Of Halogenated Hydrocarbon Patents (Class 562/520)
  • Publication number: 20150025269
    Abstract: The invention provides a simple, efficient, environmental friendly catalytic system for the direct carboxylation reaction using CO2 under mild condition. A single step heterogeneous catalytic process for preparation of alkynyl carboxylic acids of formula I is disclosed.
    Type: Application
    Filed: January 25, 2013
    Publication date: January 22, 2015
    Inventors: Ravindra Dattatray Aher, Madhuri Hanumant Gage, Reddy Santhosh Rekula, Pratibha Uttam Karabal, Gurunath Mallappa Suryavanshi, Arumugam Sudalai
  • Patent number: 8198476
    Abstract: A process for the production of acetic acid by the liquid phase carbonylation of an alcohol and/or a reactive derivative thereof in which there is employed a catalyst comprising a complex of rhodium or iridium with a pincer ligand.
    Type: Grant
    Filed: May 23, 2008
    Date of Patent: June 12, 2012
    Assignee: BP Chemicals Limited
    Inventors: Emma Louise Carrington-Smith, David John Law, Paul Gerard Pringle, John Glenn Sunley
  • Publication number: 20110201841
    Abstract: Oxidatively halogenate methane by placing a feedstream that comprises methane, a source of halogen, a source of oxygen and, optionally, a source of diluent gas in contact with a first catalyst (e.g. a solid super acid or a solid super base) that has greater selectivity to methyl halide and carbon monoxide than to methylene halide, trihalomethane or carbon tetrahalide. Improve overall selectivity to methyl halide by using a second catalyst that converts at least part of the feedstream to a mixture of methyl halide, methylene halide, trihalomethane, carbon tetrahalide and unreacted oxygen, and placing that mixture in contact with the first catalyst which converts at least a portion of the methylene halide, trihalomethane and carbon tetrahalide to carbon monoxide, hydrogen halide and water.
    Type: Application
    Filed: August 19, 2009
    Publication date: August 18, 2011
    Inventors: Robert G. Bowman, Eric E. Stangland, Mark E. Jones, Dean M. Millar, Simon G. Podkolzin, Brien A. Stears, Richard M. Wehmeyer
  • Publication number: 20100324332
    Abstract: A process for the production of acetic acid by the liquid phase carbonylation of an alcohol and/or a reactive derivative thereof in which there is employed a catalyst comprising a complex of rhodium or iridium with a pincer ligand.
    Type: Application
    Filed: May 23, 2008
    Publication date: December 23, 2010
    Inventors: Emma Louise Carrington-Smith, David John Law, Paul Gerard Pringle, John Glenn Sunley
  • Patent number: 7741512
    Abstract: Process for preparing an aliphatic carboxylic acid having (n+1) carbon atoms, where n is an integer up to 6, and/or the ester derivative thereof by contacting an aliphatic alcohol having n carbon atoms and/or a reactive derivative thereof selected from dialkyl ether, ester of the alcohol and an alkyl halide with carbon monoxide in the presence of a catalyst. The catalyst consists of mordenite which has been ion- exchanged or otherwise loaded with silver.
    Type: Grant
    Filed: March 27, 2007
    Date of Patent: June 22, 2010
    Assignee: BP Chemicals Limited
    Inventors: Harry Kaiser, David John Law, Stephan Andreas Schunk, John Glenn Sunley
  • Patent number: 7053241
    Abstract: Processes for the production of acetic acid by carbonylation of methanol, and reactive derivatives thereof, in a reaction mixture using a rhodium-based catalyst system with at least one metal salt catalyst stabilizer selected from the group of ruthenium salts, tin salts, and mixtures thereof are provided. The metal salt stabilizers minimize precipitation of the rhodium metal during recovery of the acetic acid product, particularly in flasher units in an acetic acid recovery scheme. Stability of the rhodium metal is achieved even when the acetic acid is produced in low water content reaction mixtures in the presence of an iodide salt co-promoter at a concentration that generated an iodide ion concentration of greater than about 3 wt. % of the reaction mixture. The stabilizing metal salts may be present in the reaction mixtures for the production of acetic acid at molar concentrations of metal to rhodium of about 0.1:1 to about 20:1.
