Of Alcohol Or Alcoholate Patents (Class 562/519)
  • Patent number: 6130355
    Abstract: An anhydrous process for the production of acetic acid by the reaction of methanol, and/or dimethyl ether, with a gaseous reactant comprising carbon monoxide and hydrogen, the hydrogen being present in an amount less than 9 mole %, in the presence of a catalyst system comprising at least one noble metal of Group VIII of the Periodic Table as catalyst, a halo-compound as co-catalyst and an iodide salt as catalyst stabiliser which process comprises feeding methanol, and/or dimethyl ether, and gaseous reactant to a carbonylation reactor in which there is maintained a liquid reaction composition comprising: (i) methyl acetate in an amount from 1 to 35% w/w, (ii) acetic anhydride in an amount up to 8% w/w, (iii) halo-compound in an amount from 3 to 20% w/w, (iv) Group VIII noble metal catalyst in an amount from 1 to 2000 ppm, (v) sufficient iodide salt to provide from 0.5 to 20% by weight iodine as I.sup.- and (vi) acetic acid comprising the remainder of the composition.
    Type: Grant
    Filed: December 24, 1998
    Date of Patent: October 10, 2000
    Assignee: BP Chemicals Limited
    Inventor: Michael David Jones
  • Patent number: 6127432
    Abstract: This invention relates in part to a processes and catalysts for the conversion of a feedstock comprising carbon monoxide and hydrogen to a product stream comprising at least one of an ester, acid, acid anhydride and mixtures thereof. This invention also relates in part to processes and catalysts for converting an alcohol, ether and/or ether alcohol feedstock to oxygenated products, e.g., esters, acids, acid anhydrides and mixtures thereof. The processes and catalysts are especially suitable for the production of acetic acid and methyl acetate from a synthesis gas feedstock or from an alcohol, ether or ether alcohol feedstock.
    Type: Grant
    Filed: December 24, 1998
    Date of Patent: October 3, 2000
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Richard William Wegman, David Michael Minahan, William J. Bartley, Chinsoo Stephen Lee, David McNeill Somerville
  • Patent number: 6127574
    Abstract: A process for the production of a carboxylic acid and/or a carboxylic acid anhydride which process comprises contacting a reaction composition comprising an alcohol and/or a carboxylic acid ester, optionally water, a first hydrocarbyl halide and/or a hydrocarbyl ether reactant and a second hydrocarbyl halide promoter, the first and second hydrocarbyl halides being the same or different, with carbon monoxide in the presence of a catalyst comprising an insoluble imidazole-containing resin supporting a Group VIII metal species.
    Type: Grant
    Filed: June 16, 1998
    Date of Patent: October 3, 2000
    Assignee: BP Chemicals Limited
    Inventors: Mark Julian Howard, Michael David Jones
  • 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: 6103934
    Abstract: There is provided a process control method for the production of acetic acid by the catalyzed carbonylation of methanol and a process for the manufacture of acetic acid using the process control method. The process control method comprises measuring various reactor component concentrations, specifically the active catalyst species, methyl iodide, water and methyl acetate by means of an infrared analyzer, and adjusting in response thereto the concentrations of at least the catalyst species, methyl iodide and water to optimize the acetic acid reaction.
    Type: Grant
    Filed: December 18, 1998
    Date of Patent: August 15, 2000
    Assignee: Millennium Petrochemicals, Inc.
    Inventors: Noel Hallinan, James A. Hinnenkamp
  • Patent number: 6084124
    Abstract: The present invention is a method to produce an unsaturated carboxylic acid which includes the steps of: providing an epoxy compound; contacting the epoxy compound with carbon monoxide in the presence of a catalytically effective amount of a catalyst system comprising tin and cobalt under conditions effective for carbonylation of the epoxy; and recovering a .alpha.-.beta. unsaturated carboxylic acid product. The preferred epoxy is ethylene oxide which is reacted to acrylic acid by the method of the present invention.
