Preparing Esters By Carbonylation Patents (Class 560/232)
  • Patent number: 5124300
    Abstract: A catalyst system, which comprises:a) a source of a Group VIII metal;b) a phosphine having an aromatic substituent which contains an imino nitrogen atom;c) a source of protons; andd) a tertiary amine.
    Type: Grant
    Filed: February 4, 1991
    Date of Patent: June 23, 1992
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 5124290
    Abstract: A process for removing metallic corrosion products from carbonylation reactions which are carried out under anhydrous conditions and in which methyl acetate and/or methanol and/or dimethyl ether are reacted over a noble metal catalyst system which comprises a noble metal of group VIII of the periodic table of the elements, a co-catalyst, such as iodide or bromide, in particular methyl iodide, and a promoter, such as an organophosphonium or organoammonium salt, and if appropriate a lithium salt, to give acetic acid and/or acetic anhydride is described, the process comprisinga) bringing the reaction solution which is contaminated with metallic corrosion products and contains the catalyst system into contact with an ion exchanger;b) separating this reaction solution which has been brought into contact in this way from the ion exchanger;c) desorbing the promoter adsorbed on the ion exchanger before regeneration with acetic acid and/or acetic anhydride;d) combining the eluate obtained in step c) with the reaction
    Type: Grant
    Filed: October 16, 1991
    Date of Patent: June 23, 1992
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Reinhard Gradl, Erhard Jagers, Andreas Seidel, Peter Prinz
  • Patent number: 5117046
    Abstract: Alkylidene diesters such as ethylidene diacetate are produced by reacting an ether and/or an ester under substantially anhydrous conditions with carbon monoxide and hydrogen in contact with a catalyst system comprising a rhodium compound and a halogen component at a temperature in the range from 125.degree. to 300.degree. C. and at a carbon monoxide partial pressure in the range from about 1.0 to 1100 kg/cm.sup.2. When ethylidene diacetate is the product, it can then be decomposed to produce vinyl acetate and acetic acid by well-known techniques. Since one mole of acetic acid is also produced in the synthesis of the diacetate, the invention makes possible an overall process for the production of vinyl acetate which produces acetic acid rather than consumes it.
    Type: Grant
    Filed: June 30, 1975
    Date of Patent: May 26, 1992
    Assignee: Monsanto Company
    Inventors: Frank E. Paulik, Robert G. Schultz
  • Patent number: 5047377
    Abstract: In a process for the purification and recovery of a contaminated catalyst solution produced during carbonylation of methanol and/or methyl acetate and/or dimethyl ether and containing carbonyl complexes of rhodium, organic and/or inorganic promoters, undistillable organic impurities and acetic acid, acetic anhydride and ethylidene diacetate, the organic impurities and acetic acid, acetic anhydride and ethylidene diacetate are removed from the contaminatd catalyst solution by extraction at pressures from 35 to 450 bar and temperatures from 0.degree. to 120.degree. C.
    Type: Grant
    Filed: August 6, 1990
    Date of Patent: September 10, 1991
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Eitel Goedicke, Winfried Lork, Heribert Tetzlaff
  • Patent number: 5026908
    Abstract: An alcohol such as methanol is reacted with carbon monoxide in a liquid reaction medium containing a rhodium catalyst stabilized with an iodide salt, especially lithium iodide, along with alkyl iodide such as methyl iodide and alkyl acetate such as methyl acetate in specified proportions. With a finite concentration of water in the reaction medium the product is the carboxylic acid instead of, for example, the anhydride. The present reaction system not only provides an acid product of unusually low water content at unexpectedly favorable reaction rates but also, whether the water content is low or, as in the case of prior-art acetic acid technology, relatively high, is characterized by unexpectedly high catalyst stability; i.e., it is resistant to catalyst precipitation out of the reaction medium.
    Type: Grant
    Filed: May 25, 1990
    Date of Patent: June 25, 1991
    Assignee: Hoechst Celanese Corporation
    Inventors: Brad L. Smith, G. Paull Torrence, Adolfo Aguilo', James S. Alder
  • Patent number: 5026903
    Abstract: A process for the production of ethylidene diacetate by the catalytic reaction of dimethyl acetal, methyl acetate and carbon monoxide in contact with a homogeneous catalyst system containing rhodium metal atom and lithium iodide.
