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WO2000048979A1 - Catalyseur ayant un composant solide et vaporeux pour la carbonylation d'alcools d'alkyle inferieur - Google Patents

Catalyseur ayant un composant solide et vaporeux pour la carbonylation d'alcools d'alkyle inferieur Download PDF

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Publication number
WO2000048979A1
WO2000048979A1 PCT/US1999/031264 US9931264W WO0048979A1 WO 2000048979 A1 WO2000048979 A1 WO 2000048979A1 US 9931264 W US9931264 W US 9931264W WO 0048979 A1 WO0048979 A1 WO 0048979A1
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Prior art keywords
platinum
catalyst
carbonylation
carbonylation catalyst
carbon
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PCT/US1999/031264
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English (en)
Inventor
Joseph Robert Zoeller
Andy Hugh Singleton
Gerald Charles Tustin
Donald Lee Carver
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Eastman Chemical Company
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Publication of WO2000048979A1 publication Critical patent/WO2000048979A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds

Definitions

  • the present invention relates to a carbonylation catalyst, and specifically, to a carbonylation catalyst having at least one solid-phase component and a vapor-phase component.
  • the carbonylation catalyst of the invention is particularly useful in a vapor-phase carbonylation process. More particularly, the present invention is for a vapor-phase carbonylation catalyst having a solid-phase component which includes platinum associated with a solid support material and at least one vaporous halide.
  • the carbonylation catalyst is particularly useful for the production of acetic acid, methyl acetate and mixtures thereof from alkyl alcohols, ethers, esters and ester-alcohol mixtures.
  • Acetic acid is used in the manufacture of a variety of intermediary and end-products.
  • an important derivative is vinyl acetate which can be used as monomer or co-monomer for a variety of polymers.
  • Acetic acid itself is used as a solvent in the production of terephthalic acid, which is widely used in the container industry, and particularly in the formation of PET beverage containers.
  • European Patent Application EP 0 752 406 Al teaches that ruthenium, osmium, rhenium, zinc, cadmium, mercury, gallium, indium, or tungsten improve the rate and stability of the liquid phase Ir-I catalyst system.
  • the homogeneous carbonylation processes presently being used to prepare acetic acid provide relatively high production rates and selectivity.
  • heterogeneous catalysts offer the potential advantages of easier product separation, lower cost materials of construction, facile recycle, and even higher rates.
  • Schultz in U.S. Patent 3,689,533, discloses using a supported rhodium heterogeneous catalyst for the carbonylation of alcohols to form carboxylic acids in a vapor phase reaction. Schultz further discloses the presence of a halide promoter. Schultz in U.S. Patent 3,717,670 describes a similar supported rhodium catalyst in combination with promoters selected from Groups IB, IIIB, IVB, VB, VIB, VIII, lanthanide and actinide elements of the Periodic Table.
  • Uhm in U.S. 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.
  • European Patent Application EP 0 759 419 Al pertains to a process for the carbonylation of an alcohol and/or a reactive derivative thereof.
  • EP 0 759 419 Al discloses a carbonylation process comprising 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.
  • 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 optional metal promoter on a carbon support.
  • the optional metal promoter may be iron, nickel, lithium and cobalt.
  • 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.
  • Drago et al. in U.S. 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.
  • Relevant references to the nickel-on-carbon catalyst systems are provided by Fujimoto et al. in Chemistry Letters 895-898, (1987).
  • Fujimoto et al. in Journal of Catalysis, 133, 370-382 (1992) observed increased rates when hydrogen is added to the feed mixture.
  • Liu et al., in Ind. Eng. Chem. Res., 33 488-492, (1994) report that tin enhances the activity of the nickel-on-carbon catalyst.
  • Mueller et al. in U.S.
  • Patent 4,918,2108 disclose the addition of palladium and optionally copper to supported nickel catalysts for the halide-promoted carbonylation of methanol. 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.
  • the catalyst used in the reaction includes a polyoxometallate anion in which the metal is at least one of a Group V(a) and VI(a) is complexed with at least one Group VIII cation such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt as catalysts for the halide-free carbonylation of alcohols and other compounds in the vapor phase.
  • Group VIII cation such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt
  • a catalyst for the vapor phase carbonylation of reactants comprising lower alkyl alcohols, ethers, esters and mixtures of ester- alcohols for producing esters and carboxylic acids.
