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WO1998033590A1 - Catalyseur de carbonylation - Google Patents

Catalyseur de carbonylation Download PDF

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Publication number
WO1998033590A1
WO1998033590A1 PCT/US1998/001866 US9801866W WO9833590A1 WO 1998033590 A1 WO1998033590 A1 WO 1998033590A1 US 9801866 W US9801866 W US 9801866W WO 9833590 A1 WO9833590 A1 WO 9833590A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
carbonylation
catalysts
iridium
halide
Prior art date
Application number
PCT/US1998/001866
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English (en)
Inventor
Gerald Charles Tustin
Joseph Robert Zoeller
Horace Lawrence Browning, Jr.
Andy Hugh Singleton
Original Assignee
Eastman Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO1998033590A1 publication Critical patent/WO1998033590A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium

Definitions

  • This invention pertains to a novel catalyst composition. More specifically, this invention pertains to 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.
  • the novel catalysts are especially useful to catalyze the preparation of acetic acid, methyl acetate or a mixture thereof by contacting a vapor comprising methanol, a halide and carbon monoxide with one of the catalysts.
  • Patent 5,488,143 describes the use of alkali, alkaline earth or transition metals as promoters for supported rhodium for the halide—promoted, vapor phase methanol carbonylation reaction.
  • Pimblett in U.S. Patent 5,258,549, teaches that the combination of rhodium and nickel on a carbon support is more active than either metal by itself.
  • EP 0 759 419 Al discloses supported catalysts in the carbonyla— tion of alcohols and/or reactive derivatives of alcohols. More specifically, EP 0 759 419 Al discloses a process which comprises a first carbonylation reactor wherein an alcohol is carbonylated in the liquid phase in the presence of a homogeneous catalyst system and the off gas from this first reactor is then mixed with additional alcohol and fed to a second reactor containing a supported catalyst.
  • the homogeneous catalyst system utilized in the first reactor comprises a halogen component and a Group VIII metal selected from rhodium and iridium.
  • the homogeneous catalyst system also may contain an optional co—promoter selected from the group consisting of ruthenium, osmium, rhenium, cadmium, mercury, zinc, indium and gallium.
  • an optional co—promoter selected from the group consisting of ruthenium, osmium, rhenium, cadmium, mercury, zinc, indium and gallium.
  • the supported catalyst employed in the second reactor comprises a
  • Group VIII metal selected from the group consisting of iridium, rhodium and nickel, and an oprtional metal promoter on a carbon support.
  • the optional metal promoter may be iron, nickel, lithium and cobalt.
  • Patent 5,185,462 describe heterogeneous catalysts for halide— promoted vapor phase methanol carbonylation based on noble metals attached to nitrogen or phosphorus ligands attached to an oxide support.
  • Panster et al. in U.S. Patent 4,845,163, describe the use of rhodium—containing organopolysiloxane—ammonium compounds as heterogeneous catalysts for the halide—promoted liquid phase carbonylation of alcohols.
  • Patent 4,417,077 describe the use of anion exchange resins bonded to anionic forms of a single transition metal as catalysts for a number of carbonylation reactions including the halide—promoted carbonylation of methanol.
  • supported ligands and anion exchange resins may be of some use for immobilizing metals in liquid phase carbonylation reactions, in general, the use of supported ligands and anion exchange resins offer no advantage in the vapor phase carbonylation of alcohols compared to the use of the carbon as a support for the active metal component.
  • Nickel on activated carbon has been studied as a heterogeneous catalyst for the halide—promoted vapor phase carbonylation of methanol, and increased rates are observed when hydrogen is added to the feed mixture.
  • Relevant references to the nickel—on—carbon catalyst systems are provided by Fujimoto et al. in Chemistry Letters (1987) 895—898 and in Journal of Catalysis, 133 (1992) 370—382 and in the references contained therein. Liu et al., in Ind. Eng. Chem. Res . , 33 (1994) 488-492, report that tin enhances the activity of the nickel—on- carbon catalyst.