    Type: Grant
    Filed: February 4, 1999
    Date of Patent: July 4, 2000
    Assignee: Shell Oil Company
    Inventors: Lynn Henry Slaugh, Thomas Clayton Forschner
  • Patent number: 6066762
    Abstract: A process for the production of a carbonyl compound such as acetic acid by reacting a carbonylatable compound such as methanol with a carbon monoxide in the presence of a carbonylation catalyst containing a noble metal complex supported on a porous, cross-linked vinylpyridine resin at a temperature of 140-250.degree. C., a carbon monoxide partial pressure of 7-30 kg/cm.sup.2 and a hydrogen partial pressure of 0.1-5 kg/cm.sup.2 to obtain a liquid product containing the carbonyl compound and an unreacted CO-containing gas product. The water content and the carbonylation degree of the liquid product within the reactor are maintained at 0.5-10% by weight and 0.5-0.9, respectively, The carbonyl compound is separated from the liquid product in a flasher and/or a distillation tower formed of titanium or a titanium-palladium alloy. The liquid product is introduced into a pressure reducing valve and then mixed with the CO-containing gas product before being fed to the flasher and/or distillation tower.
    Type: Grant
    Filed: December 23, 1997
    Date of Patent: May 23, 2000
    Assignee: Chiyoda Corporation
    Inventors: Noriyuki Yoneda, Takeshi Minami, Yoshihiro Nakagawa, Ikuo Ohta, Akihisa Yamaguchi, Hideki Sugiyama, Fumihiko Uemura
  • Patent number: 6031129
    Abstract: Methanol is converted to acetic acid by reaction with carbon monoxide in the presence of an improved carbonylation system which comprises a rhodium catalyst component and a liquid reaction medium containing water in low levels, acetic acid, methyl iodide, methyl acetate, and at least one pentavalent Group VA oxide wherein the concentration of pentavalent Group VA oxide to rhodium is greater than about 60:1. The present carbonylation system not only increases the yields and reaction rates but also serves to stabilize the rhodium catalyst component in an active form.
    Type: Grant
    Filed: October 3, 1995
    Date of Patent: February 29, 2000
    Assignee: Quantum Chemical Corporation
    Inventors: James A. Hinnenkamp, Noel Hallinan
  • Patent number: 6015923
    Abstract: Process for making 3-pentenoic acid acid by reacting an allylic butenyl alcohol or its corresponding ester with carbon monoxide in the presence of nickel, and a source of iodide.
    Type: Grant
    Filed: December 17, 1998
    Date of Patent: January 18, 2000
    Assignees: E. I. du Pont de Nemours and Company, DSM N. V.
    Inventor: Patrick Michael Burke
  • Patent number: 6011171
    Abstract: The present invention provides a process for synthesizing tertiary carboxylic acids or the esters thereof having one or two more carbon atoms than the raw material has, comprising reacting in a strong acid (e.g., sulfuric acid, sulfuric acid-phosphoric acid, hydrogen fluoride, fluorosulfuric acid, boron trifluoride.water complex and trifluoromethanesulfonic acid) a raw material compound (i.e., olefin, alcohol, diene, diol or saturated hydrocarbon) with carbon monoxide in the presence of a specific metal carbonyl catalyst (i.e., platinum carbonyl catalyst, palladium carbonyl catalyst and gold dicarbonyl catalyst).The metal carbonyl catalyst is formed by reacting in a strong acid at least one specific metal compounds (e.g., platinum compound such as platinum (II, IV) oxide, platinum (II, IV) hydroxide, a platinum powder, etc.; palladium compound such as palladium (II, III, IV) oxide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) carboxylate, a palladium powder, etc.
    Type: Grant
    Filed: November 4, 1997
    Date of Patent: January 4, 2000
    Assignee: Jiro Hiraishi, Director-General, Agency of Industrial Science and Technology
    Inventors: Qiang Xu, Yoshie Souma
  • 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: 5973197
    Abstract: A method for preparing carboxylic acids by carbonylating a reagent, particularly an alcohol, in the presence of a rhodium catalyst. According to the method, the liquid phase reaction is carried out in a first zone in the presence of a rhodium catalyst, and the resulting reaction mixture is partially vaporised in a second zone. The vaporised fraction containing the carboxylic acid is later purified and the unvaporised liquid fraction containing the catalyst is recirculated to the first zone. The method is charactracterised in that said unvaporised fraction is contacted with carbon monoxide in such a way that this compound is not returned to the second zone.
