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US5135901.Pdf ||||||||||||||| US005135901A United States Patent (19) (11) Patent Number: 5,135,901 Beavers 45) Date of Patent: Aug. 4, 1992 (54) A CATALYST COMPOSITION COMPRISING (56) References Cited RHODIUM, RUTHENIUMAND A PROMOTER U.S. PATENT DOCUMENTS 3,687,981 8/1972 Lawrence et al. .. ... 549/372 (75) Inventor: William A. Beavers, Longview, Tex. 4,193,942 3/1980 Gerritsen et al. ... ... 502/166 X (73) Assignee: Eastman Chemical Company, 4,453,019 6/1984 Chang .............. ... 502/166 X Rochester, N.Y. 4,668,651 3/1987 Billig et al. ... 502/161 X 4,719, 145 l/1988 Neely .............................. 502/325 X (21) Appl. No.: 711,771 Primary Examiner-W. J. Shine (22) Filed: Jun. 7, 1991 Assistant Examiner-Douglas J. McGinty Attorney, Agent, or Firm-Mark A. Montgomery; Related U.S. Application Data William P. Heath, Jr.; S. E. Reiter 62) Division of Ser. No. 568,150, Aug. 16, 1990, Pat. No. 5,043,480, which is a division of Ser. No. 372,797, Jun. (57) ABSTRACT 29, 1989, Pat. No. 4,973,741. A catalyst used in a process for producing a 3-hydrox (51) Int. Cl. ...................... B01J 23/64; B01J 27/185; yester product or a 3-hydroxyaldehyde product from B01J 27/24; B01J 23/46 ethylene oxide, carbon monoxide, and, optionally, hy (52) U.S. Cl. .................................... 502/161; 502/162; drogen, is disclosed. This process uses, as a catalyst, a 502/325; 502/200, 502/213; 502/230; 502/201; catalyst comprising rhodium, ruthenium, and a Group 502/217; 502/170, 502/167; 502/233; 502/166 Va promoter. (58) Field of Search ............... 502/325, 200, 213, 230, 502/201, 217, 170, 161, 167, 162,233, 166 4 Claims, No Drawings 5,135,901 1. 2 and acrylates suitable for inclusion in any number of A CATALYST COMPOSITION COMPRISING solvents, resins, and plastics. RHODIUM, RUTHENIUMAND A PROMOTER The invention method is based on the carbonylation of ethylene oxide to g-hydroxypropionic acid deriva This is a divisional of copending application Ser. No. 5 tives, and optionally dehydrating the intermediate into 07/568,150 filed Aug. 16, 1990, now U.S. Pat. No. acrylic acid derivatives. By selecting different alcohol 5,043,480 which is a divisional of Ser. No. 372,797 filed functionalities to make the g-hydroxypropionic acid Jun. 29, 1989 now U.S. Pat. No. 4,973,741 issued Nov. derivatives, the properties of these final products can be 27, 1990. modified, 10 This invention encompasses a general method for BACKGROUND OF THE INVENTION producing difunctional compounds which have applica 1. Field of the Invention tions in such diverse areas as solvents, resins, coatings, The present invention relates to the production of and plastics. The catalyst system described herein is p-hydroxyesters or 6-hydroxyaldehydes from ethylene both versatile and more active than prior art catalysts oxide and synthesis gas. 15 known for these reactions. One basic catalyst formula 2. Discussion of the Background tion can be used for carbonylation, hydroformylation, The hydroformylation of ethylene oxide over cobalt or homologation giving good yields of each type of catalysts has been known for some time to yield g reaction product. hydroxyaldehydes (see, e.g., "Organic Syntheses Via It has been discovered that a catalyst comprising the Metal Carbonyls," I. Wender and P. Pino (1968), John 20 metals rhodium and ruthenium along with a Group Va Wiley and Sons, Inc., pp. 384-388; "Carbon Monoxide promoter is capable of converting ethylene oxide into in Organic Synthesis;" J. Falbe, (1970), Springer-Ver useful compounds having a three-carbon chain. Carry lag, pp 58-59). A major problem with this reaction, ing out the reaction under different reaction conditions however, is that it only provides low yields of alde will produce different products in good selectivities hydes. Attempting to increase yield of aldehydes using 25 Depending on the conditions selected, the main prod more forcing reaction conditions or longer reaction ucts obtained are f3-hydroxyesters or g-hydroxyalde times produces aldol condensation products instead of hydes. The conditions under which each of these prod the desired aldehyde products. ucts are predominantly formed is described in greater Rhodium is not known to catalyze the hydroformyla detail below. tion of ethylene oxide. It is known that rhodium pro 30 motes the carbonylation of ethylene oxide to produce DETAILED DESCRIPTION OF THE B-lactones (see "Homogeneous Catalysis with Com INVENTION pounds of Rhodium and Iridium," by R. S. Dickson; D. The catalyst composition provided by the present Reidel Publishing House, 1985). invention comprises (1) 100 parts of a rhodium compo It is also known to promote the carbonylative ring 35 nent, (ii) 0.1 to 10 parts of a ruthenium component, and opening of ethylene oxide in the presence of alcohols to (iii) 10 to 10 parts of a promoter component. The rho yield 3-hydroxypropionate esters as disclosed, for ex dium component is a rhodium salt or a rhodium com ample, by Kawabata et al. in Nippon Kagaku Kaishi, plex. The ruthenium component is a soluble homoge 635 (1979). These