Preparing Esters By Carbonylation Patents (Class 560/232)
  • Patent number: 6281372
    Abstract: A process for the synthesis of vinyl esters from butene oligomers, wherein butenes are oligomerized, the butene oligomers are separated from the oligomerized mixture, the butene oligomers are converted to carboxylic acids which are longer by one carbon atom, and the resulting carboxylic acids are converted to the corresponding vinyl esters. The butene oligomers are in particular dibutene, tributene and tetrabutene. The invention also relates to the use of the vinyl esters as plasticizers or as comonomers in polymerization reactions.
    Type: Grant
    Filed: February 28, 2000
    Date of Patent: August 28, 2001
    Assignee: OXENO Olefinchemie GmbH
    Inventors: Klaus-Diether Wiese, Paul Olbrich, Juergen Gabriel
  • Patent number: 6274096
    Abstract: The retrofitting of an existing methanol or methanol/ammonia plant to make acetic acid is disclosed. The plant is retrofitted to feed carbon dioxide into a reformer to which natural gas and steam (water) are fed. Syngas is formed in the reformer wherein both the natural gas and the carbon dioxide are reformed to produce syngas with a large proportion of carbon monoxide relative to reforming without added carbon dioxide. The syngas is split into a first part and a second part. The first syngas part is converted to methanol in a conventional methanol synthesis loop that is operated at about half of the design capacity of the original plant. The second syngas part is processed to separate out carbon dioxide and carbon monoxide, and the separated carbon dioxide is fed back into the feed to the reformer to enhance carbon monoxide formation. The separated carbon monoxide is then reacted with the methanol to produce acetic acid or an acetic acid precursor by a conventional process.
    Type: Grant
    Filed: November 1, 1999
    Date of Patent: August 14, 2001
    Assignee: Acetex (Cyprus) Limited
    Inventors: Daniel Marcel Thiebaut, Kenneth Ebenes Vidalin
  • Patent number: 6232352
    Abstract: The retrofitting of an existing methanol or methanol/ammonia plant to make acetic acid is disclosed. The existing plant has a reformer to which natural gas or another hydrocarbon and steam (water) are fed. Syngas is formed in the reformer. All or part of the syngas is processed to separate out carbon dioxide, carbon monoxide and hydrogen, and the separated carbon dioxide is fed either to the existing methanol synthesis loop for methanol synthesis, or back into the feed to the reformer to enhance carbon monoxide formation in the syngas. Any remaining syngas not fed to the carbon dioxide separator can be converted to methanol in the existing methanol synthesis loop along with carbon dioxide from the separator and/or imported carbon dioxide, and hydrogen from the separator. The separated carbon monoxide is then reacted with the methanol to produce acetic acid or an acetic acid precursor by a conventional process.
    Type: Grant
    Filed: April 12, 2000
    Date of Patent: May 15, 2001
    Assignee: Acetex limited
    Inventor: Kenneth Ebenes Vidalin
  • Patent number: 6211405
    Abstract: The present invention provides a process for the carbonylation of an alcohol, ether or ester to products comprising a carboxylic acid, the anhydride thereof or coproduction of the carboxylic acid and anhydride. More particularly, the present invention provides a process for the carbonylation of methanol to produce acetic acid by reacting methanol with carbon monoxide in a liquid reaction medium containing a catalyst comprising rhodium, iridium, iodide ion, and said reaction medium further comprising water, acetic acid, methyl iodide, and methyl acetate and subsequently recovering acetic acid from the resulting reaction product.
    Type: Grant
    Filed: October 23, 1998
    Date of Patent: April 3, 2001
    Assignee: Celanese International Corporation
    Inventors: Hung-Cheun Cheung, Elaine C. Sibrel, Robin S. Tanke, G. Paull Torrence
  • Patent number: 6143930
    Abstract: Disclosed is a method to manufacture high purity acetic acid. Although described in relation to that produced by a low water carbonylation process the present invention is applicable to other mechanisms for production of acetic acid which results in formation of permanganate reducing compounds such as acetaldehyde, propionic acid, and alkyl iodide impurities in intermediate process streams. It has been found that permanganate reducing compounds and alkyl iodides may be conveniently removed from a light phase of an intermediate stream in the reaction process by employing a multiple distillation process coupled with an optional extraction of acetaldehyde. The distillation process involves first distilling a light phase to concentrate the permanganate reducing compounds, and in particular the acetaldehyde, and then separating the permanganate reducing compounds and alkyl iodides in a second distillation tower.