    Type: Grant
    Filed: March 21, 1986
    Date of Patent: June 25, 1991
    Assignee: Union Carbide Chemicals and Plastics Technology Corporation
    Inventor: Edgar C. Baker
  • Patent number: 5026904
    Abstract: Hydrocarbyl formates, convertible by hydrolysis into formic acid, are produced by reacting carbon dioxide and hydrogen with a compound of formula ROH wherein R is a hydrocarbyl group in the presence of a substantially insoluble compound of an element selected from Groups III to VIII of the Periodic Table, which element exhibits amphoteric or basic properties, and as catalyst a compound of a transition metal of Group VIa, VIIa or VIII of the Periodic Table, particularly rhodium, ruthenium or iridium.
    Type: Grant
    Filed: February 15, 1985
    Date of Patent: June 25, 1991
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Philip G. Lodge, David J. H. Smith
  • Patent number: 5003104
    Abstract: This invention involves a process for the carbonylation of a carbonylatable reactant, e.g., an alkyl ester, a dialkyl ether or mixtures thereof by reacting the same with carbon monoxide. The process comprises effecting the carbonylation in the presence of a solution of a catalyst system containing a rhodium compound, an iodide and a lithium component at a temperature of from 50.degree. C. to 400.degree. C. at a carbon monoxide partial pressure of 1 psig to 15,000 psig. Hydrogen may also be present. The invention also concerns a carbonylation catalyst system effective for the addition of carbon monoxide to a carbonylatable reactant which comprises a solution containing as essential components a rhodium containing active component, an iodide and a lithium component.
    Type: Grant
    Filed: October 31, 1988
    Date of Patent: March 26, 1991
    Assignee: BP Chemicals Limited
    Inventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, Robert G. Schultz, James F. Roth
  • Patent number: 5002914
    Abstract: A process for purifying and recovering the contaminated catalyst solution arising from the carbonylation of methanol, methyl acetate and/or dimethyl ether. The solution contains carbonyl complexes of rhodium, quaternary organophosphorus compounds as organic promoters, undistillable organic impurities, and acetic acid, acetic anhydride and ethylidene diacetate. The carbonyl complex of rhodium together with acetic acid, acetic anhydride and ethylidene diacetate are extracted from the contaminated catalyst solution by using a tri-C.sub.3 - to C.sub.8 -alkylphosphine. The trialkylphosphine phase is separated from the promoter phase and is separated into the volatile constituents acetic acid, acetic anhydride and ethylidene diacetate as well as trialkylphosphine. The rhodium carbonyl complex remaining as the residue and the recovered trialkylphosphine is used for further extraction.
    Type: Grant
    Filed: March 9, 1990
    Date of Patent: March 26, 1991
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Winfried Lork, Norbert Weferling, Peter Prinz
  • Patent number: 4994603
    Abstract: A process for the preparation of methyl formate by reacting methanol and carbon monoxide in the presence of an alkali metal alcoholate or alkaline earth metal alcoholate at from 30.degree. to 150.degree. C. and from 50 to 300 bar, wherein a nonionic complexing agent is used to bind the alkali metal cations or alkaline earth metal cations.
    Type: Grant
    Filed: September 4, 1981
    Date of Patent: February 19, 1991
    Assignee: BASF Aktiengesellschaft
    Inventors: Franz-Josef Mueller, Wolfgang Steiner, Karl-Heinz Ross, Otto Kratzer
  • Patent number: 4990654
    Abstract: A process for the production of acetate esters by the catalytic reaction of an alcohol of the formula ROH and carbon monoxide in contact with a homogeneous catalyst system of rhodium metal atom, a phosphorus containing ligand in which there is present at least one oxo (.dbd.O) oxygen atom attached to a phosphorus atom or a carbon atom to form a Z group and the ##STR1## group is located at least one carbon atom removed and preferably from 2-4 carbon atoms removed from the phosphorus atom of the molecules represented by the formulas ##STR2## and a halogen promoter, under mild reaction conditions, wherein R' is H, aryl, alkaryl, aralkyl or alkyl, and wherein 1 or more of said R' groups can be substituted with a Z group but not more than 3 of said R' groups in the molecule are so substituted; a is an integer from 0-4; b is an integer from 0-3; and Z is P(O)R'R'; --C(O)OR" or C(O)R", wherein R" is R'; and wherein ROH is methanol or a mixture of methanol and at least one higher alcohol.
    Type: Grant
    Filed: January 4, 1990
    Date of Patent: February 5, 1991
    Assignee: Union Carbide Chemicals and Plastics Company Inc.