    Type: Grant
    Filed: February 24, 2005
    Date of Patent: May 30, 2006
    Assignee: Celanese International Corporation
    Inventor: G. Paull Torrence
  • Patent number: 6849763
    Abstract: The present invention relates to a new process for the synthesis of racemic and optically active bicalutamide starting from ethyl pyruvate and methyl methacrylate. The present invention discloses processes of preparing bicalutamide intermediates including ethyl-[2-{4-fluorophenyl sulfone)]-2-hydroxy propionate, 1,2-epoxy-2-methyl propionate and 2-hydrox-2-methyl-3-(4-fluorophenylthio) propionic acid. The present invention further discloses micronized rac-bicalutamide and the preparation thereof.
    Type: Grant
    Filed: March 8, 2004
    Date of Patent: February 1, 2005
    Assignee: Biogal Gyógyszergyár Rt.
    Inventors: Ben-Zion Dolitzky, Ofer Reany, Jenny Shammai
  • Patent number: 6617471
    Abstract: A vapor-phase carbonylation method for producing esters and carboxylic acids from reactants comprising lower alkyl alcohols, lower alkyl alcohol generating compounds, and mixtures thereof. The method includes contacting the reactants and carbon monoxide in a carbonylation zone of a carbonylation reactor under vapor-phase conditions with a catalyst having a catalytically effective amount of iridium and tin associated with a solid carrier material.
    Type: Grant
    Filed: June 20, 2001
    Date of Patent: September 9, 2003
    Assignee: Eastman Chemical Company
    Inventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
  • Patent number: 6613938
    Abstract: A vapor-phase carbonylation method for producing esters and carboxylic acids from reactants comprising lower alkyl alcohols, lower alkyl alcohol generating compositions and mixtures thereof. The method includes contacting the reactants and carbon monoxide in a carbonylation zone of a carbonylation reactor under vapor-phase conditions with a catalyst having a catalytically effective amount of platinum and tin associated with a solid carrier material.
    Type: Grant
    Filed: June 19, 2001
    Date of Patent: September 2, 2003
    Assignee: Eastman Chemical Company
    Inventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
  • Patent number: 6515172
    Abstract: Process for the preparation of perfluorocarboxylic acids of the formula RF—COOH, salts thereof and esters thereof from perfluoroalkyl iodides of the formula RF′—I, in which RF and RF′ are cyclic, branched or linear, saturated or unsaturated perfluoroalkyl radicals, by activating the perfluoroalkyl iodides in the presence of oxygen and in organic solvents.
    Type: Grant
    Filed: July 10, 2001
    Date of Patent: February 4, 2003
    Assignee: Clariant GmbH
    Inventors: Ralf Grottenmüller, Wolfgang Knaup, Anton Probst, Klaus Dullinger
  • Publication number: 20030018212
    Abstract: A vapor-phase carbonylation method for producing esters and carboxylic acids from reactants comprising lower alkyl alcohols, lower alkyl alcohol generating compositions and mixtures thereof. The method includes contacting the reactants and carbon monoxide in a carbonylation zone of a carbonylation reactor under vapor-phase conditions with a catalyst having a catalytically effective amount of platinum and tin associated with a solid carrier material.
    Type: Application
    Filed: June 19, 2001
    Publication date: January 23, 2003
    Inventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
  • Patent number: 6452058
    Abstract: An oxidative halogenation process involving contacting a reactant hydrocarbon selected from methane, a halogenated C1 hydrocarbon, or a mixture thereof with a source of halogen and, preferably, a source of oxygen in the presence of a rare earth halide or rare earth oxyhalide catalyst, so as to form a halogenated C1 hydrocarbon having a greater number of halogen substituents as compared with the reactant hydrocarbon. Preferably, the product is a monohalogenated methane, more preferably, methyl chloride. The oxidative halogenation process to form methyl halide can be integrated with downstream processes to produce valuable commodity chemicals, for example, methyl alcohol and/or dimethyl ether; light olefins, including ethylene, propylene, and butenes; higher hydrocarbons, including gasolines; vinyl halide monomer, and acetic acid. Hydrogen halide, which is a co-product of these downstream processes, can be recycled to the oxidative halogenation process.