    Type: Grant
    Filed: October 17, 1997
    Date of Patent: November 7, 2000
    Assignee: Celanese International Corp
    Inventors: Madan Singh, George A. Blay, Michael L. Karnilaw, Melchior A. Meilchen, Wayne David Picard, Valerie Santillan, Mark O. Scates, Robin Suzanne Tanke, G. Paull Torrence, Richard F. Vogel, Jr., R. Jay Warner
  • 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: 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: 5965769
    Abstract: There are herein disclosed a method for heat recovery and heat utilization by the use of chemical energy which comprises the steps of doing the heat recovery by the following formula (I), and doing the heat utilization by the following formula (I'):HCOOCH.sub.3 .fwdarw.CH.sub.3 OH+CO (I)CH.sub.3 OH+CO.fwdarw.HCOOCH.sub.3 (I')the reaction of the formula (I') being carried out in the presence of an alkali fluoride and zinc oxide. According to the present invention, steam or hot water can be generated at a high temperature of 100.degree. C. or more by the use of a factory waste heat or a river water at a low temperature of 100.degree. C. or less as a heat source from which heat has scarcely been utilized so far, and the thus generated steam or hot water can effectively be used as a heat source or be used in an air conditioner. The catalyst which comprises the alkali fluoride and zinc oxide is used for preparing methyl formate or CO gas according to the formula (I) or (I').
    Type: Grant
    Filed: January 7, 1998
    Date of Patent: October 12, 1999
    Assignee: Mitsubish Gas Chemical Company, Inc.
    Inventors: Shiro Kajiyama, Futoshi Ikoma, Atsushi Okamoto, Mikio Yoneoka, Shuji Ebata, Kenji Nakamura
  • Patent number: 5952522
    Abstract: A process is disclosed for the carbonylation of acetylenically unsaturated compounds by reaction with carbon monoxide and a co-reactant in the presence of a catalyst system based on: (a) a source of platinum; (b) a bidentate ligand of the formula R.sup.1 R.sup.2 M.sup.1 -R-M.sup.2 R.sup.3 R.sup.4, wherein M.sup.1 and M.sup.2 independently are P, As or Sb, R represents a bivalent substituted or non-substituted bridging group containing from 1 to 5 atoms in the bridge, R.sup.1 and R.sup.2 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.1, and R.sup.3 and R.sup.4 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.2 or R.sup.3 and R.sup.4 independently are substituted or non-substituted hydrocarbyl groups; and (c) a source of anions.
    Type: Grant
    Filed: December 18, 1996
    Date of Patent: September 14, 1999
    Assignee: Shell Oil Company
    Inventors: Eit Drent, Willem Wabe Jager
  • 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: 5917085
    Abstract: In a process for the continuous preparation of methyl formate by reaction of carbon monoxide and methanol under elevated pressure and elevated temperature in the presence of an alkali metal methoxide, the reaction is carried out at a pressure of from 210 to 250 bar in the presence of from 0.05 to 0.2% by weight of alkali metal methoxide, based on methanol used.
    Type: Grant
    Filed: July 30, 1997
    Date of Patent: June 29, 1999
    Assignee: BASF Aktiengesellschaft
    Inventors: Ferdinand Lippert, Arthur Hohn, Jurgen Dahlhaus
  • 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: 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: 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: 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: 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: 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: 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: 5767307
    Abstract: This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.
    Type: Grant
    Filed: May 21, 1996
    Date of Patent: June 16, 1998
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Dorai Ramprasad, Francis Joseph Waller
  • 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: 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: 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: 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: 5516776
    Abstract: A process and intermediates for the enantioselective synthesis of 5,10-dideaza-5,6,7,8-tetrahydrofolic acid are disclosed.
