Of Alcohol Or Alcoholate Patents (Class 562/519)
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Patent number: 5026907Abstract: A process for the production of organic carboxylic acids and organic carboxylic acid anhydrides by the catalytic reaction of an alcohol of the formula ROH and carbon monoxide in contact with an organic ester source and a homogeneous catalyst system of rhodium metal atom, a phosphorus containing ligand in which there is present at least one oxo (.dbd.Type: GrantFiled: November 6, 1985Date of Patent: June 25, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Richard W. Wegman, David J. Schreck
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Patent number: 5026908Abstract: 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: GrantFiled: May 25, 1990Date of Patent: June 25, 1991Assignee: Hoechst Celanese CorporationInventors: Brad L. Smith, G. Paull Torrence, Adolfo Aguilo', James S. Alder
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Patent number: 5003104Abstract: 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: GrantFiled: October 31, 1988Date of Patent: March 26, 1991Assignee: BP Chemicals LimitedInventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, Robert G. Schultz, James F. Roth
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Patent number: 5001259Abstract: 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: GrantFiled: June 3, 1986Date of Patent: March 19, 1991Assignee: Hoechst Celanese CorporationInventors: Brad L. Smith, G. Paull Torrence, Adolfo Aguilo', James S. Alder
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Patent number: 4994608Abstract: The carbonylation of an alcohol to produce a carboxylic acid, especially methanol to produce acetic acid, in a low water 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 is improved by the addition of hydrogen in the feed gas to the low water reaction medium to obtain a reactor hydrogen partial pressure of at least about 4 psi. The presence of hydrogen in the reaction medium increases significantly the carbonylation reaction rate and reduces formation of byproduct carbon dioxide. 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.Type: GrantFiled: August 5, 1987Date of Patent: February 19, 1991Assignee: Hoechst Celanese CorporationInventors: G. Paull Torrence, Joel D. Hendricks, Dennis D. Dickinson, Adolfo Aguilo
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Patent number: 4985383Abstract: 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: GrantFiled: January 26, 1990Date of Patent: January 15, 1991Assignee: Hoechst AktiengesellschaftInventors: Heinz Erpenbach, Winfried Lork, Andreas Seidel, Peter Prinz
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Patent number: 4918218Abstract: 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: GrantFiled: June 25, 1984Date of Patent: April 17, 1990Assignee: BASF AktiengesellschaftInventors: Franz-Josef Mueller, Dominique Matt
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Patent number: 4908477Abstract: 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: GrantFiled: March 9, 1987Date of Patent: March 13, 1990Assignee: BASF AktiengesellschaftInventors: Horst Hartmann, Waldhelm Hochstein, Gerd Kaibel, Franz-Josef Mueller
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Patent number: 4902659Abstract: The present invention provides a process for the preparation of an improved nickel-containing catalyst suitable for the conversion of alcohols to the corresponding carboxylic acid which involves combining a nickel compound, an N-containing organic compound and an iodine promoter, bringing the combination in contact with an alcohol in the presence of carbon monoxide and subjecting the mixture to a temperature and pressure sufficient to initiate carbonylation of the alcohol. The process is characterized in that the N-containing organic compound is isoquinoline or a derivative thereof.Type: GrantFiled: July 12, 1988Date of Patent: February 20, 1990Assignee: Council of Scientific and Industrial ResearchInventors: Ashutosh A. Kelkar, Rengaswamy Jaganathan, Devidas S. Kolhe, Raghunath V. Chaudhari
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Patent number: 4894188Abstract: 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: GrantFiled: February 13, 1985Date of Patent: January 16, 1990Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Takehiko Takahashi, Makoto Takagawa, Tomiyoshi Furuta, Toshio Hidaka, Kazuo Takada