    Inventor: Richard W. Wegman
  • Patent number: 4985383
    Abstract: In a process for removing the metallic corrosion products from a contaminated catalyst solution produced on carbonylation of methanol and/or methyl acetate and/or dimethyl ether and containing carbonyl complexes of noble metals from group VIII of the Periodic Table of the elements, quaternary organo-phosphorus compounds as organic promoters, metallic corrosion products and acetic acid, acetic anhydride, ethylidene diacetate and, in some cases, undistillable organic compounds, the catalyst solution is treated with water, the noble metal carbonyl complex and the undistillable organic compounds, if present, being precipitated, while the organic promoter and the metallic corrosion products remain in solution; the aqueous phase is separated from the precipitated noble metal carbonyl complex and the organic promoter is extracted from the aqueous phase using C.sub.4 -C.sub.
    Type: Grant
    Filed: January 26, 1990
    Date of Patent: January 15, 1991
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Winfried Lork, Andreas Seidel, Peter Prinz
  • Patent number: 4981619
    Abstract: A process for preparing alpha-hydroxycarboxylic acids. An organic halide is reacted with carbon monoxide and a hydrogen donor compound, in the presence of a carbonylation catalyst and an inorganic base, at a temperature of at least 90.degree. C.
    Type: Grant
    Filed: November 28, 1986
    Date of Patent: January 1, 1991
    Assignee: Rhone Poulenc Specialities Chimiques
    Inventor: Bernard Besson
  • Patent number: 4980503
    Abstract: It has been surprisingly discovered in accordance with the present invention that glycol formates and their alkyl ether derivatives can be substantially selectively converted to monocarboxylic acids by bringing a glycol formate or an alkyl ether derivative thereof into contact with a bed of activated carbon in the presence of carbon monoxide and a halide promoted group VIII soluble transition metal catalyst optionally in the presence of a solvent.
    Type: Grant
    Filed: August 15, 1986
    Date of Patent: December 25, 1990
    Assignee: Texaco Inc.
    Inventors: John M. Larkin, George P. Speranza
  • Patent number: 4939292
    Abstract: Esters are prepared by contacting, under suitable reaction conditions, a feed stream comprising a primary alcohol of 1-4 carbon atoms per molecule (preferably methanol, ethanol) and carbon monoxide with a catalyst composition comprising (a) copper or a copper compound (preferably CuO), (b) zinc oxide, (c) at least one metal or compound of at least one metal selected from the group consisting of cobalt, ruthenium, iridium, platinum, molybdenum, and rhenium (preferably cobalt and/or rhenium) and, optionally, (d) alumina.
    Type: Grant
    Filed: October 2, 1985
    Date of Patent: July 3, 1990
    Assignee: Phillips Petroleum Company
    Inventors: David J. Elliott, Filippo Pennella
  • Patent number: 4918218
    Abstract: Preparation of acetic acid and methyl acetate by gas-phase carbonylation of methanol in the presence of a nickel-containing catalyst and in the presence of chlorine, bromine or iodine or a volatile compound of one of these halogens as a promoter, wherein the active material of the catalyst used consists of not less than 40% by weight of nickel and the catalyst contains 0.001-1 part by weight of palladium per part by weight of nickel, as well as supported catalysts whose active material contains Ni and Pd in the above ratio.
    Type: Grant
    Filed: June 25, 1984
    Date of Patent: April 17, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Franz-Josef Mueller, Dominique Matt
  • Patent number: 4908477
    Abstract: Organic iodine compounds are separated from carbonylation products of methanol, methyl acetate and dimethyl ether and from mixtures of such carbonylation products by a process wherein the iodine compounds are removed by liquid phase extraction with a non-aromatic hydrocarbon.
    Type: Grant
    Filed: March 9, 1987
    Date of Patent: March 13, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Horst Hartmann, Waldhelm Hochstein, Gerd Kaibel, Franz-Josef Mueller
  • Patent number: 4897473
    Abstract: This invention produces higher homologs, i.e., differing by at least a --CH.sub.2 -unit, of carbonyloxy-containing compounds by treating the carbonyloxy-containing compounds with carbon monoxide and hydrogen in the presence of a ruthenium-containing compound, a proton donor, an iodide promoter, and optionally, a manganese-containing compound.
    Type: Grant
    Filed: May 1, 1981
    Date of Patent: January 30, 1990
    Assignee: Union Carbide Chemicals and Plastics Company Inc.