    Type: Grant
    Filed: May 21, 2001
    Date of Patent: September 17, 2002
    Assignee: Dow Global Technologies Inc.
    Inventors: Albert E. Schweizer, Mark E. Jones, Daniel A. Hickman
  • Patent number: 6153792
    Abstract: A process for the production of a carboxylic acid in the presence of solid catalyst particles that employs a flash step with a liquid wash is disclosed. This process helps prevent the buildup of deposits of solid catalyst particles, attrited solid catalyst particles, and heavy by-products in the flash zone. This invention is useful for the production of carboxylic acids, especially acetic acid.
    Type: Grant
    Filed: December 18, 1998
    Date of Patent: November 28, 2000
    Assignee: UOP LLC
    Inventors: William A. Leet, Santi Kulprathipanja
  • Patent number: 6140535
    Abstract: A process as provided for producing an acetic acid process stream having less than 400 ppm propionic acid and less than 1500 ppm water. Methanol or a reactive derivative thereof and carbon monoxide is fed to a carbonylation reactor in which there is maintained during the course of the process a liquid reaction composition containing an iridium carbonylation catalyst, methyl iodide co-catalyst, a promoter, water at a concentration of less than about 8% by weight, methyl acetate, acetic acid, and propionic acid by-product and its precursors. Liquid reaction composition is withdrawn from the carbonylation reactor and introduced to a flash zone to form a vapor fraction comprising water, acetic acid product, propionic acid by-product, methyl acetate, methyl iodide and propionic acid precursors, and a liquid fraction comprising involatile iridium catalyst, involatile optional promoter or promoters, acetic acid and water.
    Type: Grant
    Filed: December 17, 1997
    Date of Patent: October 31, 2000
    Assignee: BP Chemicals Limited
    Inventor: Bruce L Williams
  • Patent number: 6114576
    Abstract: A process for the production of a carboxylic acid in the presence of solid catalyst particles that uses the exothermic heat of reaction with high efficiency in recovering the carboxylic acid product is disclosed. This process uses indirect heat exchange to transfer the heat of reaction to another stream, without the need for an additional heat transfer fluid such as steam. This invention is especially applicable to the production of acetic acid.
    Type: Grant
    Filed: December 18, 1998
    Date of Patent: September 5, 2000
    Assignee: UOP LLC
    Inventors: William A. Leet, Santi Kulprathipanja, Bruce A. Briggs
  • Patent number: 5990347
    Abstract: A process for preparing a carboxylic acid having n+1 carbon atoms by contacting carbon monoxide with a liquid reaction composition comprising an alcohol of n carbon atoms or an ester derivative thereof; an iridium carbonylation catalyst and a hydrocarbyl halide promoter wherein in the liquid reaction composition the concentration of water is about 2 to 8% by weight, the concentration of ester derivative of said alcohol and product acid is from 1 to 60% by weight (preferably 3-35% by weight), and the concentration of hydrocarbyl halide is from 2 to 10% weight.
    Type: Grant
    Filed: April 28, 1995
    Date of Patent: November 23, 1999
    Assignee: BP Chemicals Limited
    Inventor: Kirsten Everald Clode
  • Patent number: 5932764
    Abstract: A process for the production of a carboxylic acid having n+1 carbon atoms comprises (a) carbonylating with carbon monoxide in a first reaction zone at elevated temperature and pressure an alkyl alcohol having n carbon atoms and/or a reactive derivative thereof to produce a carboxylic acid having n+1 carbon atoms in a liquid reaction composition comprising carboxylic acid product, an iridium catalyst, an alkyl halide co-catalyst, water, an ester of the carboxylic acid product and the alkyl alcohol, and optionally one or more promoters, (b) withdrawing from the first reaction zone at least a portion of the liquid reaction composition together with dissolved and/or entrained carbon monoxide, and passing at least a portion of the withdrawn liquid reaction composition and carbon monoxide to a second reaction zone, ((c)reacting at least 1% of the dissolved and/or entrained carbon monoxide in the withdrawn reaction composition by further carbonylation at elevated temperature and pressure in the second reaction zone
    Type: Grant
    Filed: December 4, 1997
    Date of Patent: August 3, 1999
    Assignee: BP Chemicals Limited
    Inventors: George Ernest Morris, John Glenn Sunley
  • Patent number: 5883295
    Abstract: A process for the production of acetic acid comprising carbonylating with carbon monoxide methanol and/or a reactive derivative thereof in the substantial absence of a metal promoter and/or ionic iodide co-promoter in a carbonylation reactor containing a liquid reaction composition comprising an iridium carbonylation catalyst, methyl iodide co-catalyst, water, acetic acid and methyl acetate wherein there is maintained (i) in the liquid reaction composition:(a) water at a concentration of less than 5.0% by weight and(b) methyl iodide at a concentration greater than 12% by weight and (ii) in the carbonylation reactor a total pressure of less than 50 barg.