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Patent number: 4894477Abstract: A process for treating carbonylation catalyst solutions which contain a rhodium component and a lithium component to remove metallic corrosion products comprises contacting the catalyst solution with a cation exchange resin in the lithium form.Type: GrantFiled: October 14, 1986Date of Patent: January 16, 1990Assignee: Hoechst Celanese CorporationInventors: Mark O. Scates, G. P. Torrence, Ronny G. Wood
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Patent number: 4801743Abstract: Allyl alcohol is reacted with carbon monoxide in the presence of a catalytically effective amount of a heterogeneous catalyst composition comprising zero valent palladium and a catalyst promoting amount of hydrogen halide to provide a mixture of products predominantly made up of carboxylic acids containing four and five carbon atoms, e.g., 3-butenoic acid, crotonic acid, butyric acid, isobutyric acid, glutaric acid and methyl succinic acid and possibly minor amounts of other oxygenated compounds such as allyl ether and allyl 3-butenoate.Type: GrantFiled: September 19, 1983Date of Patent: January 31, 1989Assignee: National Distillers and Chemical CorporationInventors: William D. Baugh, Jawad H. Murib
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Patent number: 4792620Abstract: 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: GrantFiled: March 3, 1987Date of Patent: December 20, 1988Assignee: BP Chemicals LimitedInventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, James F. Roth
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Patent number: 4790963Abstract: 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: GrantFiled: August 20, 1984Date of Patent: December 13, 1988Assignee: The Standard Oil CompanyInventors: Thomas G. Attig, Anne M. Graham, Frederick A. Pesa
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Patent number: 4733006Abstract: 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: GrantFiled: August 18, 1983Date of Patent: March 22, 1988Assignee: Monsanto CompanyInventors: Thomas C. Singleton, Frank E. Paulik
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Patent number: 4690912Abstract: 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: GrantFiled: October 14, 1983Date of Patent: September 1, 1987Assignee: Monsanto CompanyInventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, James F. Roth
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Patent number: 4661631Abstract: 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: GrantFiled: December 28, 1983Date of Patent: April 28, 1987Assignee: The Halcon SD Group, Inc.Inventors: Mitchell Becker, Howard M. Sachs
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Patent number: 4661619Abstract: 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: GrantFiled: November 29, 1984Date of Patent: April 28, 1987Assignee: The British Petroleum Company p.l.c.Inventors: Howard Alper, Sang C. Shim, David J. H. Smith
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Patent number: 4659518Abstract: 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: GrantFiled: December 24, 1980Date of Patent: April 21, 1987Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4658053Abstract: A process for the production of an ester comprises reacting an olefin with carbon monoxide, hydrogen and another ester at elevated temperature and pressure in the presence of a catalyst comprising (1) a rhodium source, (2) a ruthenium source, and (3) cobalt or zinc iodide. The product ester comprises the acid group of the ester used as reactant esterified with a hydrocarbyl group derived from the olefin, hydrogen and carbon monoxide.Type: GrantFiled: February 25, 1985Date of Patent: April 14, 1987Assignee: BP Chemicals LimitedInventor: Michael J. Green
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Patent number: 4631348Abstract: Acetic acid is prepared by heating methyl formate in the presence of carbon monoxide by the use of a molybdenum-nickel-alkali metal, a chromium-nickel-alkali metal, or a tungsten-nickel-alkali metal co-catalyst in the presence of an iodide or bromide.Type: GrantFiled: June 19, 1985Date of Patent: December 23, 1986Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4629809Abstract: 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: GrantFiled: July 21, 1983Date of Patent: December 16, 1986Assignee: Texaco Inc.Inventors: Steven H. Vanderpool, Jiang-Jen Lin, Roger G. Duranleau