    Inventor: Bernard D. Dombek
  • Patent number: 4894188
    Abstract: Fatty acid and their derivatives are simply produced by reacting an olefin, carbon monoxide and water or reacting an alcohol or its derivative and carbon monoxide in the presence of a hydrogen fluoride catalyst and thermally decomposing the resulting reaction product in the presence of a lower hydrocarbon or a lower halogenated hydrocarbon.
    Type: Grant
    Filed: February 13, 1985
    Date of Patent: January 16, 1990
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Takehiko Takahashi, Makoto Takagawa, Tomiyoshi Furuta, Toshio Hidaka, Kazuo Takada
  • Patent number: 4886905
    Abstract: Process for the preparation of ethylidene diacetate and/or ethyl acetate by hydrogenating acetic anhydride in the presence of a homogeneous ruthenium catalyst, methyl iodide and, optionally, lithium iodide. The process can also be utilized to hydrogenate mixtures of acetic anhydride and ethylidene diacetate to produce ethyl acetate.
    Type: Grant
    Filed: May 23, 1983
    Date of Patent: December 12, 1989
    Assignee: Eastman Kodak Company
    Inventor: Thomas H. Larkins, Jr.
  • Patent number: 4843170
    Abstract: A process is disclosed for producing vinyl acetate from methanol, carbon monoxide and hydrogen which comprises the following five steps:(a) methanol is hydrocarbonylated in a hydrocarbonylation zone to produce ethanol, acetaldehyde, methyl acetate and dimethylacetal, and the products are separated in a separation zone;(b) methyl acetate is carbonylated in a carbonylation zone to produce acetic anhydride;(c) the acetaldehyde and dimethylacetal produced in the step (a) and the acetic anhydride produced in the step (b) are converted to ethylidene diacetate and methyl acetate; (d) the ethylidene diacetate produced in the step (c) is thermally decomposed to vinyl acetate and acetic acid, and the products are separated in a separation zone; and(e) the methyl acetate produced and separated in the step (a), (c) or (d) is supplied to the carbonylation step (b).
    Type: Grant
    Filed: February 15, 1983
    Date of Patent: June 27, 1989
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Tomiya Isshiki, Yasuhiko Kijima, Akira Ito, Kenji Ishii
  • Patent number: 4810821
    Abstract: Alkylidene diesters such as ethylidene diacetate are selectively produced in high yields by reacting an ether and/or an ester under substantially anhydrous conditions with carbon monoxide and hydrogen in contact with a catalyst system comprising a rhodium compound, a halogen component, a palladium cocatalyst and a promoter component which is an agent for liberation of carboxylic acid anions. The process is carried out in the liquid phase in a solvent comprising a carboxylic acid at a temperature in the range of 150.degree. to 190.degree. C. and at a carbon monoxide partial pressure in the range from about 1.0 to 1100 kg/cm.sup.2 and a carbon monoxide/hydrogen mole ratio of 6:1 to 1:2 for the ester reaction and 10:1 to 1:2 for the ether reaction. When ethylidene diacetate is the product, it can then be decomposed to produce vinyl acetate and acetic acid by well-known techniques.
    Type: Grant
    Filed: May 31, 1985
    Date of Patent: March 7, 1989
    Assignee: Monsanto Company
    Inventors: Frank E. Paulik, Robert G. Schultz
  • Patent number: 4792620
    Abstract: A catalyst system having high activity and selectivity to carbonylation products comprises a rhodium-containing catalytically active component and a halogen-containing promoter component, the halogen being selected from the group consisting of bromine, iodine, bromide compounds, and iodide compounds.
    Type: Grant
    Filed: March 3, 1987
    Date of Patent: December 20, 1988
    Assignee: BP Chemicals Limited
    Inventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, James F. Roth
  • Patent number: 4790963
    Abstract: A process for producing an ester is disclosed comprising contacting a gaseous reactant containing at least one organic hydroxy compound and a mixture of carbon monoxide and hydrogen with an ester synthesis catalyst of the formulaM.sub.a A.sub.b RuCu.sub.c N.sub.z O.sub.xwhereinM is selected from the group consisting of Ce, Cr, Fe, Mn and mixtures thereof,A is an alkali metal, alkaline earth metal or mixture thereof,a is from 0 to about 1,b is from 0.002 to about 10,c is from 0.2 to about 20,z is from 0 to about 196 by weight,x is the number of oxygens needed to fulfill the valence requirements of the other elements.The organic hydroxy compound can be provided separately or formed by contacting a mixture of carbon monoxide and hydrogen with an alcohol synthesis catalyst at an elevated temperature and pressure. The alcohol synthesis catalyst and ester synthesis catalyst can be in tandem or mixed.