    Type: Grant
    Filed: December 17, 1997
    Date of Patent: March 16, 1999
    Assignee: BP Chemicals Limited
    Inventors: John G. Sunley, Robert J Watt
  • Patent number: 5883289
    Abstract: A method for preparing carboxylic acids including (n+1) carbon atoms, or the related esters, by liquid phase carbonylation of an alcohol including (n) carbon atoms, in the presence of a uniform catalytic system based on at least one iridium compound and at least one halogenated promoter. In particular, the method is characterised in that the content of ester related to said carboxylic acid and alcohol is kept between 15 and 35% in the medium during the reaction, while the halogenated promoter content is kept between 10 and 20%, and the partial carbon monoxide pressure is 40-200 bar. Said method enables both the rate of carbonylation and the acetic acid selectivity to be increased.
    Type: Grant
    Filed: May 14, 1997
    Date of Patent: March 16, 1999
    Assignee: Acetex Chimie
    Inventors: Philippe Denis, Dominique Nobel, Robert Perron, Joel Andre Schwartz
  • Patent number: 5877348
    Abstract: A process for the production of acetic acid by carbonylating with carbon monoxide methanol and/or a reactive derivative thereof in a carbonylation reactor containing a liquid reaction composition comprising an iridium carbonylation catalyst, methyl iodide co-catalyst, a finite concentration of water, acetic acid, methyl acetate and at least one promoter wherein the water concentration is at or below that at which the maximum in the graph of carbonylation rate versus water concentration occurs and there is employed in the liquid reaction composition a co-promoter selected from alkali metal iodides, alkaline earth metal iodides, metal complexes capable of generating I.sup.-, salts capable of generating I.sup.-, and mixtures of two or more thereof.
    Type: Grant
    Filed: December 17, 1997
    Date of Patent: March 2, 1999
    Assignee: BP Chemicals Limited
    Inventors: Evert Jan Ditzel, John Glenn Sunley, Robert John Watt
  • Patent number: 5877347
    Abstract: A process for the production of acetic acid comprises (1) continuously feeding methanol and/or a reactive derivative thereof and carbon monoxide to a carbonylation reactor containing a liquid reaction composition comprising an iridium carbonylation catalyst, methyl iodide co-catalyst, a finite concentration of water, acetic acid, methyl acetate and, optionally at least one promoter, (2) carbonylating the methanol and/or reactive derivative thereof with the carbon monoxide in the liquid reaction composition to produce acetic acid; and (3) recovering acetic acid from the liquid reaction composition, there being continuously maintained (a) in the liquid reaction composition water at a concentration of no greater than 4.5% by weight, and (b) in the reactor a carbon monoxide partial pressure in the range from greater than 0 to 7.5 bar.
    Type: Grant
    Filed: December 17, 1997
    Date of Patent: March 2, 1999
    Assignee: BP Chemicals Limited
    Inventors: Evert Jan Ditzel, John Glenn Sunley, Robert John Watt
  • Patent number: 5874610
    Abstract: A process for the recovery of a carbonylation product from a liquid reaction composition of an iridium-catalysed carbonylation reaction of a carbonylatable reactant comprises subjecting the composition to a vaporization with or without the addition of heat to produce a vapor-fraction and a liquid fraction, the vapor fraction comprises carbonylation product and the liquid fraction has a water concentration of at least 0.5% by weight to stabilize the iridium catalyst.