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Patent number: 4628113Abstract: 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: GrantFiled: June 30, 1982Date of Patent: December 9, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4628041Abstract: A process for the recovery of rhodium and iodine values and the separation of rhodium from corrosion metal salts in the manufacture of acetic acid by the carbonylation of methanol wherein the reaction mixture contains from about none to about 20 wt % of water, from about 2 to about 20 wt % of alkali metal or alkaline earth metal iodide, methanol, acetic acid, methyl iodide, and carbon monoxide which comprises: (1) removing at least a portion of the reaction solution from the reactor, (2) removing at least a portion of the product acetic acid from the portion in (1) by distillation, (3) adding an excess of methyl acetate to the product depleted material in (2) and heating the resultant mixture to a sufficiently high temperature to convert the methyl acetate to methyl iodide (4) removing the resulting methyl iodide by distillation, (5) continuing to heat the resulting mixture at a temperature and time sufficient to precipitate the rhodium as rhodium iodide, and (6) separating the rhodium iodide and returning itType: GrantFiled: February 10, 1986Date of Patent: December 9, 1986Assignee: Celanese CorporationInventors: Brad L. Smith, George P. Torrence, Adolfo Aguilo
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Patent number: 4625058Abstract: This invention provides a process for producing an oxy-acetyl compound by carbonylating an oxy-methyl compound with carbon monoxide in the presence of a rhodium catalyst, an iodine compound, and a metallic accelerator, and also in the presence of at least one compound selected from the group consisting of boron compounds, bismuth compounds, and tertiary amide compounds in the reaction system. When at least one of the bismuth or boron compound is present in the reaction system, the carbonylation reaction can proceed without precipitation of any metallic accelerator.Type: GrantFiled: March 12, 1985Date of Patent: November 25, 1986Assignee: Daicel Chemical Industries, Ltd.Inventors: Takaaki Fujiwa, Hidetaka Kojima
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Patent number: 4625060Abstract: Acetic acid is prepared by heating methyl formate in the presence of carbon monoxide 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 a halide.Type: GrantFiled: May 28, 1981Date of Patent: November 25, 1986Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4625049Abstract: 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: GrantFiled: June 30, 1982Date of Patent: November 25, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4620033Abstract: A process for producing a carboxylic acid which comprises reacting a hydrocarbyl alcohol with carbon monoxide in the presence of a metal catalyst selected from nickel or cobalt, a halide and a specific promoter is disclosed. According to the present invention, formation rate of carboxylic acid is high.Type: GrantFiled: February 4, 1985Date of Patent: October 28, 1986Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Tomiya Isshiki, Yasuhiko Kijima, Yuh Miyauchi, Takao Kondo
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Patent number: 4612387Abstract: A method for making monocarboxylic acids and esters comprising contacting carbon monoxide and a monohydric alcohol containing 1 to 4 carbon atoms in the presence of a crystalline aluminosilicate zeolite having a silica to alumina ratio at least about 6 and a constraint index within the approximate range of 1 to 12 under a pressure of at least one atmosphere. Also coproduced are hydrocarbons, particularly ethylene and "gasoline".Type: GrantFiled: January 4, 1982Date of Patent: September 16, 1986Assignee: Air Products and Chemicals, Inc.Inventor: David Feitler
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Patent number: 4547590Abstract: A process is disclosed for the synthesis of alpha-amino acid by first contacting the condensation product of an aldehyde or ketone and an amine or amide with a protic or Lewis acid solvent and carbon monoxide to form an intermediate reaction product, and then hydrolyzing the intermediate to yield a product comprising the alpha-amino acid. The reaction rate and product yield can be increased by the addition of a Group 1B metal oxide catalyst in the first step.Type: GrantFiled: July 6, 1984Date of Patent: October 15, 1985Assignee: W. R. Grace & Co.Inventors: Richard A. Love, Lee R. Zehner
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Patent number: 4519956Abstract: A process for producing acetic anhydride is disclosed which comprises reacting methyl acetate 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 and cobalt-compound. A further embodiment comprises recycling product acetic anhydride with methanol to produce acetic acid.Type: GrantFiled: July 21, 1983Date of Patent: May 28, 1985Assignee: Texaco Inc.Inventors: Jiang-Jen Lin, Roger G. Duranleau