  • the catalyst includes platinum as the sole active metal component. The use of platinum would be beneficial since its compounds are both less volatile and less soluble when compared to other active catalysts, such as Ir and Rh, and therefore are less likely to be removed from the catalyst support during operation of the carbonylation process.
  • the present invention provides a catalyst useful for the vapor-phase carbonylation of lower alkyl alcohols, ethers, esters, and ester-alcohol mixtures for producing esters and carboxylic acids.
  • a method for making the catalyst is provided.
  • the catalyst includes a first component comprising platinum or salt thereof associated with a solid support material which, desirably, is inert to the carbonylation reaction and a vaporous second component comprising a halide.
  • the term "associated with” includes any manner that permits the platinum metal or its salt to reside on or in the solid support.
  • Non-limiting examples in which the platinum metal or its salt may be associated with the solid support include impregnating and coating the support with a platinum solution.
  • One means of making the solid component of the catalyst is by solubilizing the platinum metal in a suitable solvent; contacting the solubilized noble metal with the support; evaporating the solvent so that at least a portion of the noble metal is retained on the support; and heating the solid supported platinum in a stream of inert gas.
  • suitable inert gases include nitrogen, argon and helium.
  • the catalyst of the present invention is particularly useful for the continuous production of carboxylic acids and esters by reacting lower alkyl alcohols, ethers and ether alcohols in a vapor-phase carbonylation process.
  • the catalyst includes a solid state component and vaporous component.
  • the catalyst is particularly useful for vapor-phase carbonylation for producing acetic acid, methyl acetate and mixtures thereof from methanol and its derivatives.
  • the vapor-phase carbonylation process is operated at temperatures above the dew point of the product mixture, i.e., the temperature at which condensation occurs.
  • 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 about 100°C to about 500°C, with temperatures of about 100°C to about 350°C being preferred and temperatures of about 150°C 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 about 0.1 to 100 bars absolute.
  • the process preferably is carried out at a pressure in the range of about 1 to 50 bars absolute, most preferably, about 3 to 30 bar absolute.
  • Suitable feedstock, i.e., reactants, for carbonylation using the catalyst of the present invention include lower alkyl alcohols, ethers, ester-alcohol mixtures and, as more fully discussed below esters.
  • reactants include alcohols and ethers in which an aliphatic carbon atom is directly bonded to an oxygen atom of either an alcoholic hydroxyl group in the compound or an ether oxygen in the compound and may further include aromatic moieties.
  • the feedstock is one or more lower alkyl alcohols having from 1 to 10 carbon atoms and preferably having from 1 to 6 carbon atoms, alkane polyols having 2 to 6 carbon atoms, alkyl alkylene polyethers having 3 to 20 carbon atoms and alkoxyalkanols having from 3 to 10 carbon atoms.
  • the most preferred reactant is methanol.
  • methanol is preferably used in the process and is normally fed as methanol, it can be supplied in the form of a combination of materials which generate methanol. Examples of such combination of materials include (i) methyl acetate and water and (ii) dimethyl ether and water.
  • both methyl acetate and dimethyl ether are formed within the reactor and, unless methyl acetate is the desired product, they are recycled with water to the reactor where they are later consumed to form acetic acid. Accordingly, one skilled in the art will further recognize that it is possible to utilize the catalyst of the present invention produce a carboxylic acid from an ester feed material. Although 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.
  • 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.
  • 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.
  • methyl ester methyl acetate
  • dimethyl ether becomes the preferred feedstock.
  • methanol is used as the feedstock in the preparation of methyl acetate, it is necessary to remove water.
  • the primary utility of the process of the present invention is in the manufacture of acetic acid.
  • the reactant, in the vapor phase is passed through or over the catalyst of the present invention.
  • the solid phase component of the catalyst includes platinum associated with a substantially inert solid support material.
  • the form of platinum used to prepare the catalyst generally is not critical.
  • the solid phase component of the catalyst may be prepared from a wide variety of platinum containing compounds and can be in the fonn of a salt of a mineral acid halide, such as chloroplatinic acid; trivalent nitrogen compounds such as dichlorodiammine platinum; organic compounds of trivalent phosphorous, such as dichlorobis(triphenylphosphine) platinum; olefins, such as dichloro(l,5-cyclooctadiene) platinum; nitriles, such as dichlorobis(benzonitrile) platinum and oxides of platinum may be used if dissolved in the appropriate medium either alone or in combination.
