EP0888183A1 - Catalyseur colloidal palladium-or pour la production d'acetate de vinyle - Google Patents

Catalyseur colloidal palladium-or pour la production d'acetate de vinyle

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Publication number
EP0888183A1
EP0888183A1 EP97905898A EP97905898A EP0888183A1 EP 0888183 A1 EP0888183 A1 EP 0888183A1 EP 97905898 A EP97905898 A EP 97905898A EP 97905898 A EP97905898 A EP 97905898A EP 0888183 A1 EP0888183 A1 EP 0888183A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
accordance
support
alumina
palladium
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97905898A
Other languages
German (de)
English (en)
Inventor
Robin Suzanne Tanke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese International Corp
Original Assignee
Celanese International Corp
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 Celanese International Corp filed Critical Celanese International Corp
Publication of EP0888183A1 publication Critical patent/EP0888183A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J23/00—Details of transit-time tubes of the types covered by group H01J25/00
    • H01J23/36—Coupling devices having distributed capacitance and inductance, structurally associated with the tube, for introducing or removing wave energy
    • H01J23/40—Coupling devices having distributed capacitance and inductance, structurally associated with the tube, for introducing or removing wave energy to or from the interaction circuit
    • H01J23/48—Coupling devices having distributed capacitance and inductance, structurally associated with the tube, for introducing or removing wave energy to or from the interaction circuit for linking interaction circuit with coaxial lines; Devices of the coupled helices type
    • H01J23/52—Coupling devices having distributed capacitance and inductance, structurally associated with the tube, for introducing or removing wave energy to or from the interaction circuit for linking interaction circuit with coaxial lines; Devices of the coupled helices type the coupled helices being disposed coaxially around one another
    • 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
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • 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
    • B01J37/16—Reducing

Definitions

  • the present invention relates generally to catalyst preparation and specifically to preparation of a supported catalyst for use in the production of vinyl acetate ( A).
  • a preferred type of vinyl acetate catalyst is one having a content of palladium metal and gold metal distributed on the surface of a support substrate such as silica or alumina. Numerous methods are known in the art for the production of a supported catalyst for use in the production of VA. A general route employed by the art to prepare a supported catalyst for
  • VA production involves impregnating a support (e.g., alumina or silica) with metal solution, fixing the metals onto the support, and reducing the metal. It has been found that when this general technique is employed for palladium and gold, it frequently yields a catalyst in which palladium and gold are partially or wholly segregated.
  • a support e.g., alumina or silica
  • the present invention relates generally to preparation of a supported catalyst for use in the production of vinyl acetate. It relates specifically to a process for the preparation of a supported catalyst, and to the catalyst prepared from said process, for production of vinyl acetate from ethylene, acetic acid, and oxygen, which process comprises:
  • step (4) treating the microemulsion mixture with a reducing agent; and, 4) impregnating a support with the mixture of step (3) to form a supported metal catalyst.
  • the supported catalyst of step (4) may be washed and dried.
  • One or more objects of the present invention are accomplished by a process for the preparation of a catalyst for production of vinyl acetate from ethylene, acetic acid and oxygen, which process comprises 1) forming an aqueous solution of water-soluble palladium and gold compounds;
  • step (4) impregnating a support with the mixture of step (3) to form a supported metal catalyst.
  • the supported catalyst of step (4) may be washed and dried.
  • hydrophobic refers to an organic hydrocarbon solvent which has a water-solubility of less than about one gram per one hundred grams of water at 100 °C.
  • microemulsion refers to a water-in-oil type of mixture in which the dispersed aqueous phase preferably has an average droplet size less than about five microns.
  • alloy refers to a molecular mixture of at least two different metals. Discussion herein refers to the metals palladium and gold, and the term “alloy” is intended to mean molecular mixtures which are substantially free of segregated palladium and gold.
  • support support medium
  • substrate substrate
  • inventive process will be described relative to each step.
  • the description illustrates a preferred embodiment of the present invention. Generally it is directed to discussion of palladium and gold on alumina or silica support. It is to be understood by those of skill in the art that this technique is suitable for use with a variety of metal alloys and support substrates. The description herein is not intended to be limited to palladium and gold alloy on alumina or silica substrates. Other support substrates may be employed and will be discussed in further detail below. Unless indicated otherwise, the order of addition of reagents within each step is not crucial to the invention.
  • the route employed for step (1) involved dissolving the metal salts in water. It is preferred to use water which is deionized or distilled to avoid additional salt impurities.
  • the quantity of water is minimized to facilitate the formation of a water-in-oil dispersion, in which the water droplets are in a micronized form, i.e., the droplets have an average size of about or less than 5 microns in diameter. It is preferred to add a sufficient amount of water to the metal salts to form a saturated salt solution.