    Type: Grant
    Filed: April 21, 1997
    Date of Patent: October 26, 1999
    Assignee: BP Chemicals Limited
    Inventors: Philippe Denis, Robert Perron, Joel Schwartz
  • Patent number: 5939585
    Abstract: A process for the carbonylation of a C.sub.1 to C.sub.4 alkyl alcohol and/or a reactive derivative thereof by contacting a C.sub.1 to C.sub.4 alkyl alcohol and/or a reactive derivative thereof with carbon monoxide in a liquid reaction composition in a carbonylation reactor in the presence of (a) a rhodium catalyst (b) an alkyl halide, and (c) as promoter, at least one of ruthenium and osmium.
    Type: Grant
    Filed: October 20, 1997
    Date of Patent: August 17, 1999
    Assignee: BP Chemicals Limited
    Inventors: Evert Jan Ditzel, Michael David Jones, Andrew David Poole
  • 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: 5917089
    Abstract: A carbonylation process which comprises (a) contacting, in a first carbonylation reactor at elevated temperature and pressure, an alcohol having n carbon atoms and/or a reactive derivative thereof with carbon monoxide in a liquid reaction composition comprising a halogen and/or halogen compound promoter and a Group VIII noble metal carbonylation catalyst to produce a carbonylation product comprising a carboxylic acid having n+1 carbon atoms and/or an ester of the carboxylic acid having n+1 carbon atoms and the alcohol having n carbon atoms and/or any anhydride of the carboxylic acid having n+1 carbon atoms, (b) withdrawing from the first carbonylation reactor, an off-gas stream comprising carbon monoxide and optionally halogen and/or halogen compound promoter, and optionally carbonylation production; and (c) contacting in a second carbonylation reactor, the withdrawn off-gas stream with an alcohol having m carbon atoms and/or reactive derivative thereof in the presence of a halogen and/or halogen compound pro
    Type: Grant
    Filed: August 9, 1996
    Date of Patent: June 29, 1999
    Assignee: BP Chemicals Limited
    Inventor: Mark Julian Howard
  • Patent number: 5900505
    Abstract: Disclosed is a process wherein a mixture of methanol or a methanol source, a halide and carbon monoxide are contacted in the vapor phase with a supported catalyst comprising iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material.
    Type: Grant
    Filed: January 22, 1998
    Date of Patent: May 4, 1999
    Assignee: Eastman Chemical Company
    Inventors: Gerald Charles Tustin, Joseph Robert Zoeller, Horace Lawrence Browning, Jr., Andy Hugh Singleton
  • Patent number: 5900504
    Abstract: Disclosed is an improved liquid phase process for the preparation of an acetyl product comprising acetic acid, by the carbonylation of a carbonylatable reactant material comprising methanol, methyl acetate, dimethyl ether or a mixture thereof in the presence of a catalyst system comprising a nickel component and an iodide component. In the separation of the crude acetyl product mixture from a liquid containing the non-volatile catalyst components, precipitation of metals and other catalyst components is avoided or minimized by maintaining a hydrogen pressure of at least 0.34 bar absolute within the flash evaporator zone wherein the separation occurs.
    Type: Grant
    Filed: February 20, 1996
    Date of Patent: May 4, 1999
    Assignee: Eastman Chemical Company
    Inventors: Jeffrey Scott Kanel, Stanley John Okrasinski
  • 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: 5883265
    Abstract: This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof which comprise subjecting one or more substituted or unsubstituted penten-1-ols to carbonylation in the presence of a carbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof. The substituted and unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactam. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof as principal product(s) of reaction.
