Gas Phase Patents (Class 560/245)
  • Patent number: 9856200
    Abstract: The present disclosures and inventions relate to a supported catalyst composition for the catalytic oxidation of a hydrocarbon such as propane with oxygen or air, in the presence of a catalyst composition comprising a support material and a mixed metal composition comprising metals in the molar ratios described by the formula MoaVbGacPddNbeZf, wherein the support material is neutral or oxidative.
    Type: Grant
    Filed: April 22, 2014
    Date of Patent: January 2, 2018
    Assignee: Saudi Basic Industries Corporation
    Inventors: Khalid Karim, Abdulaziz Al Jodai
  • Patent number: 9616409
    Abstract: A method of making a supported catalytic species comprising an alloy of at least two metals, comprises the steps of: (i) combining a particulate support material, a solution of a first metal compound, a solution of a second metal compound, and a solution of an alkaline precipitating agent to form a slurry mixture; (ii) agitating the resultant mixture; and (iii) contacting the solids with a reducing agent, wherein the first metal in the first metal compound and the second metal in the second metal compound is each independently selected from the group consisting of gold, palladium, platinum, rhodium, iridium, silver, osmium and ruthenium; and wherein the first metal is not the same as the second metal.
    Type: Grant
    Filed: March 5, 2012
    Date of Patent: April 11, 2017
    Assignee: Johnson Matthey Public Limited Company
    Inventors: Bergeal David, Andrew Francis Chiffey, Peter Johnston, Francois Moreau, Paul Richard Phillips
  • Patent number: 9556100
    Abstract: Provided are catalyst composites useful for the production of vinyl acetate monomer, as well as methods of making using same. The catalyst composites may comprise a support comprising silica and about 1 to about 3 wt-% alumina, wherein the support has a surface area of about 175 to about 300 m2/g; and an eggshell layer on the support comprising Pd and Au.
    Type: Grant
    Filed: July 1, 2013
    Date of Patent: January 31, 2017
    Assignee: BASF CORPORATION
    Inventors: Joseph C. Dellamorte, Ronald T. Mentz
  • Patent number: 9527060
    Abstract: A catalyst is produced by a process that comprises at least a step of impregnating a carrier with an alkali solution having a mass of greater than 0.9 times and no greater than 1.0 times the amount of water absorption of the carrier, a step of further impregnating the carrier by contact with a solution A comprising at least a compound containing palladium or platinum and a compound containing a Group 11 element, a step of reduction treatment and a step of loading an acetic acid salt on the carrier, wherein the carrier is first impregnated with the alkali solution and then the contacted with solution A to form a catalyst precursor, and wherein the total amount of the alkali solution and solution A is a mass of at least 1.1 times and no greater than 10.0 times the amount of water absorption of the carrier. A catalyst for alkenyl acetate production is obtained that exhibits improved activity and selectivity.
    Type: Grant
    Filed: August 8, 2007
    Date of Patent: December 27, 2016
    Assignee: SHOWA DENKO K.K.
    Inventor: Meiko Saihata
  • Patent number: 9334226
    Abstract: A method for producing a shell catalyst which is suitable for the synthesis of alkenyl carboxylic acid esters, in particular for producing vinyl acetate monomer (VAM) from ethylene or allyl acetate monomer from propylene by means of oxy-acetylation. Also, a shell catalyst that can be obtained by the method according to the invention, as well as the use of the shell catalyst produced using the method for producing alkenyl carboxylic acid esters, in particular vinyl acetate monomer (VAM) and allyl acetate monomer.
    Type: Grant
    Filed: September 19, 2013
    Date of Patent: May 10, 2016
    Assignee: Clariant International Ltd.
    Inventors: Roman Bobka, Gerhard Mestl, Peter Scheck, Carolin Fischer, Martin Schoenfelder
  • Patent number: 9243539
    Abstract: A catalyst composition comprises a mixed metal catalyst which comprises unalloyed palladium and palladium-gold alloy disposed on a support, wherein the palladium-gold alloy is enriched in gold and at least one promoter in which said promoter comprises at least one reducible metal oxide.
    Type: Grant
    Filed: June 7, 2013
    Date of Patent: January 26, 2016
    Assignee: Johnson Matthey Public Limited Company
    Inventors: Paul Richard Phillips, Agnes Suganya Raj, Raj Rao Rajaram
  • Patent number: 9186697
    Abstract: The invention relates to methods for applying wet concrete mixtures containing cement, fillers, water, one or more polymers, and possibly further admixtures or additives according to the wet-mix shotcrete method, characterized in that the wet concrete mixtures, which contain at least one polymer based on one or more vinyl esters of unbranched or branched alkyl carboxylic acids having 1 to 15 C atoms and possibly one or more further ethylenically unsaturated monomers, are put into a concrete spraying machine and are applied to a subsurface by means of the wet-mix shotcrete method with a layer thickness of ?3 cm.