  • the preferred sources of platinum is one of it chlorides, such as any of the various salts of hexachloroplatinate(IV) or a solution of platinum dichloride in either aqueous HC1 or aqueous ammonia.
  • the amount of platinum, as metal, on the support can vary from about 0.01 weight percent to about 10 weight percent, with from about 0.1 weight percent to about 2 weight percent platinum being preferred.
  • the solid support useful for acting as a carrier for the platinum consists of a porous solid of such size that it can be employed in fixed or fluidized bed reactors. Typical support materials have a size of from about 400 mesh per inch to about '/- inch.
  • the support is carbon, including activated carbon, having a high surface area. Activated carbon is well known in the art and may be derived from coal or peat having a density of from about 0.03 grams/cubic centimeter (g/cm 3 ) to about 2.25 g/cm 3 .
  • the carbon can have a surface area of from about 200 square meters/gram (m 2 /g) to about 1200 m 2 /g.
  • solid support materials which may be used in accordance with the present invention include pumice, alumina, silica, silica-alumina, magnesia, diatomaceous earth, bauxite, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, and ceramics.
  • the shape of the solid support is not particularly important and can be regular or irregular and include extrudates, rods, balls, broken pieces and the like disposed within the reactor.
  • the platinum can be associated with the solid support by solubilizing the platinum a suitable solvent and contacting the solubilized platinum with the solid support.
  • the solvent is evaporated, i.e. the solid support is dried so that at least a portion of the platinum is associated with the solid support. Drying temperatures can range from about 100°C to about 600°C for a period greater than about one second. One skilled in the art will understand that the drying time is dependent upon the temperature, humidity, and solvent. Generally, lower temperatures require longer heating periods to effectively evaporate the solvent from the solid support.
  • the method of preparing the solid component of the catalyst further includes the step of heating the solid supported platinum in a stream of inert gas.
  • suitable inert gases include nitrogen, argon and helium.
  • the catalyst system further includes a halide vapor component selected from chlorine, bromine and iodine and preferably, the halide compounds are selected from bromine and iodine which are vaporous under vapor-phase carbonylation conditions of temperature and pressure.
  • Suitable halides include hydrogen halides such as hydrogen iodide and gaseous hydriodic acid; alkyl and aryl halides having up to 12 carbon atoms such as, methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane, 1 -iodobutane, methyl bromide, ethyl bromide, benzyl iodide and mixtures thereof.
  • the halide is a hydrogen halide or an alkyl halide having up to 6 carbon atoms.
  • preferred halides include hydrogen iodide, methyl iodide, hydrogen bromide, methyl bromide and mixtures thereof.
  • the halide may also be a molecular halide such as I 2 , Br 2 , or Cl 2 ,
  • the molar ratio of methanol or methanol equivalents to halide present to produce an effective carbonylation ranges from about 1 : 1 to 10,000 : 1 , with the preferred range being from about 5: 1 to about 1000: 1.
  • the vapor-phase carbonylation catalyst of the present invention may be used for making acetic acid, methyl acetate or a mixture thereof.
  • the process includes the steps of contacting a gaseous mixture comprising methanol and carbon monoxide with a catalyst system in a carbonylation zone and recovering a gaseous product from the carbonylation zone.
  • the catalyst system includes a solid-phase component comprising platinum deposited on a carbon support and a vapor-phase component comprising at least one halide described above.
  • the carbon monoxide may be fed to the carbonylation zone either as purified carbon monoxide or as a mixture of hydrogen and carbon monoxide.
  • hydrogen is not part of the reaction stoichiometry, hydrogen may be useful in maintaining optimal catalyst activity.
  • the preferred ratio of carbon monoxide to hydrogen generally ranges from about 99: 1 to about 2:1, but ranges with even higher hydrogen levels are also likely to be useful.
  • a solid supported platinum catalyst in accordance with the present invention was prepared by dissolving 569 milligrams (mg) of dihydrogen hexachloroplatinate having a platinum assay of 40%, (1.17 mmol of Pt, available from Strem, Dexter Industrial Park, Newbury, MA) in 30 milliliters (ml) of distilled water.