    Type: Grant
    Filed: April 15, 1997
    Date of Patent: March 16, 1999
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Erik Bruce Tjaden, John Robert Briggs, Anil Sakharam Guram, John Michael Maher
  • 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: 5880311
    Abstract: Catalyst particles are contacted with a liquid and a gas in a vertically extending cylindrical vessel. The particles and liquid are placed in the vessel into which the gas and liquid are continuously fed from the bottom thereof so that an upwardly flowing mixture comprising the particles, liquid and gas is formed. The mixture is introduced into a gas separating zone disposed adjacent to an upper portion of the vessel to separate the mixture by gravity into a gas phase, a supernatant liquid phase and a phase rich in the catalyst particles. The gas and supernatant phases are continuously withdrawn from the separating zone while the catalyst particles-rich phase is continuously recycled to the bottom of the vessel by gravity.
    Type: Grant
    Filed: March 30, 1995
    Date of Patent: March 9, 1999
    Assignee: Tonen Corporation
    Inventors: Fumihiko Uemura, Hideki Sugiyama, Chieko Nagasawa, Takeshi Minami, Kazuhiko Hamato, Noriyuki Yoneda, Akihisa Yamaguchi
  • 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: 5840969
    Abstract: A process for the preparation of acetic acid product comprising, in a first catalytic step, conversion of a hydrogen and carbon monoxide containing synthesis gas to obtain a liquid process stream comprising methanol and, in a second catalytic step, carbonylation of the process stream with carbon monoxide to a product stream being rich in the acetic acid product in presence of catalytic effective amounts of a metal compound selected from Group VIII of the Periodic Table promoted with a halide compound, the improvement comprising the further steps of:(i) withdrawing from the carbonylation step a vent gas stream comprising carbon monoxide and residual amounts of acetic acid and halide compound;(ii) separating the vent gas stream into a liquid fraction containing a part of the residual amounts of acetic acid and part of the halide compound and a gaseous fraction with the carbon monoxide and remaining amounts of acetic acid and halide compound;(iii) recycling the liquid fraction to the carbonylation step;(iv) subj
    Type: Grant
    Filed: November 26, 1997
    Date of Patent: November 24, 1998
    Assignee: Haldor Topsoe A/S
    Inventor: Finn Joensen
  • 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: 5831120
    Abstract: In the process for the production of acetic acid by carbonylation of methanol and/or a reactive derivative thereof the water concentration in the liquid reaction composition is maintained at a steady-state concentration by at least one process step selected from the group consisting of (i) recovery and disposing of water from at least part of the overhead process stream from the light ends column and (ii) replacing at least a portion of the methanol feed with a component selected from the group consisting of methyl acetate, dimethyl ether, acetic anhydride and mixtures thereof. The recovered aqueous effluent from this and other processes may be purified of carboxylic acid by reactive distillation with at least one C.sub.1 to C.sub.3 alcohol.
    Type: Grant
    Filed: November 19, 1996
    Date of Patent: November 3, 1998
    Inventors: Derrick John Watson, Bruce Leo Williams, Michael James Muskett, Stephen James Smith, Chuc Tu Nguyen, Larry Irvin Baker
  • Patent number: 5817869
    Abstract: Methanol is converted to acetic acid by reaction with carbon monoxide in the presence of an carbonylation system which comprises a rhodium catalyst component and a liquid reaction medium containing acetic acid, methyl iodide, methyl acetate, and at least one pentavalent Group VA oxide and water in specific concentrations. The present carbonylation system not only increases the yields and reaction rates but also serves to stabilize the rhodium catalyst component in an active form.
    Type: Grant
    Filed: October 3, 1996
    Date of Patent: October 6, 1998
    Assignee: Quantum Chemical Corporation
    Inventors: James A. Hinnenkamp, Noel Hallinan
  • 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: 5783731
    Abstract: A process to reduce carbonyl impurities in a carbonylation reaction for the production of acetic acid is described. The methyl iodide recycle stream which is directed to a carbonylation reactor for carbonylating methanol or methyl acetate to acetic acid, is treated to remove carbonyl impurities by reacting the methyl iodide stream formed in the reaction with an aqueous amino compound which reacts with the carbonyls to form water soluble nitrogenous derivatives, separating an organic methyl iodide phase from an aqueous derivative phase and distilling the methyl iodide phase to remove heavier impurities. The treatment of the methyl iodide recycle stream to the carbonylation reactor has been found to greatly reduce the carbonyls present in the acetic acid product. The formation of nitrile from the nitrogenous derivative during distillation may be minimized by adding water to the system.