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Patent number: 4514336Abstract: A process for homologating alcohols and/or acids to a mixture of higher acids by reaction with syngas in the presence of a ruthenium-rhodium-iodide-titanium(IV) catalyst.Type: GrantFiled: May 28, 1982Date of Patent: April 30, 1985Assignee: Shell Oil CompanyInventors: Robert C. Ryan, Lynn H. Slaugh
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Process for producing methyl acetate from methanol and carbon monoxide using a novel catalyst system
Patent number: 4484002Abstract: Methyl acetate is prepared in good yield by reacting methanol with carbon monoxide in the presence of a homogeneous catalyst composition comprising a ruthenium-containing compound, a cobalt-containing compound and a quaternary onium salt or base, and heating the resulting mixture at an elevated temperature and pressure for sufficient time to produce the desired methyl acetate, and then recovering the same from the reaction mixture.Type: GrantFiled: January 13, 1982Date of Patent: November 20, 1984Assignee: Texaco Inc.Inventor: Jiang-Jen Lin -
Patent number: 4482497Abstract: 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-alkali metal or a tungsten-nickel-alkali metal co-catalyst in the presence of an iodide or bromide.Type: GrantFiled: September 30, 1982Date of Patent: November 13, 1984Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4436889Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one vanadium compound in which the vanadium is in an oxidation state of 4 or 5, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.Type: GrantFiled: May 5, 1981Date of Patent: March 13, 1984Assignee: Rhone-Poulenc IndustriesInventors: Jean Gauthier-Lafaye, Robert Perron
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Patent number: 4433165Abstract: 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) an 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 system of a stabilizer component selected from N,N,N',N'-tetramethyl-o-phenylenediamine and 2,3'-dipyridyl.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventor: Thomas C. Singleton
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Patent number: 4433166Abstract: 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 containing a rhodium component and an 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 system of a stabilizer which is a tin component which may be tin or a tin compound.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventors: Thomas C. Singleton, Frank E. Paulik
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Patent number: 4431835Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) chromium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.Type: GrantFiled: July 6, 1981Date of Patent: February 14, 1984Assignee: Rhone-Poulenc IndustriesInventors: Jean Gauthier-Lafaye, Robert Perron
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Patent number: 4430506Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) vanadium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.Type: GrantFiled: July 6, 1981Date of Patent: February 7, 1984Assignee: Rhone-Poulenc IndustriesInventors: Jean Gauthier-Lafaye, Robert Perron
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Patent number: 4429057Abstract: A homogeneous catalytic process wherein a gaseous or vaporized reactant stream is continuously introduced into a liquid phase mixture containing (a) a volatile precious metal catalyst, and (b) methanol and/or ethanol as reactant or reaction product, at least a portion of the volatile precious metal being continuously removed from the liquid phase mixture by the effluent gas and/or vapor stream, and such effluent stream is an integral component of a cyclic process stream and/or a vent stream discharged from the process.Type: GrantFiled: August 26, 1982Date of Patent: January 31, 1984Assignee: Union Carbide CorporationInventors: Bernard D. Dombek, George L. O'Connor
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Patent number: 4429150Abstract: Method for the manufacture of ethylidene diacetate by reacting methyl acetate and/or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst comprising a Group VIII metal compound and a halogen-containing compound wherein the reaction is carried out in the presence of a sulphur-containing polar solvent.Type: GrantFiled: July 6, 1981Date of Patent: January 31, 1984Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4426537Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one lanthanide salt, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.Type: GrantFiled: May 5, 1981Date of Patent: January 17, 1984Assignee: Rhone-Poulenc IndustriesInventors: Jean Gauthier-Lafaye, Robert Perron