    Type: Grant
    Filed: October 23, 2009
    Date of Patent: November 17, 2015
    Assignee: Wacker Chemie AG
    Inventors: Klaus Bonin, Jürgen Bezler
  • Patent number: 8907123
    Abstract: Yield and selectivity of olefin acetoxylation are improved through the use of successive catalyst zones of different reactivities, the successive zones contained in one or more reaction tubes arranged is parallel.
    Type: Grant
    Filed: August 23, 2012
    Date of Patent: December 9, 2014
    Assignee: Wacker Chemie AG
    Inventors: Anja Roscher, Hans-Juergen Eberle, Roland Heidenreich, Herbert Jung
  • Patent number: 8822717
    Abstract: Disclosed is a method for controlling a vinyl acetate production process. The method comprises reacting ethylene, acetic acid, and an oxygen-containing gas in the presence of a catalyst in a reactor to produce vinyl acetate, measuring the concentration of a component involved in or associated with the reaction and/or any of the subsequent steps by Raman spectroscopic analysis, and adjusting the conditions in the reactor or in any of the subsequent steps in response to the measured concentration of the component to achieve a proper control of the reaction or any of the subsequent steps.
    Type: Grant
    Filed: November 24, 2010
    Date of Patent: September 2, 2014
    Assignee: LyondellBassell Acetyls, LLC
    Inventors: Brian A. Salisbury, Noel C. Hallinan, Jenny M. Oran Osment
  • Patent number: 8802889
    Abstract: A process for production of allyl acetate includes steps of reacting acetic acid 3, oxygen 1 and propylene 2 in the presence of a catalyst in an oxidation reactor 5 to form allyl acetate and water; separating the unreacted acetic acid by a distillation column 9; and recovering an acetic acid-containing liquid which contains acetic acid and returning the acetic acid-containing liquid to the oxidation reactor 5 via an acetic acid-water evaporator 4, the process further including a heating step of heating a process liquid which contains the acetic acid-containing liquid to a temperature of 80 to 250° C. by a heater.
    Type: Grant
    Filed: September 20, 2011
    Date of Patent: August 12, 2014
    Assignee: Showa Denko K.K.
    Inventor: Wataru Oguchi
  • Publication number: 20130172602
    Abstract: A process for production of allyl acetate includes steps of reacting acetic acid 3, oxygen 1 and propylene 2 in the presence of a catalyst in an oxidation reactor 5 to form allyl acetate and water; separating the unreacted acetic acid by a distillation column 9; and recovering an acetic acid-containing liquid which contains acetic acid and returning the acetic acid-containing liquid to the oxidation reactor 5 via an acetic acid-water evaporator 4, the process further including a heating step of heating a process liquid which contains the acetic acid-containing liquid to a temperature of 80 to 250° C. by a heater.
    Type: Application
    Filed: September 20, 2011
    Publication date: July 4, 2013
    Applicant: SHOWA DENKO K.K.
    Inventor: Wataru Oguchi
  • Publication number: 20120310006
    Abstract: A process for producing allyl acetate is disclosed. The process comprises reacting a feed comprising propylene, acetic acid, oxygen, and carbon dioxide in the presence of a supported palladium catalyst. The feed comprises from 2 to 6 mole percent carbon dioxide, which improves the selectivity to allyl acetate.
    Type: Application
    Filed: August 10, 2012
    Publication date: December 6, 2012
    Applicant: Lyondell Chemical Technology, L.P.
    Inventors: Andrew P. Kahn, Elizabeth I. Ross-Medgaarden
  • Patent number: 8258336
    Abstract: A process for preparing unsaturated carboxylic esters includes reaction of alkenes having 2 to 6 carbon atoms with alkanecarboxylic acids having 1 to 6 carbon atoms in the presence of an oxygenous gas and in the presence of a heterogeneous noble metal catalyst by means of a continuous homogeneous gas phase process in a reactor. A gaseous phase (cycle gas) is circulated, and the cycle gas is laden with alkanecarboxylic acid in an acid saturator before entry into the reactor. In a presaturator connected upstream of the acid saturator, the cycle gas is laden with a portion of the amount of alkanecarboxylic acid used for saturation, and then it is transferred to the acid saturator and laden there with the remaining amount of alkanecarboxylic acid.