  • a range consists of about 1:1, (1 g water: 1 g metal salt) to saturation of the metal salt in water. Preferably, the range is about 1 :3.
  • Step (2) relates to dispersing the aqueous solution of step (1 ) in a hydrophobic solvent with an effective amount of surfactant to form a microemulsion mixture.
  • step (2) of the process between about 0.5-5 milliliters of water are employed per 30 milliliters of microemulsion mixture in step (2) of the process.
  • the micronized dispersion of water-in-oil solution of palladium and gold compounds effectively provides a colloidal dispersion of palladium-gold alloy in the step (3) metal reduction step of the invention process.
  • Hydrophobic organic solvents suitable for use in step (2) include but are not limited to pentane, hexane, cyclohexane, heptane, octane, iso-octane, naphtha, naphthene, benzene, chlorobenzene, dichloromethane, and the like. Pentane is the preferred solvent.
  • the preferred amount of hydrophobic solvent is dependent on the pore volume of the support.
  • a sufficient or effective amount of solvent is employed to saturate the pore volume of the support. It is desirable to avoid an excess of solvent. Routine experimentation to test for abso ⁇ tivity of the support relative to the solvent will determine the quantity of solvent to employ.
  • the surfactant ingredient can be selected from a wide range of non-ionic, anionic and cationic products which are commercially available.
  • suitable surfactants are cetyltrimethylammoriium bromide; sodium lauryl sulfate; sodium dodecylbenzenesulfonate; ammonium lignosulfonate; condensation products of ethylene oxide with fatty alcohols, amines or alkylphenols; partial esters of fatty acids and hexitol anhydrides; and the like.
  • a non-ionic surfactant is preferred for purposes of the present invention process.
  • Preferred surfactants include pentaethylene glycoldodecyl ether, trioctylphosphine oxide, and Genepol® (commercially available product from Hoechst Celanese Co ⁇ oration), with the most preferred surfactant being Genepol®.
  • the surfactant ingredient can be employed in a quantity between about 2-20 grams per 30 milliliters of microemulsion mixture. It was observed that too small an amount of surfactant did not permit formation of a microemulsion. Although no upper limit for an amount of surfactant to employ was detected, an excess of surfactant is wasteful. It is desirable to utilize a sufficient or effective amount of surfactant to form a microemulsion.
  • the amount of surfactant will vary based on the amount of water employed in step (1) and the type of surfactant being used. Generally, routine laboratory experimentation can determine a satisfactory minimum amount of surfactant to employ.
  • step 2 generally involved adding solvent to surfactant, followed by mixing (mixing can be accomplished by any conventional means). Generally, the solvent/surfactant mixture was mixed until a homogeneous, pourable, solution was obtained. This pourable mixture was then added to the metal salt solution of step (1) and mixing was continued until a microemulsion was formed. Employing palladium, and gold metal salts, and pentane as solvent, a color change was observed at step (2). The color will vary depending on the metal and solvent employed.
  • Step (3) defines a particularly inventive aspect of the present invention process.
  • step (3) the microemulsion mixture is treated with an excess quantity of reducing agent, such as hydrazine, ethylene gas, or formaldehyde, to reduce the palladium and gold to the metallic state and form a suspended colloidal alloy phase of palladium and gold metal in the microemulsion mixture.
  • reducing agent such as hydrazine, ethylene gas, or formaldehyde
  • the reduction step is conducted prior to the metal mixture being impregnated on the support. If the reduction step is conducted after the microemulsion mixture is impregnated on the support, the resulting catalyst has been found to have the palladium and gold metal segregated and be less selective for production of vinyl acetate from ethylene, acetic acid and oxygen. It is highly beneficial, and recommended, to complete the reduction reaction to as near as possible.
  • the reaction can be monitored based on the evolution of gas, in which case, it is best to continue the reaction until gas ceases to evolve from the reaction.
  • hydrazine was added to the microemulsion mixture in a range of about 1 to 2 mis per 3 g of metal salts employed. The resultant reaction was exothermic. The mixture was allowed to cool before proceeding to step (4).
  • Step (4) involves impregnating an inorganic support with the reduced metals- mixture of step (3) to form a supported metal catalyst. Impregnation may be conducted following conventional procedures.
  • the support substrate for the vinyl acetate catalyst can be selected from organic or inorganic support substrates. Due to their stability for the production of VA, inorganic supports are preferred. Suitable inorganic supports include but are not limited to silica, alumina, silica alumina mixture, zirconium dioxide, titanium dioxide, calcium dioxide, and the like, as well as other types of solid carriers widely employed for the manufacture of vinyl acetate catalysts. Silica and alumina are the preferred solid carriers to employ for the production of VA, with alumina being the most preferred, and ⁇ -alumina being most preferred.
  • the vinyl acetate catalyst support medium can be in the form of spheres, tablets, Raschig rings, and the like.
  • the support medium was used as received with no preparatory treatment.
