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US5198589.Pdf |||||||||||||||| USOO5198589A United States Patent (19) 11 Patent Number: 5,198,589 Rathke et al. 45 Date of Patent: Mar. 30, 1993 54 COBALT CARBONYL CATALYZED OEFN 5,045,793 9/1991 Rathke ................................ 324/38 HYDROFORMYLATION IN SUPERCRTICAL CARBON OOXDE FOREIGN PATENT DOCUMENTS 2415902 10/1974 Fed. Rep. of Germany . (75) Inventors: Jerome W. Rathke, Lockport; Robert 3415968 10/1985 Fed. Rep. of Germany ...... 568/454 J. Kingler, Westmount, both of Ill. OTHER PUBLICATIONS (73) Assignee: The United States of America as represented by the United States R. Fowler et al., "Hydroformylate propylene at low Department of Energy, Washington, pressure', Hydrocarbon Proc. 55 (9) 247 (1976). D.C. J. W. Rathke et al., "Propylene Hydroformylation in Supercritical Carbon Dioxide', Organometallics 1991, 21 Appl. No.: 874,897 10, 1350-1355. 22 Filed: Apr. 28, 1992 Primary Examiner-Werren B. Lone (51) int. C. ....................... CO7C 45/50; CO7C 29/16 Attorney, Agent, or Firm-James W. Weinberger; John 52 U.S. C. .................................... 568/454; 568/451; M. Albrecht; William R. Moser 568/909 (58 Field of Search ............... 568/451, 454, 456, 840, 57 ABSTRACT 568/850, 882, 909 A method of olefin hydroformylation is provided (56) References Cited wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon non U.S. PATENT DOCUMENTS oxide in the presence of a supercritical reaction solvent, 4,201,728 5/1980 Hughes ............................... 568/454 such as carbon dioxide. The invention provides higher 4,275,243 6/1981 Saito et al. ...... ... 568/454 yields of n-isomer product without the gas-liquid mix 4,349,415 9/1982 DeFilippi et al. .................... 2O3/14 4,437,938 3/1984 Bhise et al. ........................... 203/14 ing rate limitation seen in conventional Oxo processes 4,492,808 1/1985 Hagen et al. ... 568/916 using liquid media. 4,508,928 4/1985 Victor ............. ... 568/916 4,528,404 7/1985 Oswald et al. .. ... 568/4.54 13 Claims, 3 Drawing Sheets HCo(CO)4, CO2, CO, H2 FLASH WAPORIZER 8 C02 FEED REACTOR OLEFINADEHYDE OLEFIN PURIFICATION CO/H2 2 6 EXTRACTORY ALDEHYDE OLEFIN COMPRESSOR COMPRESSOR 14 22 U.S. Patent Mar. 30, 1993 Sheet 1 of 3 5,198,589 BUAHHGTVNIJETO NIJETO 22 |91 HOSSE|HdW00 H010WEIH 29 300 NI-JETO 3H/00 U.S. Patent Mar. 30, 1993 Sheet 2 of 3 5,198,589 C O) S ed O CV d CD O m : o L C (?) \ E Ol Ol 5 U.S. Patent Mar. 30, 1993 Sheet 3 of 3 5,198,589 Ol Ol O CD H g - O O qm O D Q CS O S. CN O CD O -- O r C9 5, 198,589 1 2 conventional Oxoprocesses by creating a homogeneous COBALT CARBONYL CATALYZED OLEFN vapor phase reaction fluid. HYDROFORMYLATION IN SUPERCRITICAL Still another object of the present invention is to CARBON DOXDE provide more efficient conversions of olefins to desired 5 aldehydes and alcohols via the Oxo process. A feature CONTRACTUAL ORIGIN OF THE INVENTION of the present invention is higher concentrations of reactive gases. An advantage of the present invention is The United States Government has rights in this higher yields and lower costs in producing n-isomer invention pursuant to Contract No. W-31-109-ENG-38 aldehydes and alcohols. between the U.S. Government and Argonne National 10 Yet another object of the present invention is to pro Laboratories. vide a more economical Oxo process. A feature of the BACKGROUND OF THE INVENTION present invention is to provide a homogeneous vapor phase reaction environment containing supercritical 1. Field of the Invention carbon dioxide. An advantage of the present invention This invention relates to a method of olefin hydrofor 15 is a more complete and efficient separation of the reac mylation and more particularly to a method of olefin tion catalyst from the desired product, due to sharp hydroformylation in supercritical carbon dioxide result changes in solubilities of dissolved species with the ing in higher yields of the n-isoner. density of the supercritical CO2. 2. Background of the Invention In brief, the objects and advantages of the present Large scale conversion of olefins to aldehydes and/or 20 invention are achieved by mixing predetermined pres alcohols is a well-known commercial objective. Con sures of hydrogen and carbon monoxide and predeter version of ethylene, propylene, butenes and other al mined concentrations of an olefin and a carbonyl cata kenes ranging from C2-C13 and C12-C18 to aldehydes lyst together to create a mixture and supplying a super and alcohols, for example, is necessary to produce more critical reaction medium to the mixture to create and complex molecules for use as plasticizers, detergents 25 maintain a homogeneous vapor phase reaction fluid at a and in a myriad of applications. Such conversions of the predetermined pressure. The objects and advantages of alkene can be made using the Oxo process wherein the invention are further met by providing a method of