    Type: Grant
    Filed: October 23, 1997
    Date of Patent: February 23, 1999
    Assignee: BP Chemicals Limited
    Inventors: Kirsten Everald Clode, Derrick John Watson, Carl Jozef Elsa Vercauteren
  • Patent number: 5847204
    Abstract: An iridium-based solution is prepared by contacting components in a liquid phase containing (a) a carbonylated iridium compound, (b) hydriodic acid, a precursor of such an acid, or mixture thereof, and (c) a solvent; under a total pressure of between 1 and 10 bar at a temperature not greater than the boiling temperature of the solvent under conditions in which the components are brought into contact. The iridium-based solution can be used as a catalyst for carrying out carbonylation, hydroformylation or isomerization reactions.
    Type: Grant
    Filed: September 27, 1996
    Date of Patent: December 8, 1998
    Assignee: Acetex Chimie
    Inventor: Dominique Nobel
  • Patent number: 5834622
    Abstract: A process for the carbonylation of a carbonylatable reactant having a carbonylatable moiety having at least two carbon atoms and/or a reactive derivative thereof which process comprises contacting said carbonylatable reactant and/or a reactive derivative thereof with carbon monoxide in a liquid reaction composition in a carbonylation reactor characterized in that the liquid reaction composition comprises: (a) an iridium catalyst, (b) a halide, (c) at least a finite concentration of water, (d) a carbonylatable reactant having a carbonylatable moiety having at least two carbon atoms and/or a reactive derivative thereof and (e) as promoter, at least one of ruthenium and osmium.
    Type: Grant
    Filed: July 5, 1996
    Date of Patent: November 10, 1998
    Assignee: BP Chemicals Limited
    Inventor: John Glenn Sunley
  • Patent number: 5814193
    Abstract: A process for the purification of a C.sub.2 to C.sub.4 carboxylic acid and/or an anhydride thereof having halide impurities, which process comprises the steps of (a) exposing the impure acid and/or anhydride to electromagnetic radiation under conditions of intensity, wavelength and temperature, and for a time, sufficient to convert at least a portion of the halide impurities to lower--and/or higher-boiling halide components and (b) separating the lower--and/or higher-boiling halide components formed in step (a) from the C.sub.2 to C.sub.4 carboxylic acid and/or anhydride. Also, a process for the purification of a C.sub.2 to C.sub.
    Type: Grant
    Filed: August 9, 1996
    Date of Patent: September 29, 1998
    Assignee: BP Chemicals Limited
    Inventor: Barry Crowe
  • Patent number: 5808143
    Abstract: Catalysts of the formula I?A.sub.a B.sub.b O.sub.x !.sub.p ?C.sub.c D.sub.d Fe.sub.e Co.sub.f E.sub.i F.sub.j O.sub.y !.sub.q I,whereA is bismuth, tellurium, antimony, tin and/or copper,B is molybdenum and/or tungsten,C is an alkali metal, thallium and/or samarium,D is an alkaline earth metal, nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury,E is phosphorus, arsenic, boron and/or antimony,F is a rare-earth metal, vanadium and/or uranium,a is from 0.01 to 8,b is from 0.1 to 30,c is from 0 to 4,d is from 0 to 20,e is from 0 to 20,f is from 0 to 20,i is from 0 to 6,j is from 0 to 15,x and y are numbers determined by the valency and frequency of the elements other than oxygen in I, and p and q are numbers whose ratio p/q is in the range from 0.001 to 0.
    Type: Grant
    Filed: March 22, 1996
    Date of Patent: September 15, 1998
    Assignee: BASF Aktiengesellschaft
    Inventors: Lothar Karrer, Hans-Peter Neumann, Hans-Dieter Eichhorn, Robin Stuart Jarret
  • Patent number: 5773642
    Abstract: Preparation of carboxylic acids or corresponding esters by reacting an alcohol with carbon monoxide in the presence of an iridium catalyst and a halogen promoter. The reaction involves a reaction mixture composed of more than 0% to 10% water, more than 0% to 10% halogen promoter, 2% to 40% of an ester corresponding to the reaction of alcohol with the acid, soluble iodides in an amount such that the atomic ratio of iodides to iridium varies between more than 0 and 10, the carboxylic acid being used as the reaction solvent.