    Type: Grant
    Filed: April 21, 2009
    Date of Patent: September 4, 2012
    Assignee: Wacker Chemie AG
    Inventors: Heribert Westermayer, Johann Wagner, Willibald Dafinger, Peter Holl
  • Publication number: 20120130119
    Abstract: Disclosed is a method for controlling a vinyl acetate production process. The method comprises reacting ethylene, acetic acid, and an oxygen-containing gas in the presence of a catalyst in a reactor to produce vinyl acetate, measuring the concentration of a component involved in or associated with the reaction and/or any of the subsequent steps by Raman spectroscopic analysis, and adjusting the conditions in the reactor or in any of the subsequent steps in response to the measured concentration of the component to achieve a proper control of the reaction or any of the subsequent steps.
    Type: Application
    Filed: November 24, 2010
    Publication date: May 24, 2012
    Inventors: Brian A. Salisbury, Noel C. Hallinan, Jenny M. Oran Osment
  • Publication number: 20110077425
    Abstract: A process for producing allyl acetate is disclosed. The process comprises reacting a feed comprising propylene, acetic acid, oxygen, and carbon dioxide in the presence of a supported palladium catalyst. The feed comprises from 2 to 6 mole percent carbon dioxide, which improves the selectivity to allyl acetate.
    Type: Application
    Filed: September 30, 2009
    Publication date: March 31, 2011
    Inventors: Andrew P. Kahn, Elizabeth I. Ross-Medgaarden
  • Patent number: 7803965
    Abstract: The efficiency of vinyl acetate production is increased by scrubbing of off gas followed by CO2 absorption. A portion of the off gas containing substantial quantities of ethylene is recycled to the process, whereas another portion is employed in another ethylene consuming reaction. Despite not removing non-reactive gases, selectivity and yield based on ethylene are both increased.
    Type: Grant
    Filed: March 31, 2005
    Date of Patent: September 28, 2010
    Assignee: Wacker Chemie AG
    Inventors: Willibald Dafinger, Peter Holl, Wilhelm Kaiser, Jürgen Guba
  • Publication number: 20080249331
    Abstract: A microspheroidal support for the manufacture of a vinyl acetate catalyst which support comprises substantially inert microspheroidal particles of a mixture of silica and 0.5 to 5 wt % (based on the total weight of the support) of aluminium oxide. A vinyl acetate catalyst comprising the microspheroidal support, palladium, at least one metal, M, selected from the group consisting of gold, cerium, copper and mixtures thereof and at least one metal. A, selected from the group consisting of Group I, Group II, lanthanide and transition metal promoters.
    Type: Application
    Filed: June 8, 2006
    Publication date: October 9, 2008
    Inventors: Robert Edward Allan, John William Couves, George Frederick Salem, Bruce Leo Williams
  • Patent number: 7411107
    Abstract: A process for the oxidation of a C2 to C4 alkane to produce the corresponding alkene and carboxylic acid which process comprises separation of the alkene from a mixture of the alkene, the alkane and oxygen by absorption in a metallic salt solution, and recovery of an alkene-rich stream from the metallic salt solution. Integrated processes for the production of alkyl carboxylate and alkenyl carboxylate, which processes comprise oxidation of a C2 to C4 alkane to produce the corresponding alkene and carboxylic acid, separation of the alkene from a mixture of the alkene, the alkane and oxygen by absorption in a metallic salt solution, and recovery of an alkene-rich stream from the metallic salt solution for use in production of alkyl carboxylate or alkenyl carboxylate.
    Type: Grant
    Filed: February 12, 2003
    Date of Patent: August 12, 2008
    Assignee: BP Chemicals Limited
    Inventor: Andrew Richard Lucy
  • Patent number: 7265243
    Abstract: This invention relates to a catalyst which comprises palladium metal as the main catalyst, tin metal or a mixture of tin and additional metals as the promoter, in combination with an alkali or alkaline earth metal compound, supported on the outer surface of a porous carrier. The catalyst is used in the process for producing allyl acetate through the oxacylation of propylene, acetic acid and oxygen in a vapor phase. The catalyst of the present invention exhibits high catalytic activity, high catalytic selectivity and high catalytic life, which greatly increases the economic utility of the oxacylation process.
    Type: Grant
    Filed: March 1, 2004
    Date of Patent: September 4, 2007
    Assignee: Dairen Chemical Corporation
    Inventors: Shien-Chang Chen, Fu-Shen Lin, Liang-An Hsu, Pi-Fwu Jang
  • Patent number: 7202377
    Abstract: The present invention relates to a method of saturating ethylene-containing gases with acetic acid before they are fed into a vinyl acetate reactor, in which the acetic acid recovered in the vinyl acetate process is introduced into a column having a countercurrent stripping section and a rectification section and ethylene-containing gas is supplied via the bottom, wherein the liquid taken off at the bottom of the column is divided into two substreams and one substream is pumped back into the column with maintenance of a minimum pumped circulation required for sufficient saturation with acetic acid.