  • Patent 4,918,2108 disclose the addition of palladium and optionally copper to supported nickel catalysts for the halide—promoted carbonylation of methanol.
  • nickel—based catalysts In general the rates of reaction provided by nickel—based catalysts are lower than those provided by the analogous rhodium— based catalysts when operated under similar conditions.
  • Other single metals supported on carbon have been reported by Fujimoto et al. in Catalysis Letters, 2 (1989) 145-148 to have limited activity in the halide- pro oted vapor phase carbonylation of methanol. The most active of these metals is Sn. Following Sn in order of decreasing activity are Pb, Mn, Mo, Cu, Cd, Cr, Re, V, Se, W, Ge and Ga.
  • This invention pertains to supported catalysts comprising iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material.
  • the novel supported catalysts of the present invention may be used in various vapor phase processes, especially vapor phase processes for the manufacture of acetic acid and/or methyl acetate.
  • the supported catalyst of the present invention comprises a mixture of iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material.
  • a catalyst support material examples include carbon and the oxides or mixed oxides of silicon, aluminum, zinc, zirconium, or titanium.
  • the preferred support materials are selected from the wide variety of carbon, activated carbon, and silicon oxide sources available commercially. Oxides of aluminum, or materials containing oxides of aluminum are least preferred.
  • the catalyst is prepared by
  • step (2) (2) combining the solution of step (1) with the support material; (3) slowly evaporating the solvent; and, optionally, (4) heating the dried catalyst from step (3) at elevated temperature in a stream of inert gas or in a vacuum. Variations in this method of catalyst preparation are well known to those skilled in the art and may be used.
  • the compound or form of iridium used to prepare the catalyst generally is not critical, and the catalyst may be prepared from any of a wide variety of iridium containing compounds, indeed, iridium compounds containing myriad combinations of halide, trivalent nitrogen, organic compounds of trivalent phosphorous, carbon monoxide, hydrogen, and 2 ,4—pentanedione, either alone or in combination, are available commercially and may be used in the preparation of the catalysts utilized in the present invention.
  • the oxides of iridium may be used if dissolved in the appropriate medium.
  • the preferred sources of iridium is one of its chlorides, such as the hydrated trichloride and any of the various salts of hexachloroiridate(IV) .
  • Use of either iridium trichloride or the hexacholoroiridate complexes should be comparable on the basis of cost, solubility, and performance.
  • the compound or form of the second metal compound used to prepare the catalyst generally is not critical, and the catalyst may be prepared using any of a wide variety of compounds containing ruthenium, molybdenum, tungsten, palladium, platinum or rhenium.
  • a wide variety of compounds of these elements containing various combinations of halides, acetates, nitrates, trivalent nitrogen, organic compounds of trivalent phosphorous, carbon monoxide, hydrogen, and 2,4—pentanedione, either alone or in combination, are available commercially and may be used in the preparation of the catalysts utilized in the present invention.
  • the oxides of these materials may be used if dissolved in the appropriate medium.
  • the compound used to provide the second metal preferably is a water soluble form of the metal (s). Based on their availability and cost, the preferred sources are the various acetates, nitrates, and halides of the second metals.
  • the most preferred source among these salts would be dictated by its solubility (preferably water solubility) which can vary widely across this list of useful second components.
  • solubility preferably water solubility
  • the halides are generally available and quite soluble.
  • the content of iridium and the second component present on the catalysts can vary over a wide range, for example from 0.01 to 10 weight percent for each metal. However, the preferred catalysts contain 0.1 to 2 weight percent of each component.
  • the second metal component of the catalysts utilized in the present invention preferably is ruthenium or molybdenum.
  • the supported carbonylation catalysts which are particularly preferred comprise (i) iridium and ruthenium or (ii) iridium and molybdenum deposited on a catalyst support material selected from carbon, activated carbon, and silicon oxide wherein the iridium and ruthenium each constitute 0.1 to 2 weight percent of the weight of the catalyst.