    Type: Grant
    Filed: August 20, 1984
    Date of Patent: December 13, 1988
    Assignee: The Standard Oil Company
    Inventors: Thomas G. Attig, Anne M. Graham, Frederick A. Pesa
  • Patent number: 4780566
    Abstract: A process is described for producing ethyl acetate either alone or in mixture with acetic acid, by homologation of methyl acetate with CO and H.sub.2 in the presence of a catalyst in the form of a Ru compound and a catalysis promoter of hard acid type.The process has considerable advantages over known processes, in particular with regard to the reaction rate and the low formation of undesirable by-products.
    Type: Grant
    Filed: March 8, 1984
    Date of Patent: October 25, 1988
    Assignee: Consiglio Nazionale Delle Ricerche
    Inventors: Giuseppe Braca, Glauco Sbrana, Anna M. Raspolli, Franco Zanni
  • Patent number: 4746640
    Abstract: Catalyst solution contaminated during the carbonylation of methyl acetate and/or dimethylether.
    Type: Grant
    Filed: March 16, 1987
    Date of Patent: May 24, 1988
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Klaus Gehrmann, Winfried Lork
  • Patent number: 4734525
    Abstract: An alkyl ester of formic acid is prepared by reacting carbon monoxide with an alcohol in the presence, as catalyst, of (a) a guanidine or (b) an amidine and an epoxide.The amidine or guanidine structure can by cyclic. The process can be operated in the liquid phase at pressures from 20 to 120 bars and temperatures from 40.degree. to 150.degree. C. with excess carbon monoxide over that required for conversion of the alcohol to the formate ester.
    Type: Grant
    Filed: September 20, 1983
    Date of Patent: March 29, 1988
    Assignee: BP Chemicals Limited
    Inventor: Michael J. Green
  • Patent number: 4733006
    Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) and iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases and unreacted olefin, alcohol or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the carbon monoxide deficient zones of the system of a catalyst stabilizer which is a germanium (IV) compound, an alkali metal compound, and mixtures thereof.
    Type: Grant
    Filed: August 18, 1983
    Date of Patent: March 22, 1988
    Assignee: Monsanto Company
    Inventors: Thomas C. Singleton, Frank E. Paulik
  • Patent number: 4703064
    Abstract: This invention relates to the manufacture of valuable alcohols containing 1 to 2 carbon atoms, especially ethylene glycol, methanol, and ethanol, from the reaction of hydrogen and carbon monoxide, by a homogeneous catalytic process using as the catalyst a synergistic mixture of solubilized ruthenium carbonyl complexes.
    Type: Grant
    Filed: November 28, 1983
    Date of Patent: October 27, 1987
    Assignee: Union Carbide Corporation
    Inventor: Bernard D. Dombek
  • Patent number: 4694108
    Abstract: A process of producing higher ketones comprises the step of contacting under suitable conditions a feed comprising (a) at least one C.sub.3 -C.sub.6 aliphatic ketone, (b) at least one C.sub.2 -C.sub.6 aliphatic aldehyde and, preferably, also (c) carbon monoxide with a catalyst composition comprising (i) copper or an oxide thereof and (ii) zinc oxide. Preferably, the feed ketone is methyl ethyl ketone, the feed aldehyde is propanal, and the product comprises at least one C.sub.7 ketone.
    Type: Grant
    Filed: August 1, 1986
    Date of Patent: September 15, 1987
    Assignee: Phillips Petroleum Company
    Inventor: David J. Elliott
  • Patent number: 4690912
    Abstract: A catalyst system having high activity and selectivity to carbonylation products comprises a rhodium-containing catalytically active component and a halogen-containing promoter component, the halogen being selected from the group consisting of bromine, iodine, bromide compounds, and iodide compounds.
    Type: Grant
    Filed: October 14, 1983
    Date of Patent: September 1, 1987
    Assignee: Monsanto Company
    Inventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, James F. Roth
  • Patent number: 4681707
    Abstract: Carboxylic acid esters are produced by reacting an unsaturated hydrocarbon, for example an olefin or an alkyne, with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper. In a modification of the invention carboxylic acids are produced by omitting the alcohol reactant and replacing it with water in an amount up to 8 mole equivalents based on the unsaturated hydrocarbon and a solvent other than an alochol, for example tetrahydrofuran.