    Type: Grant
    Filed: September 12, 1994
    Date of Patent: May 14, 1996
    Assignee: Eli Lilly and Company
    Inventors: Charles J. Barnett, Thomas M. Wilson
  • Patent number: 5502243
    Abstract: Oxygenated acetyl compounds ethylidene diacetate, acetic acid, acetic anhydride, acetaldehyde, and methyl acetate are produced directly from synthesis gas and dimethyl ether in a catalyzed liquid phase reaction system. The inclusion of carbon dioxide in the synthesis gas in selected amounts increases the overall yield of oxygenated acetyl compounds from the reactant dimethyl ether. When methanol is included in the reactor feed, the addition of carbon dioxide significantly improves the molar selectivity to ethylidene diacetate.
    Type: Grant
    Filed: September 16, 1994
    Date of Patent: March 26, 1996
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Francis J. Waller, David W. Studer
  • Patent number: 5488153
    Abstract: A process or the liquid phase carbonylation of methanol or a reactive derivative thereof comprises contacting carbon monoxide with a liquid reaction composition comprising methanol or a reactive derivative thereof, a halogen promoter and a rhodium catalyst system comprising a rhodium component and a bidentate phosphorus-sulphur ligand, the ligand comprising a phosphorus dative center linked to a sulphur dative or anionic center by a substantially unreactive backbone structure comprising two connecting carbon atoms or a connecting carbon and a connecting phosphorus atom. Novel rhodium ligand complexes of formula [Rh(CO)L].sub.m and Rh(CO)LY] wherein Y is a halogen, m is a number less than 10 and L is ##STR1## wherein the R groups are independently selected from C.sub.1 to C.sub.20 alkyl, cycloalkyl, aryl, substituted aryl and optionally substituted aralkyl; the R.sup.5 groups are selected from hydrogen, C.sub.1 to C.sub.
    Type: Grant
    Filed: June 21, 1994
    Date of Patent: January 30, 1996
    Assignee: BP Chemicals Limited
    Inventors: Michael J. Baker, Jonathan R. Dilworth, John G. Sunley, Nigel Wheatley
  • Patent number: 5488143
    Abstract: The present invention provides an improved process for selectively producing acetic acid and/or methyl acetate by the gas phase carbonylation of methanol with carbon monoxide; an improved process for producing acetic anhydride directly from the methyl acetate; and a novel method for sustaining the life time of a carbonylation or a hydroformylation catalyst by pretreating the carbon monoxide or the synthesis gas to be used in carrying out the gas phase carbonylation or the hydroformylation.
    Type: Grant
    Filed: January 19, 1994
    Date of Patent: January 30, 1996
    Assignee: Korea Institute of Science and Technology
    Inventors: Sung J. Uhm, Sung H. Han, Jun W. Oh, Oh S. Joo
  • Patent number: 5430178
    Abstract: Acetic ester is produced economically by a gas phase carbonylation of methanol with carbon monoxide followed by a transesterification. Specifically, the inventive process comprises (a) carbonylating methanol in a gas phase with carbon monoxide to produce a mixture of acetic acid and methyl acetate; (b) separating from the production mixture the acetic acid, and a mixture of the methyl acetate and the co-catalyst; (c) further separating said methyl acetate and the co-catalyst and recycling the separated co-catalyst to the carbonylation reactor; (d) introducing the separated methyl acetate into a lower region of a transesterification reactor at a temperature of above its boiling point; (e) introducing an C.sub.
    Type: Grant
    Filed: July 27, 1994
    Date of Patent: July 4, 1995
    Assignee: Korea Institute of Science and Technology
    Inventors: Sung J. Uhm, Sung H. Han, Jun W. Oh, Oh S. Joo, Kwang D. Jung, Moon S. Lee
  • Patent number: 5414161
    Abstract: Ethanol is produced economically by a gas phase carbonylation of methanol with carbon monoxide followed by a hydrogenation.
