol, ‘(2) hydrogen, (3) carbon monoxide, mers of such alcohols. In particular, these alcohols and (4) a cobalt carbonyL'ahydrido cobalt carbonyl or a their derivatives are produced by reacting the oxides of cobalt-containing,material convertible to a cobalt car carbon and hydrogen in the presence of a quaternary“ bonyl or a hydrido cobalt carbonyl, (5) a tertiary or phosphonium cation and a rhodium carbonyl complex ganol Group VA compound of the Periodic Table, (6) at elevated temperature and pressure. an iodine compound and (7) a ruthenium compound, Another process is set forth in US. Pat. No. and then subjecting the contents‘of said reaction zone to 3,248,432, entitled PROCESS FOR THE PRODUC an elevatedtemperature and an elevated pressure‘for a TION OF ETHYL ALCOHOL, issued to Riley et al. time‘siif?cie'nt to‘ convert methanol to ethanol. on Apr. 26, 1966, which relates to a process for the 2'. Description of the ‘Prior Art , 40 production of ethyl alcohol by the interaction of methaQ 0' ‘Ethanol is a compound‘ which has been used by man nol, carbon monoxide and hydrogen at elevated temper since time immemorial. Historically, ethanol has been ature and pressure in the presence of a cobalt catalyst, produced for various purposes by the fermentation of an iodine promoter and an phosphorus compound solu- ‘ common grainsf‘However, within recent years syn ble in methanol. Examples of suitable cobalt sources are thetic processes have'been developed to synthesize this 45 described as any water-soluble source of cobalt, for alcohol for industrial use. Such synthetic processes example, the cobalt carbonyls, the lower salts of alkano permit the use of more economical starting materials ate cobalt, such as cobalt acetate, cobalt formate, cob'alt than those used in the fermentation processes, andaddi propionate, and the like. tionally, permit production and reproduction of a more US Pat. No. 2,623,906, entitled PREPARATION ' standardized product and more easily predictable yields OF ORGANIC HYDROXY-CONTAINING COM~ of end product. Methanol can easily and economically POUNDS BY REACTING ALCOHOLS WITH‘ be produced in great quantities from‘ hydrogen and CARBON MONOXIDE AND HYDROGEN, issued carbon monoxide or from almost anything containing to Gresham on June 16, 1948, relates to a procedure for carbon and hydrogen, for example, from methane to synthesizing mono- and poly-functional oxygen-con; manure and from coal to crude oil’ residues. One such 55 taining organic compounds by the reaction of alcohols, process for producing ethanol synthetically involves ‘carbon monoxide and hydrogen. Catalysts described as reacting methanol with carbon monoxide and hydrogen suitable for use include various cobalt compounds, for at elevated temperatures and pressures in’ the presence example, cobalt ' carbonyl, cobalt carbonyl hydride, of a catalyst system. metallic cobalt, and organic and inorganic cobalt salts. The conversion of an alcohol, for example, methanol, 60 The process, however, suffers from the disadvantage of to the primary alcohol containing one carbon atom poor product distribution. more than the original alcohol, namely ethanol, is nor Dutch Pat. No. 760.6138, entitled PROCESS FOR mally a tedious and time~consuming procedure involv THE FORMATION OF ETHANOL FROM METH ing a series of steps. Additionally, catalysts‘ which pos ANOL AND SYNTHESIS GAS, issued to Shell Inter sess acceptable activity generally tend to" give a wide national Research on June 8, 1976, relates to a process _ spectrum of products, in addition‘ to ethanol, for exam for producing alcohols which utilizes any soluble cobalt ple, hydrocarbons and oxygenated hydrocarbons hav source which can generate a cobalt carbonyl or hydro ing a broad distribution of carbon atoms. This not only carbonyl by reaction with the synthesis gas. For exam 4,409,404 3 4 ple, sources of cobalt suitable for use are cobalt iodide cobalt (II) carbonate, or cobalt metal from which ions can be generated in cobalt (II) propionate, situ. Organic salts of cobalt such as cobalt acetate, for cobalt (II) octoate, mate, or propionate, are described as especially good cobalt (II) butyrate, sources; an iodide or bromide promoter is also utilized. cobalt (II) benzoate, In addition, the use of a tertiary phosphine is described cobalt (II) valerate, ' as affording improved selectivity to the formation of cobalt (II) formate, v alcohols. ' cobalt (II) cyclohexanebutyrate, In our U.S. Pat. No. 4,133,966 dated Jan. 9, 1979, a cobalt (II) 2-ethyl-hexoate, process is disclosed for the selective formation of etha cobalt (II) gluconate, nol, which comprises contacting methanol, hydrogen cobalt (II) lactate, and carbon monoxide with a catalyst system comprising cobalt (II) naphthenate, cobalt acetylacetonate,

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