authors disclose the use of dicobalt nous ruthenium compound or a finely divided ruthe octacarbonyl/pyridine catalysts. The resulting prod nium metal. The promoter component is a nitrogen ucts, at present, have limited utility, being used for the containing compound, a phosphorus-containing com preparation of acrylate esters which in turn can be used pound, an arsenic-containing compound, or an antimo for the preparation of acrylate resins and polyesters. iny-containing compound. There is thus a distinct need for a process for readily The process for preparing a g-hydroxyproponate producing useful products from ethylene oxide 45 ester provided by the invention comprises contacting synthesis gas, ethylene oxide, a primary C1-6 alkyl alco OBJECTS OF THE INVENTION hol or benzyl alcohol, and a catalyst at a temperature . Accordingly, one object of this invention is to pro from 40 C. to 120° C.; wherein the catalyst comprises vide a novel process for producing a 3-hydroxyester rhodium, ruthenium, and a group Va promoter, and product from ethylene oxide, carbon monoxide, hydro 50 wherein the synthesis gas has a hydrogen to carbon gen, and a primary alcohol. monoxide molar ratio of from 0 to 0.5. It is another object of this invention to provide a The process for preparing a £3-hydroxypropionalde novel process for producing a g-hydroxyaldehyde hyde (or its dimer, 2013-hydroxyethyl)-4-hydroxy-1,3- product from ethylene oxide, carbon monoxide, and dioxane) provided by the present invention comprises hydrogen. 55 contacting synthesis gas, ethylene oxide, and a catalyst It is another object of this invention to provide a at a temperature of from 50' C. to 130' C.; wherein the novel catalyst composition useful for catalyzing the catalyst comprises rhodium, ruthenium, and a Group transformation of ethylene oxide, carbon monoxide, and Va promoter, and wherein the synthesis gas has a hy hydrogen into useful products. drogen to carbon monoxide molar ratio of from 0.3 to These and other objects of the invention will become 3.0. - apparent from the description of the invention given Any soluble form of rhodium is acceptable for the herein below. preparation of invention catalyst, including any insolu BRIEF DESCRIPTION OF THE INVENTION ble form which will dissolve under the conditions of the reaction. These forms include rhodium salts such as In accordance with the present invention, there is 65 rhodium nitrate, rhodium sulfate, rhodium chloride, provided a method for converting ethylene oxide into rhodium bromide, rhodium iodide, rhodium fluoride, difunctional compounds having a three-carbon chain. rhodium oxide, rhodium phosPhate, and the like; or These products include 1,3-disubstituted compounds organic rhodium salts such as rhodium formate, rho 5,135,901 3 4. dium acetate, rhodium propionate, rhodium butyrate, divided finely enough by mechanical means such as and the like; or aromatic rhodium salts such as rhodium ruthenium powder, ingot, shot, sponge, or wire. Of benzoate, rhodium phthalate, rhodium naphthenate, and course, one preferred form, by analogy to its nickel the like. More preferable forms because of their greater analog, would be Raney ruthenium. solubilities are rhodium complexes including any of the The Group Va promoter can be from any member of rhodium carbonyls, rhodium(III)tris(2,4-pentanedion the series of elements including nitrogen, phosphorous, ate), rhodium(I)dicarbonyl(2,4-pentanedionate), dir arsenic, or antimony. Preferably, the promoter used is hodium tetracarbonyl dichloride, iodo rhodium(I)tris(- present in their most reduced forms as tertiary organic triphenylphosphine), bromo rhodium(I)tris(triphenyl derivatives. phosphine), chloro rhodium(I)tris(triphenylphosphine), 10 Examples of suitable Group Va bond promoter cata fluoro rhodium(I)tris(triphenylphosphine), rhodium(I)- lysts include tertiary alkyl amines such as triethyl carbonyl chlorobis(triphenylphosphine), rhodium(I)hy amine, tripropyl amine, tributyl amine, etc.; cyclicter drido carbonyl tris(triphenylphosphine), or other solu tiary amines such as N-methylpiperidine, N-methylpyr ble rhodium complexes within the spirit of this group. rolidine, and 1,4-diazabicyclo2,2,2Octane; tertiary aro The concentrations of rhodium under which the in 15 matic amines such as triphenyl amine, trinaphthyl vention reactions will take place are 106 molar to 10 anine, etc.; mixed alkyl, aromatic, and alkyl-aromatic molar more preferably 10 to 3 molar; and most pref amines from the previous examples; and, pyridines. erably 102 molar to 1 molar. Suitable phosphines include tertiary alkyl phosphines The ruthenium component, which is optional for the such as trimethyl phosphine, triethyl phosphine, tri production of 3-hydroxyester products, but which is 20 propylphosphine, tributyl phosphine, trioctylphos more important in the production of 6-hydroxypro phine, tricyclohexylphosphine, tribenzyphosphine, etc.; pionaldehyde, should be present in concentrations de tertiary aromatic phosphines such as triphenylphos pendent upon that of the primary rhodium component.
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