    Type: Grant
    Filed: March 17, 1994
    Date of Patent: May 9, 1995
    Assignee: Korea Institute of Science and Technology
    Inventors: Sung J. Uhm, Sung H. Han, Jun W. Oh, Oh S. Joo, Kwang D. Jung, Jung Y. Beak
  • Patent number: 5414110
    Abstract: The present invention relates to(1) a Ru-Sn hetero-polynuclear complex as a novel catalyst which has a high catalytic activity and is useful for producing acetic acid and/or methyl acetate from methanol, and(2) a process for producing acetic acid and/or methyl acetate through a one-stage reaction starting with methanol wherein a catalyst can be used at a high concentration and the catalytic activity is maintained throughout the reaction.
    Type: Grant
    Filed: March 10, 1994
    Date of Patent: May 9, 1995
    Assignee: Daicel Chemical Industries, Ltd.
    Inventor: Sumio Shinoda
  • Patent number: 5401873
    Abstract: Preparation of methyl formate by the reaction of carbon monoxide and methanol under conditions of elevated pressure and temperature in the presence of an alkali metal methylate, in whichA) the starting materials are mixed in a mixing zone, are allowed to react partially, and the reaction solution is saturated with CO andB) the reaction is allowed to reach completion in one or more secondary reaction zones without the addition of further starting materials.
    Type: Grant
    Filed: March 11, 1994
    Date of Patent: March 28, 1995
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Zehner, Klaus Bittins, Wilhelm Haarde, Ulrich Eiden, Dietrich Wolff, Manfred Herr, Leopold Hupfer
  • Patent number: 5371275
    Abstract: The present invention relates to a process for preparing a catalyst useful in producing ethylidene diacetate and to a process for producing ethylidene diacetate by a continuous process using the catalyst prepared. In the preparation of ethylidene diacetate from carbon monoxide and hydrogen, the conventional preparation method using a homogeneous catalyst system comprising a transition metal catalyst is hampered by difficulty in separating the catalyst from the reaction product after completion of the reaction. The catalyst of the present invention is separated easily from the reaction product. The heterogeneous catalyst of the present invention is prepared by adding a compound of a group VIII metal, preferably rhodium or palladium, to a carrier, preferably .alpha.-alumina, kieselguhr or silica, together with an accelerator containing phosphorus or nitrogen, preferably triphenylphosphine. Using the improved catalyst of the present invention also resulted in increased yield of product over conventional methods.
    Type: Grant
    Filed: July 23, 1993
    Date of Patent: December 6, 1994
    Assignee: Korean Research Institute of Chemical Technology
    Inventors: Dae C. Park, Sung Y. Cho
  • Patent number: 5371274
    Abstract: The present invention relates to the field of catalyst technology, and more particularly to the preparation of a supported catalyst and a method of producing ethylidene diacetate using that supported catalyst. The catalyst is represented by the formula M.sub.a X. Compound M includes a group VIII transition metal which catalyzes the formation of ethylidene diacetate, preferably a compound of rhodium or palladium. Carrier X is an organic carrier, preferably selected from the divinylbenzene-polystyrene copolymers, most preferably copolymers having about 1-20% crosslinking. The weight percent of metal M contained in the catalyst is represented by the latter a. The supported heterogenized catalyst results from covalent bonding of the transition metal compound to the organic polymer carrier. Ethylidene diacetate was produced by reacting methyl acetate, iodomethane, carbon monoxide and hydrogen in the presence of this supported catalyst and an accelerator at elevated temperature and pressure.
    Type: Grant
    Filed: July 19, 1993
    Date of Patent: December 6, 1994
    Assignee: Korean Research Institute of Chemical Technology
    Inventors: Dae C. Park, Sung Y. Cho, Woo S. Chang
  • Patent number: 5364979
    Abstract: A catalyzed, continuous vapor phase process to convert a C.sub.2 or higher alcohol and, optionally, one or more C.sub.1 or higher alcohols, for example methanol and ethanol, to a mixture containing at least one higher molecular weight alcohol, for example, isobutanol, over a catalyst which is essentially magnesium oxide. The process also may have a lower aldehyde and/or ketone in the feed.