    Type: Grant
    Filed: October 28, 2005
    Date of Patent: April 10, 2007
    Assignee: Celanese Chemicals Europe GmbH
    Inventors: Bernd Rinne, Stefan Hess, Johann Stamm, Berthold Nuber
  • Patent number: 7166742
    Abstract: A fluid bed process for the manufacture of vinyl acetate from ethylene, acetic acid and oxygen comprising feeding ethylene and acetic acid into a fluid bed reactor through a first inlet, introducing the oxygen into the reactor through a second inlet, co-joining the oxygen, ethylene and acetic acid in the reactor in contact with a fluid bed catalyst to produce vinyl acetate. The particle size diameter of the particulate catalyst material has a range of 60% of the particles being below 200 microns (0.1 mm) with no more than 40% of the particles being below 40 microns (0.04 mm).
    Type: Grant
    Filed: November 25, 2003
    Date of Patent: January 23, 2007
    Assignee: The Standard Oil Company
    Inventors: Larry M. Cirjak, Michael F. Lemanski, David R. Wagner, Nancy C. Benkalowycz, Patricia R. Blum, Marc A. Pepera, Christos Paparizos
  • Patent number: 6987200
    Abstract: The invention relates to a method for producing a catalyst containing one or several metals from the group of metals comprising the sub-groups Ib and VIIIb of the periodic table on porous support particles, characterized by a first step in which one or several precursors from the group of compounds of metals from sub-groups Ib and VIIIb of the periodic table is or are applied to a porous support, and a second step in which the porous, preferably nanoporous support to which at least one precursor has been applied is treated with at least one reduction agent, to obtain the metal nanoparticles produced in situ in the pores of said support.
    Type: Grant
    Filed: March 24, 2003
    Date of Patent: January 17, 2006
    Assignee: Celanese Chemicals Europe GmbH
    Inventors: Alfred Hagemeyer, Uwe Dingerdissen, Klaus Kuhlein, Andreas Manz, Roland Fischer
  • Patent number: 6852877
    Abstract: A process for the production of vinyl acetate comprising contacting in a first reaction zone a gaseous feedstock comprising essentially ethane with a molecular oxygen-containing gas in the presence of a catalyst to produce a first product stream comprising acetic acid; contacting in a second reaction zone a gaseous feedstock comprising essentially ethane with a molecular oxygen-containing gas in the product stream comprising ethylene; contacting in a third reaction one the first gaseous product stream and the second gaseous product stream with a molecular oxygen-containing gas in the presence of a catalyst to produce a fourth product stream comprising vinyl acetate; separating the product stream from step (3) and recovering vinyl acetate from said product stream from step (3).
    Type: Grant
    Filed: May 19, 2000
    Date of Patent: February 8, 2005
    Assignee: Celanese International Corp.
    Inventors: Sabine Zeyss, Uwe Dingerdissen, John Fritch
  • Patent number: 6825149
    Abstract: A shell impregnated catalyst of Pd-Au produced on a silica support to have a Pd loading of 1.8 g/L of catalyst to about 7.2 g/L and a Au to Pd weight ratio of 0.3 to 2.0 by impregnating the support with aqueous solutions of palladium and gold salts or acids and thereafter precipitating water insoluble compounds of Pd and Au on the with alkali metal silicate or hydroxide solutions, then dried, and the surface precipitated compounds of Pd and Au are then reduced by reaction with ethylene or hydrogen at a temperature of greater than 150° C. up to 310° C. or with hydrogen up to 299° C. until substantially all of the Pd and Au contents are reduced to a free metal state, after which the support is impregnated with potassium acetate to an extent of 6 to 7 weight percent of the weight of the total catalyst.
    Type: Grant
    Filed: June 19, 2002
    Date of Patent: November 30, 2004
    Assignee: Saudi Basic Industries Corporation
    Inventor: Alla Konstantin Khanmamedova
  • Patent number: 6815394
    Abstract: A phenyl ester is produced by allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the presence of a catalyst comprising (A) palladium, (B) at least one element selected from elements of groups 13, 14, 15, and 16 and the fourth to sixth periods of the periodic table, and (C) at least one element selected from elements of groups 3, 4 and lanthanoid elements of the periodic table. Preferably, element (B) is selected from elements of group 16 and the fourth to sixth periods of the periodic table, and element (C) is contained in a metal oxide form in the catalyst.