  • novel supported catalysts of the present invention may be used in a vapor phase process for the preparation of acetic acid, methyl acetate or a mixture thereof which comprises the steps of:
  • a gaseous mixture comprising methanol, carbon monoxide, and a halide selected from chlorine, bromine, iodine and compounds thereof to a carbonylation zone which (i) contains 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 and (ii) is maintained under carbonylation conditions of temperature and pressure; and
  • the methanol utilized in the process normally is fed as methanol, it can be supplied in the form of a combination of materials which generate methanol reactant. Examples of such combination of materials include (i) methyl acetate and water and
  • the presence of water in the gaseous feed mixture is not essential when using methanol, the presence of some water is desirable to suppress formation of methyl acetate and/or dimethyl ether.
  • the molar ratio of water to methanol can be 0:1 to 10:1, but preferably is in the range of 0.01:1 to 1:1.
  • the amount of water fed usually is increased to account for the mole of water required for hydrolysis of the methanol alternative. Therefore, when using either methyl acetate or dimethyl ether, the mole ratio of water to ester or ether is in the range of 1:1 to 10:1, but preferably in the range of 1:1 to 3:1.
  • acetic acid it is apparent that combinations of methanol, methyl ester, and/or dimethyl ether are equivalent, provided the appropriate amount of water is added to hydrolyze the ether or ester to provide the methanol reactant.
  • the gaseous mixture fed to the carbonylation zone also contains a halide component selected from chlorine, bromine, iodine and compounds thereof.
  • the preferred halide components are selected from bromine, bromine compounds and, especially, iodine and iodine compounds which are gaseous under the carbonylation conditions of temperature and pressure.
  • the halide components may be fed in various forms although the preferred forms are as an alkyl halide, especially as methyl halide, the hydrogen halide, or as the molecular halide, i.e., I 2 , Br 2 , or Cl 2 .
  • the molar ratio of methanol (or methanol equivalents) to halide or halide compound may vary substantially but typically is in the range of 1:1 to
  • the carbon monoxide may be fed to the carbonylation zone either as purified carbon monoxide or as a mixture of hydrogen and carbon monoxide.
  • a small quantity of hydrogen may be useful in maintaining optimal catalyst activity, e.g. , CO:hydrogen volume ratios of 99.5:0.5 to 95:5, the ratio of carbon monoxide to hydrogen, the presence of hydrogen, is believed to be of only minor importance.
  • CO:hydrogen ratios of 100:0 to 25:75 all seem to be useful.
  • the preferred CO:hydrogen ratios normally are in the range of 99:1 to 2:1.
  • the carbonylation process is operated in the vapor phase and, therefore, is practiced at temperatures above the dew point of the product mixture, i.e., the temperature at which condensation occurs.
  • the dew point is a complex function of dilution (particularly with respect to non—condensable gases such as unreacted carbon monoxide, hydrogen, or inert diluent gas) , product composition, and pressure
  • the process may still be operated over a wide range of temperatures, provided the temperature exceeds the dew point of the product effluent. In practice, this generally dictates a temperature range of 100 to 350°C, with temperatures in the range of 150 to 275°C being particularly useful.
  • the useful pressure range is limited by the dew point of the product mixture.
  • a wide range of pressures may be used, e.g., pressures in the range of 0.1 to 100 bars absolute (bara) (10 to 10,000 kPa) .
  • the process preferably is carried out at a pressure in the range of 1 to 50 bara (100 to 5,000 kPa) , most preferably, 3 to 30 bara (300 to 3,000 kPa) .
  • Iridium trichloride hydrate (418.9 g) and ruthenium trichloride hydrate (275.7 mg) were dissolved in deionized water (30 mL) .
  • This mixture was added to 12 X 40 mesh activated carbon granules (20.0 g) having a BET surface area in excess of 800 m 2 /g contained in an evaporating dish.