    Type: Grant
    Filed: April 23, 1984
    Date of Patent: July 21, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, Bertrand Despeyroux, David J. H. Smith, James B. Woell
  • Patent number: 4673753
    Abstract: Complex rhodium compounds containing rhodium in combination with the ligands carbon monoxide and a plurality of triarylphosphines and have the formulae:[(aryl.sub.3 P).sub.2 Rh(CO)(alkylCN)].sub.8-n X.sup.+n M.sub.12 O.sub.40, I[(aryl.sub.3 P).sub.2 Rh(CO)(alkylCN)].sub.9-n X.sup.+n M.sub.12 O.sub.40, II[(aryl.sub.3 P).sub.2 Rh(CO)].sub.8-n X.sup.+n M.sub.12 O.sub.40, III[(aryl.sub.3 P).sub.2 Rh(CO)].sub.9-n X.sup.+n M.sub.12 O.sub.40, IV[(aryl.sub.3 P).sub.2 Rh(CO).sub.3 ].sub.8-n X.sup.+n M.sub.12 O.sub.40, and V[(aryl.sub.3 P).sub.2 Rh(CO).sub.3 ].sub.9-n X.sup.+n M.sub.12 O.sub.40, VIwherein alkyl is lower alkyl (C.sub.1 to C.sub.4), X is a transition element selected from Periodic Table groups IIIA, IVA, VA, or VIII, aryl can be phenyl or phenyl substituted by 1 to 3 lower alkyl (C.sub.1 and C.sub.4) and lower alkoxy (C.sub.1 to C.sub.4) groups, M is molybdenum (Mo) or tungsten (W), and n is an integer having a value 2 to 5.
    Type: Grant
    Filed: February 3, 1986
    Date of Patent: June 16, 1987
    Assignee: Minnesota Mining and Manufacturing Company
    Inventor: Allen R. Siedle
  • Patent number: 4670570
    Abstract: A process for the production of organic carboxylic acids by the catalytic reaction of an alcohol and, carbon monoxide in contact with a homogeneous catalyst system of rhodium metal atom, a phosphorus containing ligand in which there is present at least one oxo oxygen atom attached to a phosphorus atom or a carbon atom to form a Z group and the ##STR1## in said Z group is located at least one carbon atom removed from the phosphorus atom of the molecules represented by the formulas ##STR2## and a halogen promoter, under mild reaction conditions, wherein R' is aryl, alkaryl, aralkyl or alkyl, and wherein 1 or more of said R' groups can be substituted with a Z group but not more than 3 of said R' groups in the molecule are so substituted; a is an integer from 0-4; b is an integer from 0-3; and Z is P(O)R'R'; --C(O)OR" or C(O)R", wherein R" is R' or --H.
    Type: Grant
    Filed: July 31, 1986
    Date of Patent: June 2, 1987
    Assignee: Union Carbide Corporation
    Inventors: Richard W. Wegman, Anthony G. Abatjoglou
  • Patent number: 4668816
    Abstract: High yields of aromatic, aromatic acetic and olefinic acids, esters, amides and the like are derived from a process wherein a halo-hydrocarbon is carbonylated in the presence of a palladium catalyst, a hindered amine base and phosphine in excess. The hindered amine base can comprise C.sub.3 -C.sub.10 branched alkyls, cyclic compounds, or mixtures of the above. The preferred amine is N,N-diisopropylethyl amine. The preferred catalyst is PdCl.sub.2 (PPH.sub.3).sub.2 with the excess phosphine generally supplied by a compound of the formula PR.sup.1 R.sup.2 R.sup.3 where R.sup.1, R.sup.2 and R.sup.3 are preferably phenyl.
    Type: Grant
    Filed: November 12, 1985
    Date of Patent: May 26, 1987
    Assignee: Stauffer Chemical Company
    Inventor: Ronald A. Epstein
  • Patent number: 4664753
    Abstract: The disclosure relates to a process for separating iodine and its compounds from the carbonlyation products acetic acid, acetic anhydride or ethylidene diacetate obtained by subjecting dimethylether, methyl acetate or methanol to a carbonylation reaction. For reducing the quantity of total iodine contaminating the carbonlyation products to less than 20 ppb iodine, the disclosure provides for the carbonylation products to be treated at temperatures of 20.degree. to 250.degree. C. with an alkyl or aryl phosphine or a heterocyclic aromatic nitrogen compound and at least one of the metals copper, silver, zinc or cadmium or their compounds and to be distillatively separated from the iodine thereby fixed in non-volatile form.