    Type: Grant
    Filed: January 5, 1994
    Date of Patent: November 15, 1994
    Assignee: Amoco Corporation
    Inventors: Cecelia A. Radlowski, Gary P. Hagen, Lewis E. Grimes, David F. Tatterson
  • Patent number: 5354886
    Abstract: The present invention relates to a catalyst, a process for preparing the catalyst and a process for using the catalyst to produce ethylidene diacetate. The conventional preparation methods of ethylidene diacetate suffer from difficulty in separating the catalyst from the product after completion of the reaction. The catalyst of the present invention is simply separated from the product by mere filtration following the completion of reaction. This is a result of using a heterogenized catalyst which is obtained by supporting a homogeneous catalyst in an inorganic carder. The catalyst of the present invention is of the general formula M.sub.a X where M is a compound of a group VIII transition metal, most preferably RhCl.sub.3 .multidot.xH.sub.2 O, and X is an inorganic carrier, preferably selected from the group consisting of kieselguhr, .gamma.-alumina, silica, TiO.sub.2, MgO, ZnO and activated charcoal.
    Type: Grant
    Filed: July 26, 1993
    Date of Patent: October 11, 1994
    Assignee: Korea Research Institute of Chemical Technology
    Inventors: Dae C. Park, Sung Y. Cho
  • Patent number: 5352813
    Abstract: An improved process is provided for the carbonylation of methanol to acetic acid and/or its derivatives, especially methyl acetate, under mild reaction conditions using a novel catalyst precursor. The precursor is a transition metal complex having a heterodifunctional bidentate phosphorus--nitrogen ligand attached to the metal. The carbonylation reaction can now typically be carried out at 80.degree. C. and CO pressure of 40 p.s.i.g.
    Type: Grant
    Filed: September 3, 1991
    Date of Patent: October 4, 1994
    Assignee: University of Alberta
    Inventors: Ronald G. Cavell, Kattesh V. Katti
  • Patent number: 5286900
    Abstract: From a synthesis gas mainly consisting of hydrogen and carbon oxides an acetic acid product consisting of acetic acid, acetic anhydride and/or methyl acetate is prepared by reactions known per se in a technically simple reaction sequence and a high conversion degree when the reactions are combined such that in a first step at a pressure of 5-200 bar and a temperature of 150.degree.-400.degree. C. the synthesis gas is converted in the gas phase in a first reactor to methanol, of which at least a substantial proportion is converted to dimethyl ether in the same reactor in the presence of one or more catalysts which together catalyze the reactionsCO+2H.sub.2 .revreaction.CH.sub.3 OH (1)2 CH.sub.3 OH.revreaction.CH.sub.3 OCH.sub.3 +H.sub.2 O (2)andCO+H.sub.2 O.revreaction.CO.sub.2 +H.sub.2 (3)and then passing the entire effluent from the first reactor to a second reactor in which methanol and dimethyl ether at a pressure of 1-800 bar and a temperature of 100.degree.-500.degree. C.
    Type: Grant
    Filed: September 4, 1992
    Date of Patent: February 15, 1994
    Assignee: Haldor Topsoe A/S
    Inventors: John B. Hansen, Finn H. Joensen, Haldor F. A. Topsoe
  • Patent number: 5258546
    Abstract: The invention relates to a catalyst system, which comprises a source of a Group VIII metal and a polyphosphine. The invention further relates to a process for the preparation of alpha, beta-olefinically unsaturated compounds utilizing this catalyst system.
    Type: Grant
    Filed: November 20, 1992
    Date of Patent: November 2, 1993
    Assignee: Shell Oil Company
    Inventors: Peter A. Klusener, Hans A. Stil, Fit Drent, Peter Arnoldy
  • Patent number: 5239109
    Abstract: A process for making alkyl formates from a synthesis gas is described in which a synthesis gas stream is separated into a first stream and a second stream which contain CO and H.sub.2. The CO and H.sub.2 are reacted under high pressures to produce methanol. The CO of the second stream is reacted with water to produce formic acid. The formic acid and methanol are reacted in the presence of an alkali or alkaline earth metal catalyst such as NaOH to produce an effluent stream which includes alkyl formate and H.sub.2. The H.sub.2 is separated and recycled to the alcohol synthesis zone as a second source of H.sub.2.