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Patent number: 4381221Abstract: In a process for recovering an aliphatic carboxylic acid and/or an ester thereof by distilling a liquid mixture containing the aliphatic carboxylic acid and/or the ester thereof and a catalyst of a metal of Group VIII of the periodic table of elements, the improvement wherein the distillation is carried out in the presence of carbon monoxide at a partial pressure of at least 0.01 kg/cm.sup.2 (absolute) in the distillation system to prevent the decomposition of said catalyst.Type: GrantFiled: August 14, 1981Date of Patent: April 26, 1983Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Tomiya Isshiki, Hisashi Yoshino, Kaoru Tsuyuki
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Patent number: 4356320Abstract: A carboxylic acid, such as acetic acid, is prepared from a hydrocarbyl alcohol, such as methanol, in carbonylation processes comprising the use of an iodide, carbon monoxide and a nickel catalyst in the presence of a promoter comprising an organo-phosphorus compound wherein the phosphorus is trivalent.Type: GrantFiled: October 6, 1977Date of Patent: October 26, 1982Assignee: The Halcon SD Group, Inc.Inventors: Anthony N. Naglieri, Nabil Rizkalla
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Patent number: 4356126Abstract: Process for the carbonylation of alkanols and/or ethers at elevated temperature and pressure in the presence of a Group VIII metal compound and pentachlorobenzenethiol and/or salts thereof, using a pentachlorobenzenethiol compound: Group VIII metal compound molar ratio of not more than 10. The process is of special interest for the production of methyl acetate from methanol using an active, iodine-free catalytic system.Type: GrantFiled: June 17, 1981Date of Patent: October 26, 1982Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4351953Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a .PHI.--C.sub.n H.sub.2n -- radical wherein .PHI. is phenyl and 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 --OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one chromium salt in which the chromium is in a state of oxidation (p) of greater than zero (p>0), and in an initial carboxylic acid reaction medium having the formula R.sup.2 --COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.Type: GrantFiled: March 26, 1981Date of Patent: September 28, 1982Assignee: Rhone-Poulenc IndustriesInventors: Jean Gauthier-Lafaye, Robert Perron
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Patent number: 4336399Abstract: A process for producing a carboxylic acid and/or its ester, which comprises reacting an alcohol or ether with carbon monoxide in the presence of elemental nickel or a nickel compound, iodine or an iodine compound and an organic compound of a trivalent nitrogen-group element; wherein the iodine or iodine compound is selected from the following formulae (I) to (IV),RX.sub.n (I)wherein R represents a hydrogen atom or an alkyl or alkylene group, X represents an iodine or bromine atom, and n is an integer of 1 to 3, at least one of n.multidot.X's being an iodine atom,I.sub.2 or I.sub.3 - (II)RCOI (III)wherein R represents an alkyl group,MI.sub.2 (IV)wherein M represents an alkaline earth metal, and the amount of the iodine or iodine compound is such that the amount of the free iodine or iodine compound not chemically bonded to the nickel or nickel compound or the organic compound of a nitrogen-group element is at least 0.Type: GrantFiled: November 10, 1980Date of Patent: June 22, 1982Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Tomiya Isshiki, Yasuhiko Kijima, Yuh Miyauchi
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Patent number: 4334093Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more nickel-containing catalysts in combination with a Group VB tertiary donor ligand and in the presence of an iodide or bromide promoter.Type: GrantFiled: June 30, 1980Date of Patent: June 8, 1982Assignee: Texaco, Inc.Inventor: John F. Knifton
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Patent number: 4334094Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more palladium-containing catalysts in combination with a Group VB tertiary donor ligand and in the presence of an iodide or bromide promoter.Type: GrantFiled: June 30, 1980Date of Patent: June 8, 1982Assignee: Texaco Inc.Inventor: John F. Knifton
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Patent number: 4334092Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more rhodium-containing catalysts and an iodide or bromide promoter.Type: GrantFiled: June 30, 1980Date of Patent: June 8, 1982Assignee: Texaco Inc.Inventor: John F. Knifton