    Type: Grant
    Filed: August 6, 1984
    Date of Patent: May 12, 1987
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Klaus Gehrmann, Winfried Lork, Peter Prinz
  • Patent number: 4665213
    Abstract: Carboxylic acid esters are produced by reacting an olefinic hydrocarbon with an ester of formic acid in the presence of both carbon monoxide and oxygen at a temperature of up to 200.degree. and a pressure of up to 300 bar in the presence of water, typically in an amount of from 0.01 to 5% w/w, a source of protons, which is preferably a mineral acid or a tectometallosilicate in the hydrogen form, and as catalyst (a) a source of palladium, and (b) a source of copper.
    Type: Grant
    Filed: August 25, 1986
    Date of Patent: May 12, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, David J. H. Smith
  • Patent number: 4661623
    Abstract: A method of producing methyl formate from methanol and carbon monoxide using an anionic transition metal catalyst including a metal selected from Fe, Ru, Os, W, Mo, Cr, Co, Rh and Ir. The reaction is characterized as a low pressure reaction conducted at a pressure less than 3,000 psia and using concentrated anhydrous methanol solutions and, preferably neat methanol. The catalyst can be a mixed metal catalyst including a second metal selected from Group VIII metals. The reaction is highly selective towards methyl formate and excellent turnover numbers are obtained using these catalysts.
    Type: Grant
    Filed: March 19, 1985
    Date of Patent: April 28, 1987
    Assignee: Ashland Oil, Inc.
    Inventors: Biau-Hung Chang, Robert A. Grimm, Bhupendra C. Trivedi
  • Patent number: 4661624
    Abstract: A process for the production of alkyl formates such as methyl formate from the reaction of a carbon monoxide containing gas and an alkyl alcohol, such as methanol, is disclosed. The process features low conversions of alkyl alcohol to alkyl formate, high catalyst concentrations, higher reaction zone temperatures, improved process thermal efficiencies, and reduced apparatus requirements.
    Type: Grant
    Filed: August 13, 1984
    Date of Patent: April 28, 1987
    Inventors: Tsuan Y. Chang, Neil Yeoman, Ronald F. Cascone
  • Patent number: 4661619
    Abstract: Carboxylic acids and/or esters thereof are produced by reacting either a benzylic or an aromatic mercaptan with carbon monoxide and either water or an aqueous alcohol at elevated temperature, suitably in the range from 100.degree. to 300.degree. C., in the presence as catalyst of a cobalt carbonyl, the product using water as the reactant being a carboxylic acid and using aqueous alcohol as the reactant a carboxylic acid ester, mixtures of acids and esters being formed using aqueous alcohols having high water concentrations.
    Type: Grant
    Filed: November 29, 1984
    Date of Patent: April 28, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, Sang C. Shim, David J. H. Smith
  • Patent number: 4661631
    Abstract: Acetic acid is produced by reacting methanol with carbon monoxide in the presence of hydrogen, in the presence of a catalyst comprising a molybdenum-nickel or a tungsten-nickel cocatalyst component, in the presence of an iodide, and in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound, the ratio of the partial pressure of hydrogen to the partial pressure of carbon monoxide in the reaction zone being 0.05 to 0.4.
    Type: Grant
    Filed: December 28, 1983
    Date of Patent: April 28, 1987
    Assignee: The Halcon SD Group, Inc.
    Inventors: Mitchell Becker, Howard M. Sachs
  • Patent number: 4659518
    Abstract: A carboxylic acid, such as acetic acid, is prepared by carbonylation of a hydrocarbyl alcohol, such as methanol, by the use of a molybdenum-nickel or tungsten-nickel co-catalyst in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent and in the presence of an iodide.
    Type: Grant
    Filed: December 24, 1980
    Date of Patent: April 21, 1987
    Assignee: The Halcon SD Group, Inc.