  • the metal salt solution was added to 20.0 g of 12 X 40 mesh activated carbon granules contained in an evaporating dish.
  • the granules had a BET surface area in excess of 800 m 2 /g.
  • the mixture was heated using a steam bath and continuously stirred until it became free flowing at which point the mixture was transferred to a 106 cm long X 25 mm (outer diameter) quartz tube.
  • the quartz tube was placed in a three-element electric tube furnace so that the mixture was located substantially in the center of the furnace heat zone. Nitrogen, at a flow rate of 100 standard cubic centimeters per minute, was continuously passed through the catalyst bed while the tube was heated from ambient temperature to 300°C over a 2 hour period. The temperature was held at about 300°C for 2 hours and then allowed to naturally cool back to ambient temperature.
  • the catalyst prepared in this manner designated as Catalyst 1, contained 1.10 weight % platinum and had a density of 0.57 g/ml.
  • a second catalyst, C-l was prepared using the same procedure as above except 290 milligrams (mg), (1.18 millimoles, (mmol)) of nickel acetate tetrahydrate was used instead of dihydrogen hexachloroplatinate.
  • the catalyst contained 0.34 weight % Ni.
  • a third catalyst, C-2 was prepared using the same procedure as above except 207 mg (1.17 mmol) of palladium chloride was used instead of the dihydrogen hexachloroplatinate. An additional 10 ml of concentrated HC1 was added to the 30 ml of distilled water to solubilize the palladium chloride.
  • the catalyst contained 0.61 weight % Pd.
  • a fourth catalyst, C-3 was prepared using the same procedure as above except 418 mg (1.17 mmol) of iridium trichloride hydrate was used instead of the dihydrogen hexachloroplatinate.
  • the catalyst contained 1.10 weight % Ir.
  • the reactor consisted of a clean Hastelloy alloy tubing having dimensions of 800 to 950 mm (31.5 and 37 inch) long and an inside diameter of 6.35 mm (% inch).
  • the preheat and carbonylation reaction zones of the reactor were prepared by inserting into the tube a quartz wool pad approximately 410 mm from the top.
  • the quartz wool acted as a support for the catalyst.
  • Adjacent to the quartz wool pad the following materials were added: (1) a 0.7 g bed of fine quartz chips (840 microns); (2) 0.5 g of one of the above described catalysts; and (3) an additional 6 g of fine quartz chips which acted as a heat exchange surface to vaporize the liquid feeds.
  • the top of the tube was attached to an inlet manifold for introducing liquid and gaseous feeds.
  • the remaining lower length of tubing (product recovery section) acted as a condenser and 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. Care was taken not to allow any liquid feeds to contact the solid catalyst materials at any time, including assembly, start-up, and shutdown.
  • the product reservoir tank was placed downstream from the reactor system. The pressure of the reactor was maintained using a Tescom 44-2300 pressure regulator 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 tube.
  • Hydrogen and carbon monoxide were fed to the reactor when the reactor equilibrated at a temperature of about 240°C and a pressure of 17.2 bara (250 psia).
  • the hydrogen flow rate was maintained at 25 standard cubic centimeters per minute (cc/min).
  • the carbon monoxide flow rate was maintained at 100 cc/min.
  • the reactor was maintained under these conditions for 1 hour or until the temperature and pressure had stabilized, whichever was longer.
  • the high pressure liquid chromatography pump was then started, feeding at a rate of 10-12 g per hour a mixture consisting of 70 weight percent methanol and 30 weight percent methyl iodide. Samples of the liquid product were collected and analyzed as indicated in Table 1 using gas chromatographic techniques known to those skilled in the art.
  • Acetyl Produced (Sample weight (grams)) X 10 X ((weight % of MeOAc / 74) + (weight % of AcOH / 60)).
  • “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 determined as follows:
  • the catalyst produced 2.23 moles of acetyl. This represents a rate of 89 moles of acetyl per kilogram of catalyst per hour (acetyl/kg cat -h) or, represented as an hourly space velocity, 45 mol of acetyl/L cat -h.
  • Comparative catalysts, C- 1 , C-2 and C-3 above were used in the carbonylation of methanol using the same procedure and parameters as described above.