    Type: Grant
    Filed: September 11, 1995
    Date of Patent: July 21, 1998
    Assignee: Hoechst Celanese Corporation
    Inventors: Darrell Andrew Fisher, Michael L. Karnilaw, Kenneth Paul Kidwell, Melchior Albert Meilchen, Valerie Santillan, Mark O. Scates, G. Paull Torrence, Richard F. Vogel, Jr., R. Jay Warner
  • 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: 5770768
    Abstract: A method for preparing carboxylic acids by carbonylating a reagent, particularly an alcohol, in the presence of an iridium catalyst. According to the method, the liquid phase reaction is carried out in a first zone in the presence of an iridium catalyst, and the resulting reaction mixture is partially vaporised in a second zone. The vaporised fraction containing the carboxylic acid is later purified and the unvaporised liquid fraction containing the catalyst is recirculated to the first zone. The method is characterised in that said unvaporised fraction is contacted with carbon monoxide in such a way that this compound is not returned to the second zone.
    Type: Grant
    Filed: June 3, 1997
    Date of Patent: June 23, 1998
    Assignee: Acetex Chimie
    Inventors: Philippe Denis, Robert Perron, Joel Schwartz
  • Patent number: 5763654
    Abstract: A process for the production of acetic acid which comprises reacting carbon monoxide with a carbonylatable reactant comprising greater than 10%, typically from 30 to 100%, by weight dimethyl ether introduced to a reactor in which there is maintained at elevated temperature a liquid reaction composition comprising a Group VIII noble metal catalyst, for example rhodium or iridium, methyl iodide promoter, an optional co-promoter and water at a concentration in the liquid reaction composition of from 1.0 to 10% by weight.
    Type: Grant
    Filed: October 15, 1996
    Date of Patent: June 9, 1998
    Assignee: BP Chemicals Limited
    Inventors: Michael David Jones, Andrew David Poole
  • 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: 5756836
    Abstract: The present invention relates to a process for producing a highly purified acetic acid characterized in that in the process for producing acetic acid comprising the step of continuously reacting methanol and/or an aqueous solution of methyl acetate with carbon monoxide in a reactor, a treatment is conducted to limit the concentration of unsaturated compounds in crude acetic acid obtained in the process to 5 ppm or lower, and the resultant crude acetic acid is ozonized. The present invention also relates to a process for producing a highly purified acetic acid, characterized by comprising the step of continuously reacting methanol and/or an aqueous solution of methyl acetate with carbon monoxide in a reactor while maintaining the concentration of acetaldehyde in a reaction fluid in the reactor at 1500 ppm or lower.
    Type: Grant
    Filed: January 23, 1996
    Date of Patent: May 26, 1998
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Masahiko Shimizu, Kazuyuki Akita, Yasuteru Kajikawa, Takashi Ueno, Yasuo Tsuji, Yoshiaki Morimoto
  • Patent number: 5750007
    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 includes 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 includes carbonylation product and the liquid fraction has a water concentration of at least 0.5% by weight to stabilise the iridium catalyst.
    Type: Grant
    Filed: May 31, 1995
    Date of Patent: May 12, 1998
    Assignee: BP Chemicals Limited
    Inventors: Kirsten Everald Clode, Derrick John Watson, Carl Josef Elsa Vercauteren
  • Patent number: 5731252
    Abstract: A process for treating low water content carbonylation catalyst solutions which contain a rhodium component and an alkali metal component to remove metallic corrosion products is disclosed. The process comprises contacting the catalyst solution with an ion exchange resin, preferably in the lithium form, and a sufficient amount of water to decrease the concentration of alkali metal ions to optimize removal of corrosion metal products.