    Type: Grant
    Filed: November 13, 2002
    Date of Patent: November 9, 2004
    Assignee: Tosoh Corporation
    Inventors: Yoshihiko Mori, Takao Doi, Tetsuo Asakawa, Takanori Miyake
  • Patent number: 6806382
    Abstract: A process for preparing a supported metal catalyst composition which comprises impregnating microspheroidal support particles with a solution of at least one catalytically active metal, or precursor, drying the impregnated support particles and then treating the mobile metal, or precursor in a mobile state with a liquid comprising at least one reducing agent to deposit and immobilize the metal, or its precursor, in the support particles such that the metal, or its precursor, is distributed in the support particle in a layer below the surface of the support particle, the layer being between an inner and an outer region having a lower concentration of metal or precursor. Also, a composition comprising microspheroidal support particles having at least one catalytically active metal or precursor thereof distributed in a layer below the surface of the particles, the layer being between an inner and an outer region of the support particle each having a lower concentration of metal or precursor.
    Type: Grant
    Filed: January 6, 2003
    Date of Patent: October 19, 2004
    Inventors: Michael James Baker, John William Couves, Kenneth George Griffin, Peter Johnston, James Colin McNicol, George Frederick Salem
  • Patent number: 6768013
    Abstract: A novel process for the direct oxidation of hydrogen and hydrocarbons is disclosed, where the explosion risks inherent in gas phase oxidations are substantially eliminated. Gaseous oxidation reactants are soluble in a first reaction solvent phase such as a perfluorocarbon (e.g. C8F18) and the oxidation product is preferentially soluble in a second product solvent phase such as water or a dilute acid. A solid catalyst such as palladium on alumina is then contacted with the dissolved reactants. The oxidation product such as hydrogen peroxide may be separated from the reaction solvent phase by extraction into the immiscible product solvent phase and then separated from it by distillation, thereby allowing re-use of the aqueous phase. The present invention may be carried out using a two-phase reaction system whereby both the reaction solvent and product solvent are contained within a reaction vessel into which the solid catalyst is slurried and mechanically agitated to promote the reaction.
    Type: Grant
    Filed: June 15, 2001
    Date of Patent: July 27, 2004
    Assignee: UOP LLC
    Inventor: Peter R. Pujado
  • Patent number: 6696596
    Abstract: A process for preparing vinyl acetate in the gas phase from ethylene, acetic acid and oxygen or oxygen-containing gases over a catalyst, consisting essentially of palladium and/or its compounds, gold and/or its compounds and alkali metal compounds on a support, wherein the catalyst further comprises vanadium and/or its compounds and catalyst therefrom.
    Type: Grant
    Filed: October 24, 2001
    Date of Patent: February 24, 2004
    Assignee: Celanese Chemicals Europe GmbH
    Inventors: Bernhard Herzog, Axel Schafer, Karl H Renkel
  • Publication number: 20030176730
    Abstract: In yielding diacetoxybutene by feeding butadiene, acetic acid, and oxygen in the presence of a solid catalyst containing palladium, the butadiene can be efficiently reacted to produce diacetoxybutene in high yield by feeding an oxygen-containing gas containing 7 mol % or more oxygen as fine bubbles to a reaction zone containing the solid catalyst.
    Type: Application
    Filed: April 14, 2003
    Publication date: September 18, 2003
    Applicant: MITSUBISHI CHEMICAL CORPORATION
    Inventors: Kazuhiro Makino, Hiroshi Iwasaka, Kazuyuki Okubo, Koji Hata
  • Patent number: 6620965
    Abstract: A process for producing vinyl acetate comprising reacting ethylene, acetic acid and oxygen together in at least partially liquid phase in the presence of a catalyst comprising a noble metal component.
    Type: Grant
    Filed: March 8, 2002
    Date of Patent: September 16, 2003
    Assignee: Catalytic Distillation Technologies
    Inventors: John R. Adams, Willibrord A. Groten, Speros P. Nemphos
  • Patent number: 6605739
    Abstract: Methods for the catalytic production of vinyl acetate monomer from ethane, ethylene or an ethanelethylene mixture using a first catalyst containing MoVNbPd, MoVLaPdbX (where X is Al, Ga, Ge or Si) or MoVNbX (where X is P, B, Hf, Te, As or mixtures thereof) in the first step of oxidation and using a conventional VAM catalyst for the second step. The method produces high yields to acetic acid and vinyl acetate without the coproduction of carbon monoxide. Furthermore, the ethylene and acetic acid produced in the first step may be utilized in the second step for VAM production.