    Type: Grant
    Filed: May 14, 1997
    Date of Patent: June 30, 1998
    Assignee: Acetex Chimie
    Inventors: Philippe Denis, Dominique Nobel, Robert Perron, Philippe Perrona, Joel Schwartz
  • Patent number: 5760279
    Abstract: The use of manganese at a molar ratio of manganese:rhodium of (0.2 to 20):1 to stabilize the rhodium catalyst during the rhodium catalyzed carbonylation of alkyl alcohols and/or recovery of carbonylation product therefrom at low partial pressure of carbon monoxide of less than or equal to 7 bar.
    Type: Grant
    Filed: June 12, 1996
    Date of Patent: June 2, 1998
    Assignee: BP Chemicals Limited
    Inventor: Andrew David Poole
  • Patent number: 5648527
    Abstract: New saturated fluoroalkylamines and carboxyalkylbetaines and alkylsulfobetaines derived therefrom, and mixtures containing the new fluoroalkylamines and mixtures containing the new fluorobetaines are described. The saturated fluoroalkylamines conform to the formula below ##STR1## in which n is an integer from 3 to 17 and R.sup.1 and R.sup.2 are C.sub.1 to C.sub.4 -alkyl, C.sub.1 to C.sub.4 -hydroxyalkyl or hydrogen, with the proviso that only one of the two substituents R.sup.1 and R.sup.2 is hydrogen. The carboxyalkylbetaines and sulfobetaines and the mixtures thereof are highly effective products for reducing the surface tension of water/air systems and the interfacial tension of water/hydrocarbon systems.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: July 15, 1997
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Gunter Prossel, Wolfgang Knaup, Frank Wehowsky
  • Patent number: 5625094
    Abstract: Process for the preparation of a carboxylic acid or ester thereof. The process includes reacting at least one alcohol, alkyl or aryl halide, ether or ester, with carbon monoxide, in the presence of a catalytically effective amount of at least one rhodium compound or rhodium metal, at least one iridium compound or iridium metal, or at least one mixed rhodium/iridium compound, and at least one halogen-containing promoter therefor.
    Type: Grant
    Filed: May 26, 1995
    Date of Patent: April 29, 1997
    Assignee: Rhone-Poulenc Chimie
    Inventors: Dominique Nobel, Robert Perron, Philippe Denis
  • Patent number: 5416237
    Abstract: In a process for the production of acetic acid by carbonylation of methanol in the presence of a rhodium carbonylation catalyst, methyl iodide and an iodide salt stabiliser the improvement resides in maintaining a finite concentration of water of up to about 10% by weight and a methyl acetate concentration of at least 2% by weight in the liquid reaction composition and recovering the acetic acid product by passing the liquid reaction composition through a flash zone to produce a vapour fraction which is passed to a single distillation column from which an acetic acid product is removed.
    Type: Grant
    Filed: July 18, 1994
    Date of Patent: May 16, 1995
    Assignee: BP Chemicals Limited
    Inventors: Simon D. Aubigne, Jeremy B. Cooper, Bruce L. Williams, Derrick J. Watson
  • Patent number: 5312969
    Abstract: Difunctional butenes are linearly dicarbonylated into 3-hexene-1,6-dioic acid or alkyl diesters thereof, well suited for the ultimate production of, e.g., adipic acid, by reacting such difunctional butene with carbon monoxide and, if appropriate, an alcohol, at an elevated temperature under superatmospheric pressure, in the presence of at least one source of hydrogen chloride and a catalytically effective amount of palladium, at least a portion of which palladium being in the zero oxidation state, as well as a quaternary onium chloride of nitrogen or phosphorus, the nitrogen or phosphorus atom being tetracoordinated to carbon atoms, with the proviso that the nitrogen atom may be coordinated to two pentavalent phosphorus atoms.
    Type: Grant
    Filed: May 18, 1992
    Date of Patent: May 17, 1994
    Assignee: Rhone-Poulenc Chimie
    Inventors: Marc Huser, Sylvain Mutez, Robert Perron
  • Patent number: 5214203
    Abstract: Carboxylic acids are produced in the liquid phase carbonylation reaction from an alcohol or its derivative and carbon monoxide in the presence of a catalyst system containing a rhodium component and an alkyl halide and water, adding an iodide salt to the rhodium/alkyl halide catalyst system so as to maintain the iodine ion concentration in the carbonylation reaction solution at 0.3 mol/.lambda. or higher.