  • the mixture was heated on the steam bath with occasional stirring until it became free flowing and then transferred to a quartz tube measuring 106 cm long by 25 mm outer diameter.
  • the quartz tube containing the mixture was placed in a three—element electric tube furnace so that the mixture was located in the approximate center of the 61 cm long heated zone of the furnace.
  • Catalyst I contained 1.00 weight percent Ir and 0.49 weight percent Ru and had a density of 0.57 g per mL.
  • Example 2 The procedure described in Example 1 was repeated except that 206.7 mg (1.166 mmol) of palladium chloride was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst II) which contained 1.00 weight percent Ir and 0.49 weight percent Pd and had a density of 0.57 g per mL.
  • Example 2 The procedure described in Example 1 was repeated except that 312.7 mg (1.166 mmol) of ammonium perrhenate (NH 4 Re0 4 ) was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst III) which contained 1.00 weight percent Ir and 0.49 weight percent Re and had a density of 0.57 g per mL.
  • NH 4 Re0 4 ammonium perrhenate
  • Example 4 The procedure described in Example 1 was repeated except that 20 g of silica gel (Davison Chemical Company, Baltimore, Md, Grade 57, mesh 8) was substituted for carbon during catalyst preparation to produce a catalyst comprising 1.00 weight percent Ir and 0.49 weight percent Ru on silica (Catalyst IV).
  • silica gel Davis Chemical Company, Baltimore, Md, Grade 57, mesh 8
  • Example 2 The procedure described in Example 1 was repeated except that 331.06 mg (1.166 mmol of tungsten) of ammonium tungsten oxide [ (NH ) 6 W 1 0 41 ) -5 H 2 0] was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst V) which contained 1.08 weight percent Ir and 1.03 weight percent tungsten on activated carbon.
  • Example 2 The procedure described in Example 1 was repeated except that 205.85 mg (1.166 mmol of molybdenum) of ammonium molybdenum oxide [ (NH 4 ) 6 Mo 7 0 24 ) «5 H 2 0] was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst VI) which contained 1.05 weight percent Ir and 0.52 weight percent molybdenum on activated carbon.
  • Catalyst VI which contained 1.05 weight percent Ir and 0.52 weight percent molybdenum on activated carbon.
  • Example 2 The procedure described in Example 1 was repeated except that 1.153 g (4.665 mmol) of chromium acetate monohydrate was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VI) which contained 1.09 weight percent Ir and 0.29 weight percent chromium on activated carbon.
  • COMPARATIVE CATALYST EXAMPLE C-7 The procedure described in Example 1 was repeated except that 290.4 mg (1.166 mmol) of cobalt acetate tetrahydrate was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VII) which contained 1.08 weight percent Ir and 0.33 weight percent cobalt on activated carbon.
  • Example 2 The procedure described in Example 1 was repeated except that 106.46 mg (1.166 mmol) of ferrous chloride was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VIII) which contained 1.09 weight percent Ir and 0.32 weight percent iron on activated carbon.
  • the reactor system consisted of a 800 to 950 mm (31.5 and 37 inch) section of 6.35 mm ( " inch) diameter tubing constructed of Hastelloy alloy.
  • the upper portion of the tube constituted the preheat and reaction (carbonylation) zones which were assembled by inserting a quartz wool pad 410 mm from the top of the reactor to act as support for the catalyst, followed sequentially by (1) a 0.7 g bed of fine quartz chips (840 microns), (2) 0.5 g of one of the catalysts prepared as described in the preceding examples, and (3) an additional 6 g of fine quartz chips.
  • the top of the tube was attached to an inlet manifold for introducing liquid and gaseous feeds.
  • the six g of fine quartz chips acted as a heat exchange surface to vaporize the liquid feeds. Care was taken not to allow any liquid feeds to contact the catalyst bed at any time, including assembly, start—up, operation, and shutdown.