    Type: Grant
    Filed: November 13, 2001
    Date of Patent: August 12, 2003
    Assignee: Saudi Basic Industries Corporation
    Inventors: Khalid Karim, Alaa E. M. Adris
  • Patent number: 6534672
    Abstract: A catalytically active material useful to prepare vinyl acetate monomer from ethylene, acetic acid, and an oxygen-containing gas under fluid bed conditions comprises a porous microspheroidal support containing catalytically active palladium crystallites finely dispersed within the support. This catalyst material does not require incorporation of gold to maintain activity and selectivity. A process to produce a vinyl acetate fluid bed catalyst in which catalytically active small palladium crystallites are finely dispersed within the support comprises dispersing selected metal species within the support which have an affinity to palladium to form very fine crystallites of palladium. The affinity metal species may be dispersed by impregnation onto a preformed microspheroidal support or may be intimately incorporated within the support before impregnation with a soluble palladium species.
    Type: Grant
    Filed: December 4, 2001
    Date of Patent: March 18, 2003
    Assignee: The Standard Oil Company
    Inventors: George Frederick Salem, Michael James Baker
  • Patent number: 6528679
    Abstract: A phenyl ester is produced by allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the presence of a catalyst comprising (A) palladium, (B) at least one element selected from elements of groups 13, 14, 15, and 16 and the fourth to sixth periods of the periodic table, and (C) at least one element selected from elements of groups 3, 4 and lanthanoid elements of the periodic table. Preferably, element (B) is selected from elements of group 16 and the fourth to sixth periods of the periodic table, and element (C) is contained in a metal oxide form in the catalyst. The phenyl ester can be converted to phenol by hydrolysis or ester exchange.
    Type: Grant
    Filed: September 27, 2000
    Date of Patent: March 4, 2003
    Assignee: Tosoh Corporation
    Inventors: Yoshihiko Mori, Takao Doi, Tetsuo Asakawa, Takanori Miyake
  • Patent number: 6472556
    Abstract: A catalyst for use in the production of vinyl acetate which comprises (1) a catalyst support, (2) palladium, (3) an acid, (4) at least one acetic acid catalyst promoter and (5) at least one vinyl acetate promoter and/or co-promoter. A process for the production of vinyl acetate from ethylene and an oxygen-containing gas using the catalyst.
    Type: Grant
    Filed: March 27, 2001
    Date of Patent: October 29, 2002
    Assignee: BP Chemicals Limited
    Inventors: Simon James Kitchen, Daiyi Qin
  • Patent number: 6448432
    Abstract: A process for the fluid bed production of vinyl acetate which comprises reacting ethylene, acetic acid and an oxygen-containing gas in a fluid bed reactor at elevated temperature in the presence of a fluidised bed of catalyst, in which process, catalyst is added to said fluidised bed of catalyst, wherein the overall catalytic activity of the fluidised bed of catalyst is controlled to a pre-determined value by adjusting the activity and/or adjusting the rate of addition of said added catalyst.
    Type: Grant
    Filed: June 11, 2001
    Date of Patent: September 10, 2002
    Assignee: BP Chemicals Limited
    Inventor: Bruce Leo Williams
  • Patent number: 6420308
    Abstract: A shell impregnated catalyst of Pd—Au produced on a silica support to have a Pd loading of 1.8 g/L of catalyst to about 7.2 g/L and a Au to Pd weight ratio of 0.3 to 2.0 by impregnating the support with aqueous solutions of palladium and gold salts or acids and thereafter precipitating water insoluble compounds of Pd and Au on the with alkali metal silicate or hydroxide solutions, then dried, and the surface precipitated compounds of Pd and Au are then reduced by reaction with ethylene or hydrogen at a temperature of greater than 150° C. up to 310° C. or with hydrogen up to 299° C. until substantially all of the Pd and Au contents are reduced to a free metal state, after which the support is impregnated with potassium acetate to an extent of 6 to 7 weight percent of the weight of the total catalyst.
    Type: Grant
    Filed: July 7, 2000
    Date of Patent: July 16, 2002
    Assignee: Saudi Basic Industries Corp
    Inventor: Alla Konstantin Khanmamedova
  • Patent number: 6420595
    Abstract: A method of real time process control in a reaction system for the production of vinyl acetate from the oxidation of ethylene and acetic acid. Reaction system samples are collected from the reactor vessel feed and/or effluent and/or from columns and/or transfer lines downstream of the reactor vessel, and the concentration of one or more components in the sample is measured by an infrared analyzer. The concentration measurements are then used to make adjustments in the concentration of components in the reaction system, directly or indirectly, such as by adjusting the temperature profile in a particular column, the flow rate of solution in to or out of a column, or the addition or extraction of a component to or from the solution. For optimum process control, the measurements are transmitted to a control unit for real time analysis, and the adjustments are made almost instantly after the infrared analysis.