    Type: Grant
    Filed: April 27, 1992
    Date of Patent: May 25, 1993
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Hiroshi Koyama, Hidetaka Kojima
  • 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: 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: 4855487
    Abstract: An improved process for preparing a fluorine-containing carboxylic acid ester useful as an intermediate for producing a fluorine-containing carboxylic acid is disclosed. The process comprises reacting a fluorine-containing alkyl halide with carbon monoxide and an alcohol in the presence of a transition metal catalyst of the Group VIII of the Periodic Table and a base, and provides the desired carbonylated compound in high yield.
    Type: Grant
    Filed: July 10, 1987
    Date of Patent: August 8, 1989
    Assignee: Sagami Chemical Research Center
    Inventors: Takamasa Fuchikami, Hisao Urata, Yoshimitsu Ishii, Yoshiko Obata
  • Patent number: 4820823
    Abstract: In accordance with a process of the present invention, .alpha.-keto acids of the general formula RCOCOOH wherein R is aryl, alkenyl or heterocyclic group, can be obtained through one-step carbonylation reaction of an organic halogenide of the general formula RX wherein R is the same as above and X is a halogen atom, with carbon monoxide and water in the presence of a basic compound and a palladium containing catalyst.
    Type: Grant
    Filed: February 21, 1986
    Date of Patent: April 11, 1989
    Assignee: Director-General of Agency of Industrial Science and Technology
    Inventors: Masato Tanaka, Toshiaki Kobayashi, Toshiyasu Sakakura
  • Patent number: 4761499
    Abstract: High yields of olefinic esters and amides, and the like are derived from a process wherein vinyl dihalides are carbonylated in the presence of a palladium catalyst and a primary or secondary amine base or tertiary amine, depending on the desired product, and a solvent.
    Type: Grant
    Filed: June 2, 1987
    Date of Patent: August 2, 1988
    Assignee: Akzo America Inc.
    Inventor: Ronald A. Epstein
  • Patent number: 4738802
    Abstract: A process for the production of an alkyl .alpha.-keto-carboxylic acid of the general formula: ##STR1## wherein: R is a linear or branched alkyl radical having from 1 to about 20 carbon atoms which comprises reacting an alkyl halide of the formula:RXwhere R is as defined above and X represents halogen, in a liquid solvent medium, with carbon monoxide at elevated temperature and pressure in the presence of a catalytic amount of a metal carbonyl compound and an alkali metal inorganic base or an alkaline earth metal inorganic base. Optionally, small amounts of LiI and/or bis(1,2-diphenylphosphino)ethane may be present in the reaction as co-catalysts.
    Type: Grant
    Filed: November 16, 1983
    Date of Patent: April 19, 1988
    Assignee: Ethyl Corporation
    Inventor: John Y. Lee
  • 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: 4713484
    Abstract: A process for preparing carboxylic acid salts by the reaction of carbon monoxide with substituted or unsubstituted aromatic halides or an aliphatic organic halide. The process comprises the catalytic single phase carbonylation of the halide utilizing in addition to carbon monoxide, a palladium catalyst, an excess of tertiary phosphine, optionally an amine compound, with an alkali metal or alkaline earth metal base added during the reaction to form the salt.
    Type: Grant
    Filed: December 22, 1986
    Date of Patent: December 15, 1987
    Assignee: Stauffer Chemical Company
    Inventor: Ronald A. Epstein
  • 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: 4582929
    Abstract: This invention is a process for the carbonylation of an organic halide to prepare a carbonyl-containing compound, and recovery of halogen values in a useful form which comprises(a) contacting an organic halide with carbon monoxide and an esterifying agent, a primary or secondary amine, or hydrogen gas, in an inert organic solvent in the presence of a water-insoluble tertiary amine or pyridine ring-containing compound, and a catalytic amount of a Group VIII metal catalyst, under conditions such that an organic ester, amide or aldehyde is prepared and the halide generated in the process forms a salt with tertiary amine or pyridine compound wherein the halide is bromine or iodine;(b) separating the organic ester, amide or aldehyde from the reaction mixture which contains the tertiary amine or pyridine compound-halide salt;(c) contacting the reaction mixture containing the tertiary amine or pyridine compound-halide salt mixture with a concentrated aqueous solution of an alkali metal base or alkaline earth metal b
    Type: Grant
    Filed: December 24, 1984
    Date of Patent: April 15, 1986
    Assignee: The Dow Chemical Company
    Inventor: Robert A. DeVries
  • Patent number: 4544505
    Abstract: Halo-.alpha.-keto-carboxylic acids are prepared by reacting a dihaloalkane in a liquid solvent medium with carbon monoxide at elevated temperature and pressure in the presence of a catalytic amount of a metal carbonyl compound and an alkali metal inorganic base or an alkaline earth metal inorganic base.