    Type: Grant
    Filed: January 21, 1997
    Date of Patent: March 24, 1998
    Assignee: Hoechst Celanese Corporation
    Inventors: R. Jay Warner, Jerry Allen Broussard
  • Patent number: 5728871
    Abstract: A process for the preparation of acetic acid by catalytic conversion of a synthesis gas being rich in hydrogen and carbon monoxide, comprising steps of:(i) introducing a stream of the synthesis gas into a first reaction step at a predetermined pressure and temperature and reacting the synthesis gas in the presence of a catalyst being active in formation of methanol and dehydration of methanol, so as to obtain a gaseous process phase containing methanol, dimethyl ether, and water;(ii) cooling the gaseous process phase of step (i) and obtaining a liquid phase with the methanol, dimethyl ether and water and a gaseous phase comprising carbon dioxide and residual amounts of dimethyl ether;(iii) introducing the liquid phase formed in step (ii) into a second reaction step at a predetermined pressure and temperature and adding a predetermined amount of carbon monoxide; and(iv) carbonylating methanol and dimethyl ether in the liquid phase with carbon monoxide by contact with a catalyst being active in the carbonylatio
    Type: Grant
    Filed: April 4, 1997
    Date of Patent: March 17, 1998
    Assignee: Haldor Topsoe A/S
    Inventors: Finn Joensen, Bodil Voss, Ib Dybkj.ae butted.r
  • Patent number: 5723660
    Abstract: The present invention provides a process for producing acetic acid by reacting continuously methanol, methyl acetate and the like with carbon monoxide in the presence of an eighth group metal-containing catalyst, methyl iodide and water, which is characterized in that wherein a liquid separation state in a decanter at the top of the first distillation column is maintained by adding water to the first distillation column. High quality acetic acid which has not so far been achieved can be obtained while controlling the purifying energy in a low level.
    Type: Grant
    Filed: December 13, 1996
    Date of Patent: March 3, 1998
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Yoshiaki Morimoto, Hiroyuki Nakayama, Takashi Ueno
  • Patent number: 5696284
    Abstract: In a process for the liquid phase carbonylation of an alkyl alcohol such as methanol, and/or a reactive derivative thereof to produce the corresponding carboxylic acid and/or ester, in the presence of an iridium catalyst, an alkyl halide and water, the reaction is promoted by the presence of at least one promoter selected from cadmium, mercury, zinc, gallium, indium and tungsten, optionally with a co-promoter selected from ruthenium, osmium and rhenium.
    Type: Grant
    Filed: February 5, 1996
    Date of Patent: December 9, 1997
    Assignee: BP Chemicals Limited
    Inventors: Michael James Baker, Carl Sherman Garland, Martin Francis Giles, Georgios Rafeletos
  • Patent number: 5679831
    Abstract: Process for the preparation of a terminal ester by carbonylation of an internally unsaturated organic compound in the presence of an alcohol, carbon monoxide, palladium, an acid with a pK.sub.a of less than 2 (measured at 18.degree. C. in an aqueous solution) and a bidentate organic phosphorus, antimony or arsenic ligand compound having a bridging group, wherein the bridging group comprises a bis(.eta.-cyclopentadienyl) coordination group of a transition metal.
    Type: Grant
    Filed: January 5, 1995
    Date of Patent: October 21, 1997
    Assignees: DSM N.V., E. I. Du Pont de Nemours and Company
    Inventor: Otto E. Sielcken
  • Patent number: 5672744
    Abstract: By employing a process for the preparation of acetic acid which comprises carbonylating methanol with carbon monoxide in a first reactor in the presence of a reaction fluid comprising a rhodium catalyst, methyl iodide, an iodide salt, methyl acetate and water, while continuously withdrawing the reaction fluid from the first reactor and introducing it into a flash zone to separate it into an evaporated part and an unevaporated part, characterized in that second reactor is provided between the first reactor and the flash zone and methanol is carbonylated with the carbon monoxide contained in the reaction fluid in a state in which it is dissolved therein in the second reactor with a residence time of 7 to 60 seconds at 150.degree. to 220.degree. C.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: September 30, 1997
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Masahiro Kagotani, Yasuteru Kajikawa
  • Patent number: 5672743
    Abstract: A process for the production of acetic acid by carbonylation of methanol or a reactive derivative thereof by contacting the methanol or derivative with carbon monoxide in a liquid reaction composition comprising (a) acetic acid, (b) an iridium catalyst, (c) methyl iodide, (d) at least a finite quantity of water and (e) methyl acetate is improved by the use as promoter of at least one of ruthenium and osmium.