    Type: Grant
    Filed: September 10, 2001
    Date of Patent: July 16, 2002
    Assignee: Millennium Petrochemicals, Inc.
    Inventors: Noel Hallinan, Wayne Brtko
  • Patent number: 6407283
    Abstract: A process for the production of vinyl acetate which comprises contacting ethylene, acetic acid and an oxygen-containing gas with a supported palladium catalyst prepared by a process comprising the steps of (a) impregnating a catalyst support with a palladium compound, (b) converting the palladium compound to substantially metallic palladium, and (c) sintering the supported palladium at a temperature of greater than 500° C.
    Type: Grant
    Filed: June 28, 2001
    Date of Patent: June 18, 2002
    Assignee: BP Chemicals Limited
    Inventors: John William Couves, Simon James Kitchen
  • Patent number: 6399813
    Abstract: A process for the preparation of a fluid bed vinyl acetate (VAM) catalyst comprising impregnating a support comprising a mixture of substantially inert microspheroidal particles with a solution comprising a metal salt of Pd and M, wherein M comprises Ba, Cd, Au, La, Nb, Ce, Zn, Pb, Ca, Sr, Sb or mixtures thereof, reducing the metal salts to form a deposit of Pd and M on the support surface and impregnating the support with at least one alkali metal salt. At least 50% of the particles used for the microspheroidal support have a particle size below 105 microns.
    Type: Grant
    Filed: August 14, 2001
    Date of Patent: June 4, 2002
    Assignee: The Standard Oil Company
    Inventors: Patricia Rae Blum, Larry Michael Cirjak, Marc Anthony Pepera, Christos Paparizos, George Frederick Salem, Michael James Baker
  • Patent number: 6376706
    Abstract: A catalyst for use in the production of vinyl acetate which comprises (1) a catalyst support, (2) palladium, (3) an acid, (4) at least one acetic acid catalyst promoter and (5) at least one vinyl acetate promoter and/or co-promoter. A process for the production of vinyl acetate from ethylene and an oxygen-containing gas using the catalyst.
    Type: Grant
    Filed: May 21, 1999
    Date of Patent: April 23, 2002
    Assignee: BP Chemical Ltd.
    Inventors: Simon James Kitchen, Daiyi Qin
  • Publication number: 20020028966
    Abstract: A process for the preparation of a fluid bed vinyl acetate (VAM) catalyst comprising impregnating a support comprising a mixture of substantially inert microspheroidal particles with a solution comprising a metal salt of Pd and M, wherein M comprises Ba, Cd, Au, La, Nb, Ce, Zn, Pb, Ca, Sr, Sb or mixtures thereof, reducing the metal salts to form a deposit of Pd and M on the support surface and impregnating the support with at least one alkali metal salt. At least 50% of the particles used for the microspheroidal support have a particle size below 105 microns.
    Type: Application
    Filed: August 14, 2001
    Publication date: March 7, 2002
    Inventors: Patricia Rae Blum, Larry Michael Cirjak, Marc Anthony Pepera, Christos Paparizos, George Frederick Salem, Michael James Baker
  • Patent number: 6350901
    Abstract: In a process for production of vinyl acetate in which ethylene, liquid acetic acid and an oxygen-containing gas are fed to a fluid bed reactor containing a catalyst comprising a Group VIII metal, a promoter and a co-promoter, stickiness of the catalyst is reduced by limiting the amount of co-promoter to up to 6% by weight of the catalyst.
    Type: Grant
    Filed: July 29, 1999
    Date of Patent: February 26, 2002
    Assignee: BP Chemicals Limited
    Inventors: Simon James Kitchen, George Frederick Salem, Bruce Leo Williams
  • Patent number: 6350900
    Abstract: A catalyst for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid comprising a porous support on the porous surfaces of which is deposited catalytically effective amounts of metallic palladium and gold, said catalyst having been prepared by steps comprising impregnating a porous support, the porous surfaces of which contain a catalytically effective amount of a prereduced metallic palladium, with a solution of potassium aurate, and reducing the potassium aurate to a catalytically effective amount of metallic gold. Alternate embodiments are also disclosed.
    Type: Grant
    Filed: June 2, 1998
    Date of Patent: February 26, 2002
    Assignee: Celanese International Corporation
    Inventors: Tao Wang, Jerry A. Broussard
  • Patent number: 6342628
    Abstract: In a process for production of vinyl acetate by the reaction of ethylene, acetic acid and oxygen, ethylene is recovered from the gases withdrawn from the reactor and recycled such that the amount of ethylene in the combined feed to the reactor is at least 60 mol %.