  • the Production Rate expressed in terms of moles of Acetyl Produced per kilogram of catalyst per hour and moles per liter of catalyst volume per hour, for Catalyst 1 and Comparative catalysts C-1-C3 is shown in Table 3 below.
  • Table 3 the platinum catalyst in accordance with the invention is nearly 30 times more active for the vapor phase carbonylation of methanol than Ni, or Pd.
  • Comparative Example C-3 demonstrates that rates with platinum on activated carbon are comparable to those obtained with Ir on an activated carbon support, which is quite unexpected in view of Yagita and Fujimoto, Journal of Molecular Catalysis, 69, 191-197 (1991), discussed above. TABLE 3

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un catalyseur utile pour l'obtention d'esters et d'acides carboxyliques à partir d'alcools d'alkyle inférieur, d'éthers, d'esters et des mélanges ester-alcool lors d'une carbonylation en phase vaporeuse. Le catalyseur comprend un premier composant contenant du platine reposant sur une matière de support solide et au moins un second composant d'halogénure vaporeux. La matière de support pour le platine est de préférence un charbon actif. L'invention concerne un procédé d'obtention du premier composant solide consistant à solubiliser un composé de platine avec un solvant, à mettre la matière de support de charbon en contact avec le composé de platine solubilisé, à évaporer le solvant et à faire chauffer le composé de platine solide contenu dans un courant de gaz inerte.
PCT/US1999/031264 1999-02-16 1999-12-31 Catalyseur ayant un composant solide et vaporeux pour la carbonylation d'alcools d'alkyle inferieur WO2000048979A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002102755A1 (fr) * 2001-06-19 2002-12-27 Eastman Chemical Company Procede de carbonylation d'alcools aliphatiques inferieurs a l'aide de catalyseur de platine active par l'etain
WO2003000408A1 (fr) * 2001-06-20 2003-01-03 Eastman Chemical Company Catalyseur contenant du tungstene active pour la carbonylation d'alcools alkyliques inferieurs
US6646154B2 (en) 2001-06-20 2003-11-11 Eastman Chemical Company Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461322A1 (fr) * 1990-06-13 1991-12-18 Bromine Compounds Ltd. Procédé pour la fabrication d'acides aromatiques-hydroxy-monocarboxyliques
EP0488515A1 (fr) * 1990-11-28 1992-06-03 Ford Motor Company Limited Méthode de préparation d'un catalyseur pour des gaz d'échappement d'autombile
EP0802175A1 (fr) * 1996-04-16 1997-10-22 Ube Industries, Ltd. Procédé de préparation de l'oxalate de dialkyle
WO1998033590A1 (fr) * 1997-02-04 1998-08-06 Eastman Chemical Company Catalyseur de carbonylation
WO1998033759A1 (fr) * 1997-02-04 1998-08-06 Eastman Chemical Company Procede de carbonylation en phase vapeur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461322A1 (fr) * 1990-06-13 1991-12-18 Bromine Compounds Ltd. Procédé pour la fabrication d'acides aromatiques-hydroxy-monocarboxyliques
EP0488515A1 (fr) * 1990-11-28 1992-06-03 Ford Motor Company Limited Méthode de préparation d'un catalyseur pour des gaz d'échappement d'autombile
EP0802175A1 (fr) * 1996-04-16 1997-10-22 Ube Industries, Ltd. Procédé de préparation de l'oxalate de dialkyle
WO1998033590A1 (fr) * 1997-02-04 1998-08-06 Eastman Chemical Company Catalyseur de carbonylation
WO1998033759A1 (fr) * 1997-02-04 1998-08-06 Eastman Chemical Company Procede de carbonylation en phase vapeur

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002102755A1 (fr) * 2001-06-19 2002-12-27 Eastman Chemical Company Procede de carbonylation d'alcools aliphatiques inferieurs a l'aide de catalyseur de platine active par l'etain
US6613938B2 (en) 2001-06-19 2003-09-02 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using tin promoted platinum catalyst
WO2003000408A1 (fr) * 2001-06-20 2003-01-03 Eastman Chemical Company Catalyseur contenant du tungstene active pour la carbonylation d'alcools alkyliques inferieurs
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
CN100421786C (zh) * 2001-06-20 2008-10-01 伊士曼化工公司 用于低级烷基醇的羰基化的钨促进催化剂

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