    Type: Grant
    Filed: December 16, 1991
    Date of Patent: August 24, 1993
    Assignee: Mobil Oil Corporation
    Inventor: Tsoung Y. Yan
  • Patent number: 5237097
    Abstract: A process is disclosed for the carbonylation of an organic compound selected from the group consisting of an olefin, an alcohol, an acid and an ester. In this process the organic compound is reacted with carbon monoxide in the presence of a Group VIII metal-containing catalyst. The liquid carbonylation product solution of this reaction is conveyed to a separation zone maintained at a lower total pressure than is the pressure in the reaction zone. Simultaneously with the conveyance of the liquid product solution to the separation zone is the introduction therein of a carbon monoxide-containing gaseous stream, the carbon monoxide therein contributing a partial pressure of up to 30 psia of the total pressure in said separation zone. A portion of the liquid carbonylation product solution is flashed and removed from the separation zone. The unflashed liquid carbonylation product solution is recycled back into the reaction zone.
    Type: Grant
    Filed: December 22, 1992
    Date of Patent: August 17, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: David W. Smith, Ronnie M. Hanes
  • Patent number: 5218140
    Abstract: A process and novel catalyst for the carbonylation of one or more of alcohols, ethers and ether alcohols to esters and, optionally, to carboxylic acids. The reaction is effected in the vapor state over a solid catalyst comprising a polyoxometalate anion in which the metal is at least one taken from Group V and VI of the Periodic Chart of the Elements complexed with a cation from a member of Group VIIIA of the Periodic Chart of the Elements. Preferably, the catalyst is deposited on a support that is inert to the reaction. The preferred support is silica.
    Type: Grant
    Filed: August 2, 1988
    Date of Patent: June 8, 1993
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventor: Richard W. Wegman
  • 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: 5206434
    Abstract: Esters such as methyl acetate which contain carbonyl impurities including aldehydes are purified by adding to the esters an amino compound which reacts with the carbonyls to form water soluble nitrogenous derivatives, separating an organic ester phase from an aqueous derivative phase, and distilling the ester phase to further remove heavier impurities. The formation of nitrile from the nitrogenous derivative is minimized by adding water to the distillation column or washing the aqueous bottoms from distillation with water to further remove the derivatives from any ester contained in the bottoms. The organic phase recovered from the bottoms can be recycled to the distillation to recover ester.
    Type: Grant
    Filed: November 19, 1990
    Date of Patent: April 27, 1993
    Assignee: Hoechst Celanese Corporation
    Inventors: Mark O. Scates, Russell K. Gibbs, Jr., G. Paull Torrence
  • Patent number: 5194676
    Abstract: Saturated carboxylic esters are produced from alkyl formate and an olefin, without the presence of substantial amounts of carbon monoxide, at a temperature of 120.degree. to 280.degree. C., under a pressure of 1 to 3,000 bars, in the presence of a catalyst based on ruthenium coordinated by ligands selected from carbon monoxide, halogen atoms and amines, and in the presence of an amide as a solvent. The catalyst is selected from catalysts consisting essentially of RuCl.sub.3.3H.sub.2 O; catalysts consisting essentially of the combination of an RuCl.sub.3.3H.sub.2 O together with at least one stabilizer selected from iodine, covalent iodides and quaternary ammonium halides; catalysts comprising Ru.sub.3 (CO).sub.12 together with at least one stabilizer such as is mentioned above; and catalysts selected from RuI.sub.3, [RuCl.sub.2 (CO).sub.3 ].sub.2, Ru(NH.sub.3).sub.6 Cl.sub.3 and [Ru(NH.sub.3).sub.5 Cl]Cl.sub.2, comprising, where appropriate, in addition, at least one stabilizer such as is mentioned above.
    Type: Grant
    Filed: March 26, 1991
    Date of Patent: March 16, 1993
    Assignee: Atochem
    Inventors: Yves Castanet, Christophe Legrand, Andre Mortreux, Francis Petit
  • Patent number: 5189203
    Abstract: The present invention relates to a process for preparing acetic acid, acetic acid methyl ester or acetic anhydride or mixtures thereof by converting a synthesis gas mainly containing hydrogen and carbon oxides, by first converting the synthesis gas catalytically into a gas mixture containing methanol and dimethyl ether and then carbonylating this mixture catalytically into acetic acid and/or methyl acetate and/or acetic anhydride.