    Type: Grant
    Filed: July 29, 1999
    Date of Patent: January 29, 2002
    Assignee: BP Chemicals Limited
    Inventors: Bruce Leo Williams, Robert William Clarke, Timothy Crispin Bristow, Michael James Baker
  • Publication number: 20010056201
    Abstract: A process for the production of vinyl acetate which comprises contacting ethylene, acetic acid and an oxygen-containing gas with a supported palladium catalyst prepared by a process comprising the steps of (a) impregnating a catalyst support with a palladium compound, (b) converting the palladium compound to substantially metallic palladium, and (c) sintering the supported palladium at a temperature of greater than 500° C.
    Type: Application
    Filed: June 28, 2001
    Publication date: December 27, 2001
    Applicant: BP Chemicals Limited
    Inventors: John William Couves, Simon James Kitchen
  • Patent number: 6303536
    Abstract: This invention relates to a preparation process of a catalyst which comprises a noble metal and a metal as catalysis promoter in combination with an alkali or alkaline earth metal compound, supported on the outer surface of a carrier. The preparation process comprises impregnating the carrier with a solution containing an oxidative state noble metal as the main catalyst and an oxidative state metal as catalysis promoter, reducing the oxidative state metals into the metallic state in gaseous phase with a gaseous reducing agent under certain temperature, pressure, moisture and gas concentration, then impregnating the reduced carrier with a solution of an alkali or alkaline earth metal compound. The metal components-supporting catalyst prepared by the process according to the present invention has a high surface area and exhibits high catalytic activity, which leads to increase the catalytic efficiency and life of this heterogeneous catalyst.
    Type: Grant
    Filed: August 16, 1999
    Date of Patent: October 16, 2001
    Assignee: Dairen Chemical Coorporation
    Inventors: Shien-Chang Chen, Fu-Shen Lin, Yuh-Lih Jong, Pi-Fwu Jang
  • Patent number: 6288269
    Abstract: Apparatus for introducing a fluid into a process stream such as promoter into the feed stream of a reactor for manufacturing vinyl acetate comprises: (a) a process stream pipe having a bend and (b) a nozzle for introducing the fluid into the process stream downstream of the bend characterised in that the pipe has a flow-correction device downstream of the bend and the nozzle is mounted downstream of the flow-correction device to an end of a support arm which extends into the pipe in a direction substantially parallel to the direction of the pipe downstream of the bend.
    Type: Grant
    Filed: December 16, 1999
    Date of Patent: September 11, 2001
    Assignee: BP Chemicals Limited
    Inventor: Derek Alan Colman
  • Publication number: 20010018401
    Abstract: A process for the preparation of a fluid bed vinyl acetate (VAM) catalyst comprising impregnating a support comprising a mixture of substantially inert microspheroidal particles with a solution comprising a metal salt of Pd and M, wherein M comprises Ba, Cd, Au, La, Nb, Ce, Zn, Pb, Ca, Sr, Sb or mixtures thereof, reducing the metal salts to form a deposit of Pd and M on the support surface and impregnating the support with at least one alkali metal salt. At least 50% of the particles used for the microspheroidal support have a particle size below 105 microns.
    Type: Application
    Filed: June 30, 1999
    Publication date: August 30, 2001
    Inventors: PATRICIA RAE BLUM, LARRY MICHAEL CIRJAK, MARC ANTHONY PEPERA, CHRISTOS PAPARIZOS, GEORGE FREDERICK SALEM, MICHAEL JAMES BAKER
  • Patent number: RE37744
    Abstract: A process for the production of vinyl acetate which comprises contacting ethylene, acetic acid and an oxygen-containing gas with a supported palladium catalyst prepared by a process comprising the steps of (a) impregnating a catalyst support with a palladium compound, (b) converting the palladium compound to substantially metallic palladium, and (c) sintering the supported palladium at a temperature of greater than 500° C.
    Type: Grant
    Filed: July 19, 2000
    Date of Patent: June 11, 2002
    Assignee: BP International Limited
    Inventors: John William Couves, Simon James Kitchen
  • Patent number: RE43859
    Abstract: Methods for the catalytic production of vinyl acetate monomer from ethane, ethylene or an ethane/ethylene mixture using a first catalyst containing MoVNbPd, MoVLaPdNbX (where X is Al, Ga, Ge or Si) or MoVNbX (where X is P, B, Hf, Te, As or mixtures thereof) in the first step of oxidation and using a conventional VAM catalyst for the second step. The method produces high yields to acetic acid and vinyl acetate without the coproduction of carbon monoxide.
    Type: Grant
    Filed: February 8, 2006
    Date of Patent: December 11, 2012
    Assignee: Saudi Basic Industries Corporation
    Inventors: Khalid Karim, Alaa E. M. Adris