  • the remaining lower length of tubing (product recovery section) consisted of a vortex cooler which varied in length depending on the original length of tubing employed and was maintained at approximately 0—5°C during operation.
  • the gases were fed using Brooks flow controllers and liquids were fed using a high performance liquid chromatography pump.
  • the gaseous products leaving the reaction zone were condensed using a vortex cooler operating at 0—5°C.
  • the product reservoir was a tank placed downstream from the reactor system.
  • the pressure was maintained using a modified Research control valve on the outlet side of the reactor system and the temperature of the reaction section was maintained using heating tape on the outside of the reaction system.
  • Feeding of hydrogen and carbon monoxide to the reactor was commenced while maintaining the reactor at a temperature of 240°C and a pressure of 17.2 bara (250 psia; 1,720 kPa) .
  • the flow rate of hydrogen was set at 25 standard cubic cm.
  • “Production Rate” is the moles of Acetyl Produced per liter of catalyst volume per hour during each increment of Time (Time Increment), i.e., the time of operation between samples.
  • the formula for determining moles of Acetyl Produced per liter of catalyst volume per hour is:
  • Catalysts II—VI and Comparative Catalysts C—I — C—IX were utilized in the carbonylation of methanol according to the above—described procedure.
  • the Production Rate i.e., the moles of Acetyl Produced per liter of catalyst volume per hour, provided by each of Catalysts II—VI and Comparative Catalysts C—I — C—IX is shown in Table III.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a trait à des catalyseurs sur support comprenant de l'iridium et au moins un second métal sélectionné dans le groupe constitué par le ruthénium, le molybdène, le tungstène, le palladium, le platine et le rhénium, déposés sur un matériau support pour catalyseurs. Ces catalyseurs sont utiles pour des procédés en phase vapeur de préparation d'acide acétique, d'acétate de méthyle ou d'un mélange de ceux-ci, par mise en contact d'une vapeur renfermant du méthanol, un halogénure et du monoxyde de carbone avec l'un de ces catalyseurs.
PCT/US1998/001866 1997-02-04 1998-01-30 Catalyseur de carbonylation WO1998033590A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US3718497P 1997-02-04 1997-02-04
US60/037,184 1997-02-04
US1077598A 1998-01-22 1998-01-22
US09/010,775 1998-01-22

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000048976A1 (fr) * 1999-02-16 2000-08-24 Eastman Chemical Company Catalyseur d'iridium pour la carbonylation d'alcools aliphatiques inferieurs
WO2000048979A1 (fr) * 1999-02-16 2000-08-24 Eastman Chemical Company Catalyseur ayant un composant solide et vaporeux pour la carbonylation d'alcools d'alkyle inferieur
WO2001014055A1 (fr) * 1999-08-25 2001-03-01 Eastman Chemical Company Catalyseur de carbonylation a base d'iridium dope par un metal du groupe 5
WO2001014056A1 (fr) * 1999-08-25 2001-03-01 Eastman Chemical Company Catalyseur de carbonylation a base d'iridium dope par un metal du groupe 4
WO2001077059A3 (fr) * 2000-04-05 2002-04-25 Eastman Chem Co Carbonylation d'alkyl alcools inferieurs et derives associes mettant en oeuvre des metaux supportes sur des copolymeres divinylbenzene-styrene carbones polysulfonates
US6458995B1 (en) 2000-03-31 2002-10-01 Celanese International Corporation Catalytic composition for carbonylation including iridium and pyridine polymers
US6537944B1 (en) 2001-06-20 2003-03-25 Eastman Chemical Company Tungsten promoted catalyst for carbonylation of lower alkyl alcohols
US6627770B1 (en) 2000-08-24 2003-09-30 Celanese International Corporation Method and apparatus for sequesting entrained and volatile catalyst species in a carbonylation process