    Type: Grant
    Filed: August 1, 1994
    Date of Patent: September 30, 1997
    Assignee: BP Chemicals Limited
    Inventors: Carl Sherman Garland, Martin Francis Giles, John Glenn Sunley
  • Patent number: 5663430
    Abstract: In a process for purifying a carboxylic acid fraction obtained by liquid phase carbonylation of an alkyl alcohol and/or its reactive derivative in which volatile iridium- and/or volatile co-promoter contaminants are converted to involatile forms by contacting with an iodide in the absence of carbon monoxide or at a partial pressure less than that of the carbonylation reaction. The involatile contaminants are then separated from the carboxylic acid.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: September 2, 1997
    Assignee: BP Chemicals Limited
    Inventors: George Ernest Morris, Stephen James Smith, John Glenn Sunley, Robert John Watt, Bruce Leo Williams
  • Patent number: 5663429
    Abstract: A process for preparing acetic acid from methanol and carbon monoxide or a mixed gas of carbon monoxide with hydrogen, which process comprises contacting methanol with a gaseous component selected from a group consisting of carbon monoxide and a mixed gas of carbon monoxide with hydrogen of 2% by volume or less in the presence of a carbon-supported rhodium metal catalyst and methyl iodide promoter in vapor phase under the conditions of a reaction temperature of 180.degree.-220.degree. C., a reaction pressure of 5-10 kg/cm.sup.2 .multidot.G, and a weight of catalyst to feed gas flow rate ratio (W/F) of 10-20 g.multidot.h/mole; and a process for preparing acetic acid from methanol and carbon monoxide, which process comprises contacting methanol with carbon monoxide in the presence of a carbon-supported rhodium metal catalyst, methyl iodide promoter and water in vapor phase.
    Type: Grant
    Filed: September 27, 1995
    Date of Patent: September 2, 1997
    Assignee: Tokyo Gas Company, Ltd.
    Inventors: Kenichi Yamaseki, Yasuo Konishi, Hiroshi Uchida
  • Patent number: 5650537
    Abstract: A process for the preparation of N-acylglycine derivatives of the formula (I) ##STR1## which comprises reacting a carboxylic acid amide with an aldehyde in the presence of a solvent and an acid to give an acylaminomethylol and then carbonylating the acylaminomethylol in the presence of a cobalt carbonyl catalyst.
    Type: Grant
    Filed: May 2, 1995
    Date of Patent: July 22, 1997
    Assignee: Hoechst AG
    Inventors: Matthias Beller, Hartmut Fischer, Thomas Gerdau, Peter Gross
  • Patent number: 5648531
    Abstract: A process for continuously producing acetic anhydride alone or acetic anhydride and acetic acid by reacting methyl acetate and/or dimethyl ether and, optionally, water and/or methanol, with carbon monoxide alone or carbon monoxide and hydrogen in the presence of a rhodium compound and methyl iodide as principal catalysts. Trace impurities causative of tar formation are distilled and separated in an evaporator and/or a subsequent refining step to remove the same. The removal of the trace impurities causative of tar formation serves to decrease the amount of tar formed as an impurity.
    Type: Grant
    Filed: March 22, 1995
    Date of Patent: July 15, 1997
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Yoshiaki Morimoto, Hiroto Tanigawa, Kazuyuki Akita
  • Patent number: 5639894
    Abstract: A process for the carbonylation of allylic alcohols such as nerolidol, farnesol, or their monocyclic analogues with carbon monoxide at a pressure of at least 30 bar in the presence of a polar solvent and a palladium halide catalyst, optionally an alkali metal halide salt, and optionally an alcoholic solvent. The carbonylated product may then be reduced to the corresponding alcohol, which is cyclized in the presence of Lewis or Bronsted acids to afford an ambergris fragrance compound.
    Type: Grant
    Filed: March 23, 1994
    Date of Patent: June 17, 1997
    Assignee: Henkel Kommanditgesellschaft auf Aktien
    Inventors: Jonathan M. Cassel, Steven M. Hoagland, James M. Renga
  • 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