    Type: Grant
    Filed: October 21, 1983
    Date of Patent: October 1, 1985
    Assignee: Ethyl Corporation
    Inventor: Joachim W. Wolfram
  • Patent number: 4473706
    Abstract: Cyclic-keto-acids of the general formula: ##STR1## wherein R is hydrogen or a monovalent alkyl radical which can be either straight chain or branched having from 1 to about 20 carbon atoms and X=1, 3, or 4, are prepared by reacting a functionalized 1-bromoalkane of the formula: ##STR2## wherein R and X are as defined above and Y is a leaving group, preferably the halogens, in a liquid solvent medium with carbon monoxide at elevated temperature and pressure in the presence of a catalytic amount of a metal carbonyl compound and an alkali or an alkaline earth metal inorganic base.
    Type: Grant
    Filed: August 6, 1982
    Date of Patent: September 25, 1984
    Assignee: Ethyl Corporation
    Inventors: John Y. Lee, Thomas J. Walter
  • Patent number: 4451670
    Abstract: A process for the production of isobutyryl fluoride by reacting isopropyl fluoride and carbon monoxide in the presence of anhydrous hydrofluoric acid is described.
    Type: Grant
    Filed: November 2, 1982
    Date of Patent: May 29, 1984
    Assignee: Ashland Oil, Inc.
    Inventors: Dace Grote, Robert A. Grimm, Richard V. Norton
  • Patent number: 4435575
    Abstract: A process is herein described for preparing carboxylated organic compounds (acids, esters, alkaline salts) of formula ##STR1## wherein R is a hydrocarbyl group having up to 11 carbon atoms (an aliphatic, alicyclic, aryl- or heteroarylalkyl group), also substituted, in its turn, by groups inert under the reaction conditions (alkyl, aryl, etheric, thioetheric, halogen, nitrile, ester, amide, ketonic groups), and R' is a hydrogen atom or an alkyl C.sub.1 -C.sub.8 group, by reaction of carbon monoxide with the corresponding hydrocarbyl halides, having the halogen bound to a non-tertiary carbon atom, in the presence of catalysts which are salts of cobalt hydrocarbonyl, or precursors thereof, in a hydro-alcoholic or alcoholic solvent and in the presence of bases.The process is characterized in that the catalytic system composed by the salt of cobalt hydrocarbonyl is supported on an anion exchange resin.
    Type: Grant
    Filed: June 30, 1981
    Date of Patent: March 6, 1984
    Assignee: Montedison S.p.A.
    Inventors: Gianfranco Cainelli, Marco Foa', Achille U. Ronchi, Andrea Gardano
  • Patent number: 4433166
    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 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: Grant
    Filed: December 29, 1980
    Date of Patent: February 21, 1984
    Assignee: Monsanto Company
    Inventors: Thomas C. Singleton, Frank E. Paulik
  • Patent number: 4433165
    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) 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: Grant
    Filed: December 29, 1980
    Date of Patent: February 21, 1984
    Assignee: Monsanto Company
    Inventor: Thomas C. Singleton
  • Patent number: H53
    Abstract: Processes for producing 4,4-dimethyl-3-isoxazolidinone and intermediates for it from known and inexpensive starting materials are described and exemplified.
    Type: Grant
    Filed: February 21, 1984
    Date of Patent: April 1, 1986
    Assignee: FMC Corporation
    Inventors: Borivoj R. Franko-Filipasic, Sol A. Mednick, James Snyder