olefins react with carbon monoxide and hydrogen in the propylene hydroformylation involving mixing prede presence of a catalyst. termined pressures of hydrogen and carbon monoxide There are problems with the conventional Oxo pro 30 and predetermined concentrations of propylene and a cess, however, such as gas-liquid mixing inefficiencies cobalt carbonyl catalyst together to create a mixture wherein reactive gases do not adequately mix with each and supplying supercritical carbon dioxide to the mix other. Gas-liquid mixing problems lower the yield of ture to create and maintain a homogeneous vapor phase the desired n-isomer and limit the upper reaction tem reaction fluid at a predetermined pressure. perature of the process. For example, typical Oxo pro 35 cesses yield isomer selectivity ratios of approximately BRIEF DESCRIPTION OF THE DRAWINGS 3.0:1 to 4:1, or a 75% to 80% n-isomer yield. R. Fowler, The present invention together with the above and H. Connor and R. A. Baehl. Hydrocarbon Proc. 55(9), other objects and advantages may best be understood 247 (1976). A need exists in the art to increase n-isomer from the following detailed description of the embodi yields significantly as straight chain products are the 40 ment of the invention illustrated in the drawings, desired feed stocks for more complex molecule build wherein: ling. FIG. 1 is a diagram of an exemplary process illustrat Another significant shortcoming of the Oxo process ing the present invention; is the low concentrations of carbon monoxide and hy FIG. 2 is a H NMR spectrograph depicting relative drogen in the reaction solvent, leading to low catalysts 45 yields of n-isomer to branched isomers as produced by efficiencies and lower overall product yields. the invention; and Conventional Oxo processes suffer from yet another FIG. 3 is a 13C NMR spectrograph depicting free and shortcoming wherein the separation of catalysts from combined CO resonances in supercritical CO2. products involve energy intensive distillations. A need exists in the art to provide a hydroformylation 50 DETAILED DESCRIPTION OF THE process wherein gas-liquid mixing problems are mini INVENTION mized, concentrations of synthesis gases in the reaction Supercritical fluids (i.e., compounds and elements solvent are maximized, higher ratios of n-isomer to maintained above their critical temperature) have gas iso-isomers are achieved, and more efficient separation like viscosities that ar frequently one order of magni procedures can be utilized for product and catalyst 55 tude lower than those of typical liquids. For example, at recovery. its critical point, carbon dioxide has a viscosity of only 0.025 centipoises (cp) while benzene, at 25' C., has a SUMMARY OF THE INVENTION viscosity of 0.61 cp. This phenomenon is seen even It is an object of the present invention to provide a when supercritical fluids are compressed to achieve method for overcoming many of the disadvantages of 60 liquid-like densities. the approaches or methods of the prior art. It has been found quite unexpectedly that the use of a It is another object of the present invention to pro supercritical fluid, such as carbon dioxide, as the reac vide a method for producing aldehydes and/or alcohols tion medium in Oxo processes improves both the de from olefins via the Oxo process. A feature of the pres sired product yield and product/catalyst separation ent invention is using a supercritical solvent, such as 65 efficiencies. carbon dioxide, as a reaction medium. An advantage of The inventors have found, for example, that the use the present invention is that the use of a supercritical of supercritical carbon dioxide as a reaction medium in solvent eliminates the gas-liquid mixing problems of olefin hydroformylation results in a significant increase 5, 198,589 3 4. in the selectivity ratio of the n-isomer to 7.3:1, com used, however, it is suggested that the temperature of pared to approximately 4:1 seen in conventional pro the reactor 16 is such that the CO2, or another reaction cesses, mentioned supra. Table 1 below compared solvent, is maintained above its critical temperature to known selectivity ratios, obtained with propylene hy prevent liquid formation. droformylation using conventional solvents, with selec The mixture reacts for a predetermined period of tivity ratios experimentally derived, using supercritical time and is then distilled in a flash vaporizer 18. Formu CO2. Specifically, it was found that at 80 C., hydrofor lated aldehyde and alcohol and unreacted olefin are mylation of propylene proceeds cleanly in carbon diox then separated via an extractor 20, with the olefin being ide providing improved yields of linear to branched repressurized by a feedback compressor 22 and readmit butyraldehyde products of 7.3 to 1 (or 88 percent) with 10 ted into the reactor 16 with additional and unspent out use of stirring.
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