US6646154B2 (en) 2001-06-20 2003-11-11 Eastman Chemical Company Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst
EP3257836A1 (fr) 2007-04-25 2017-12-20 Celanese International Corporation Procédé et appareil améliorés de carbonylation avec réduction de la perte de catalyseur

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848377A (en) * 1953-10-19 1958-08-19 Standard Oil Co Platinum catalyst composite employed in the hydroforming of a naphtha
US3719739A (en) * 1970-01-29 1973-03-06 Exxon Research Engineering Co Method of preparing a catalyst
US3839192A (en) * 1970-05-22 1974-10-01 Universal Oil Prod Co Hydrocarbon conversion with a catalytic composite of palladium, iridium and halogen
US4018670A (en) * 1971-11-01 1977-04-19 Exxon Research And Engineering Company Hydrocarbon conversion process
GB2171925A (en) * 1985-02-02 1986-09-10 Agency Ind Science Techn Process for the manufacture of ethanol based, oxygen-containing carbon compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848377A (en) * 1953-10-19 1958-08-19 Standard Oil Co Platinum catalyst composite employed in the hydroforming of a naphtha
US3719739A (en) * 1970-01-29 1973-03-06 Exxon Research Engineering Co Method of preparing a catalyst
US3839192A (en) * 1970-05-22 1974-10-01 Universal Oil Prod Co Hydrocarbon conversion with a catalytic composite of palladium, iridium and halogen
US4018670A (en) * 1971-11-01 1977-04-19 Exxon Research And Engineering Company Hydrocarbon conversion process
GB2171925A (en) * 1985-02-02 1986-09-10 Agency Ind Science Techn Process for the manufacture of ethanol based, oxygen-containing carbon compounds

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000048979A1 (fr) * 1999-02-16 2000-08-24 Eastman Chemical Company Catalyseur ayant un composant solide et vaporeux pour la carbonylation d'alcools d'alkyle inferieur
US6159896A (en) * 1999-02-16 2000-12-12 Eastman Chemical Company Iridium catalyst for carbonylation of lower aliphatic alcohols
WO2000048976A1 (fr) * 1999-02-16 2000-08-24 Eastman Chemical Company Catalyseur d'iridium pour la carbonylation d'alcools aliphatiques inferieurs
WO2001014055A1 (fr) * 1999-08-25 2001-03-01 Eastman Chemical Company Catalyseur de carbonylation a base d'iridium dope par un metal du groupe 5
WO2001014056A1 (fr) * 1999-08-25 2001-03-01 Eastman Chemical Company Catalyseur de carbonylation a base d'iridium dope par un metal du groupe 4
US6355595B1 (en) 1999-08-25 2002-03-12 Eastman Chemical Company Group 5 metal promoted iridium carbonylation catalyst
US6458995B1 (en) 2000-03-31 2002-10-01 Celanese International Corporation Catalytic composition for carbonylation including iridium and pyridine polymers
WO2001077059A3 (fr) * 2000-04-05 2002-04-25 Eastman Chem Co Carbonylation d'alkyl alcools inferieurs et derives associes mettant en oeuvre des metaux supportes sur des copolymeres divinylbenzene-styrene carbones polysulfonates
JP2003530378A (ja) * 2000-04-05 2003-10-14 イーストマン ケミカル カンパニー 炭化ポリスルホン化ジビニルベンゼン−スチレンコポリマー上に支持されている金属を使用する低級アルキルアルコールおよびそれらの誘導体のカルボニル化
US6627770B1 (en) 2000-08-24 2003-09-30 Celanese International Corporation Method and apparatus for sequesting entrained and volatile catalyst species in a carbonylation process
US6537944B1 (en) 2001-06-20 2003-03-25 Eastman Chemical Company Tungsten promoted catalyst for carbonylation of lower alkyl alcohols
US6646154B2 (en) 2001-06-20 2003-11-11 Eastman Chemical Company Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst
EP3257836A1 (fr) 2007-04-25 2017-12-20 Celanese International Corporation Procédé et appareil améliorés de carbonylation avec réduction de la perte de catalyseur

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