    Type: Grant
    Filed: June 30, 1988
    Date of Patent: February 23, 1993
    Assignee: Haldor Topsoe A/S
    Inventors: John B. Hansen, Finn H. Joensen, Haldor F. A. Topsoe
  • Patent number: 5185462
    Abstract: A process for the production from an alcohol having n carbon atoms, wherein n is a number from 1 to 20, of a carboxylic acid having n+1 carbon atoms and/or an ester of the alcohol having n carbon atoms with the carboxylic acid by reacting the alcohol at a temperature of at least 50.degree. C.
    Type: Grant
    Filed: October 4, 1991
    Date of Patent: February 9, 1993
    Assignees: BP Chemicals Limited, The University of Southampton
    Inventors: John Evans, Steven L. Scruton
  • Patent number: 5169982
    Abstract: Iodine and its compounds are separated from the carbonylation products acetic acid, acetic anhydride or ethylidene diacetate obtained on subjecting dimethylether, methyl acetate or methanol to a carbonylation reaction in the presence of an iodine-containing catalyst. The quantity of total iodine contaminating the carbonylation products is reduced to less than 20 ppb iodine by treating the products at 20.degree.-200.degree. C. with peracetic acid, diacetyl peroxide or a compound yielding these two agents under the reaction conditions, and separating them distillatively.
    Type: Grant
    Filed: September 16, 1986
    Date of Patent: December 8, 1992
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Erpenbach Heinz, Klaus Gehrmann, Peter Horstermann
  • Patent number: 5158921
    Abstract: A catalyst system, which containsa) a source of a group VIII metal, andb) a phosphine of general formula: ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 are independently selected from an optionally substituted aryl group and a group of general formula: ##STR2## wherein eachh of A, X, Y and Z is independently selected from a nitrogen atom, a CH group and a group of formula CR wherein R represents a hydroxyl group, an amino group, an amido group, a cyano group, an aryl group, an aryloxy group, a halogen atom, an optionally substituted hydrocarbyl group or an optionally substituted hydrocarbyloxy group, it also being possible for two adjacent CR groups to form a ring, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 represents a group of formula (II) in which at least one of A and Z represents a group of formula CR; or an acid addition salt thereof.Also disclosed is the use of the catalyst system in the selective carbonylation of unsaturated hydrocarbons.
    Type: Grant
    Filed: February 28, 1990
    Date of Patent: October 27, 1992
    Assignee: Shell Oil Company
    Inventors: Eit Drent, Petrus H. M. Budzelaar, Willem W. Jager
  • Patent number: 5144068
    Abstract: An alcohol such as methanol is reacted with carbon monoxide in a liquid reaction medium containing a rhodium catalyst stabilized with an iodide salt, especially lithium iodide, along with alkyl iodide such as methyl iodide and alkyl acetate such as methyl acetate in specified proportions. With a finite concentration of water in the reaction medium the product is the carboxylic acid instead of, for example, the anhydride. The present reaction system not only provides an acid product of unusually low water content at unexpectedly favorable reaction rates but also, whether the water content is low or, as in the case of prior-art acetic acid technology, relatively high, is characterized by unexpectedly high catalyst stability; i.e., it is resistant to catalyst precipitation out of the reaction medium.
    Type: Grant
    Filed: January 7, 1991
    Date of Patent: September 1, 1992
    Assignee: Hoechst Celanese Corporation
    Inventors: Brad L. Smith, G. Paull Torrence, Adolfo Aguilo, James S. Alder
  • Patent number: 5138093
    Abstract: Ethylidene diacetate is prepared by treating at least one member of the group consisting of methyl acetate and dimethyl ether with carbon monoxide in the presence of a source of halide under substantially anhydrous conditions.
    Type: Grant
    Filed: February 5, 1976
    Date of Patent: August 11, 1992
    Assignee: Eastman Kodak Company
    Inventors: Nabil Rizkalla, Charles N. Winnick