    Inventor: Nabil Rizkalla
  • Patent number: 4659865
    Abstract: A process for producing ethylidenediacetate which comprises reacting methyl acetate or dimethyl ether, carbon monoxide and hydrogen in the presence of catalyst comprising as a secondary-component at least one material selected from the group consisting of, iodides and bromides and as a main component combination of (1) at least one material selected from the group consisting of nickel and nickel compounds, at least one material selected from the group consisting of cobalt and cobalt compounds under substantially anhydrous conditions is disclosed. According to the present invention synthesis of ethylidenediacetate is achieved by using a cheaper catalyst than the prior catalyst.
    Type: Grant
    Filed: July 30, 1984
    Date of Patent: April 21, 1987
    Assignee: Mitsubishi Gas Chemical Co., Inc.
    Inventors: Tomiya Isshiki, Yasuhiko Kijima, Yuh Miyauchi, Takayuki Yasunaga
  • Patent number: 4642370
    Abstract: Carboxylic acid esters are produced by reacting (i) carbon monoxide, (ii) a compound of the formula M(OR).sub.x wherein M is either boron, silicon, aluminum, titanium or zirconium, x is the valency of M and R is a hydrocarbyl group and (iii) a hydrocarbyl halide, wherein the halide moiety is bromide, chloride or iodide, in the presence of a catalyst comprising one or more of the metals rhodium, iridium and cobalt in either elemental or compound form. When M is boron, silicon or aluminum and the halide moiety is chloride, there is preferably added a source of iodide.
    Type: Grant
    Filed: March 14, 1985
    Date of Patent: February 10, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, David J. H. Smith, James B. Woell
  • Patent number: 4640802
    Abstract: Process for the co-production of carboxylic acids of the general formula R.sup.1 --COOH and R.sup.2 --COOH and carboxylic acid esters of the general formula R.sup.1 --COOCH.sub.2 R.sup.2 and R.sup.2 --COOCH.sub.2 R.sup.1 from carboxylic acid esters of the general formula R.sup.1 --COOR.sup.2 and/or ethers of the general formula R.sup.3 OR.sup.4 (R.sup.1, R.sup.2, R.sup.3, R.sup.4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R.sup.1 also representing H), carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound, a further Group VIII metal compound, a phosphine oxide and a compound R.sup.5 Hal or R.sup.5 COHal where R.sup.5 has one of the meanings given for R.sup.2 and Hal is iodine or bromine, the reaction mixture being substantially free from other transition metal or Group II metal iodides or bromides, and containing a tertiary phosphine oxide.
    Type: Grant
    Filed: July 7, 1982
    Date of Patent: February 3, 1987
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4629809
    Abstract: A process for producing acetic acid is disclosed which comprises reacting methanol with carbon monoxide at an elevated temperature and pressure in the presence of an iodine-free catalyst system wherein the catalyst consists of ruthenium compound, quaternary phosphonium salt, cobalt-compound and inorganic acid or an organic acid, reacted in combination in a liquid form or a ruthenium on inert solid support catalyst with a sulfur-containing acid promoter.
    Type: Grant
    Filed: July 21, 1983
    Date of Patent: December 16, 1986
    Assignee: Texaco Inc.
    Inventors: Steven H. Vanderpool, Jiang-Jen Lin, Roger G. Duranleau
  • Patent number: 4629711
    Abstract: Catalyst solution contaminated during the carbonylation of methyl acetate and/or dimethylether, containing carbonyl complexes of rhodium, quaternary heterocyclic aromatic nitrogen compounds or quaternary organophosphorus compounds as organic promoters, undistillable organic contaminants, acetic acid, acetic anhydride and ethylidene diacetate, is purified and recovered.
    Type: Grant
    Filed: April 15, 1986
    Date of Patent: December 16, 1986
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Heinz Erpenbach, Klaus Gehrmann, Winfried Lork, Peter Prinz
  • Patent number: 4628114
    Abstract: A process for the conversion of carboxylic acid esters to homologous carboxylic acid esters which comprises reacting a carboxylic acid ester having from two to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VI-B of the Periodic Table.
    Type: Grant
    Filed: June 23, 1983
    Date of Patent: December 9, 1986
    Assignee: Chevron Research Company
    Inventor: Steven P. Current
  • Patent number: 4628113
    Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising cobalt in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.
    Type: Grant
    Filed: June 30, 1982
    Date of Patent: December 9, 1986
    Assignee: Chevron Research Company
    Inventor: Steven P. Current
  • Patent number: 4625049
    Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising nickel in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.
    Type: Grant
    Filed: June 30, 1982
    Date of Patent: November 25, 1986
    Assignee: Chevron Research Company
    Inventor: Steven P. Current