  • the support was added to the cooled mixture of step (3) under atmospheric conditions and mixed. Mixing occurred manually, however any conventional suitable means is acceptable.
  • the supported catalyst is impregnated with an activator ingredient such as an alkali metal alkanoate (e.g., potassium acetate, potassium borate), to provide a catalyst product with enhanced selectivity for vinyl acetate production from ethylene, acetic acid and oxygen.
  • an activator ingredient such as an alkali metal alkanoate (e.g., potassium acetate, potassium borate)
  • Step (5) the impregnated catalyst support formed during step (4) was repeatedly washed with a co-solvent for water and solvent and surfactant, such as alcohol (ethanol) followed by a water wash. This washing removed any residual hydrophobic solvent, surfactant, and salts from the supported catalyst. If desired, the wash step may be omitted since catalyst residues would burn off in the reactor during use of the supported catalyst.
  • the supported catalyst was then dried in a standard convection oven or fluid bed drier. Drying by conventional means is acceptable. Drying temperatures employed ranged from about 150 °C to about 300 °C under a nitrogen atmosphere. If this step is employed, KOAc impregnation follows.
  • alumina is a preferred type of support medium.
  • a supported catalyst was prepared utilizing the present technique with silica, it was observed that greater metal retention to substrate was obtained when employing alumina.
  • the palladium-gold supported catalysts have a silica substrate. It was observed that these supported catalysts did not possess as uniform, homogeneous physical appearance, as the catalyst supported on an alumina substrate. It was further observed that the catalyst examples 1-3, with a silica substrate, had insufficient metal loading on the surface to conduct performance testing. This is in contrast to Example 9, which exhibited a high retention of colloidal palladium-gold alloy on the alumina surfaces of the substrate, and exhibited excellent selectivity for the production of vinyl acetate from ethylene, acetic acid and oxygen.
  • this invention provides a catalyst composition for the preparation of vinyl acetate from ethylene, acetic acid and oxygen, which comprises colloidal palladium-gold alloy on a support medium, preferably on an alumina support.
  • colloidal herein refers to a uniform particle composition on the support with respect to palladium and gold; "Uniform” as compound to supported P ⁇ VAu catalyst produced by prior art support techniques.
  • the colloidal palladium-gold alloy on the alumina support typically has an average particle size between about 1-20 nanometers.
  • An invention vinyl acetate catalyst on alumina can have a palladium metal content between about 0.1-2.5 weight percent, and a gold metal content between about 0.05-0.6 weight percent based on the catalyst weight.
  • the catalyst palladium-gold weight ratio can vary between about 1-10:1.
  • a present invention catalyst composition has particular advantage when utilized in the manufacture of vinyl acetate monomer from ethylene, acetic acid and oxygen.
  • a typical vinyl acetate process involves the reaction of ethylene, acetic acid and oxygen or air in the gas phase at about 100 -250 °C and normal or elevated pressure in the presence of a supported catalyst which contains palladium.
  • Various vinyl acetate processing embodiments are described in the references recited in the Background section.
  • VAST Vinyl Acetate Stirred Tank Reactor
  • the VAST is a Berty reactor, or a continuous stirred tank reactor of the recirculating type that is run at constant oxygen conversion (about 45%).
  • the supported catalyst is loaded in a basket in the reactor, a measured amount of acetic acid, ethylene, and oxygen is added in a nitrogen diluent, and the reactor is brought up to temperature by means of a heating mantle., The temperature in the reactor is measured above and below the catalyst.
  • the reaction is terminated after approximately 18 hours at a temperature at which 45% oxygen conversion is maintained. Products are measured by gas-phase chromatography. CO 2 selectivities tend to be a little higher for the same catalyst when tested in the VAST Unit compared to the VAMU since the product vinyl acetate is recirculated in contact with the catalyst during the reaction sequence.
  • the Vinyl Acetate Micro Unit (VAMU) reaction in the Examples is a plug flow type reaction system operated at constant temperature.
  • the VAMU reactor is a 3 ft-long, 16 mm i.d. stainless steel tube with a 3 mm concentric thermocouple well.
  • the reactor is equipped with a heating jacket through which hot water and steam are circulated.
  • a 30 cc sample of catalyst is diluted with support up to 150 cc and loaded to the reactor.
  • the catalyst support mixture is topped with 30 cc of support. After a single pass-through of the oxygen, ethylene and acetic acid in a nitrogen diluent at constant temperature, the products are analyzed by gas-phase chromatography.
  • This Example illustrates the preparation of a Pd-Au metal on a silica support type of catalyst by a microemulsion method.
  • the formed supported catalyst was shaken for 10 minutes, and purged under nitrogen to remove the pentane solvent.
  • the supported catalyst was washed with ethanol, and then washed with demineralized water for 16 hours.
  • the supported catalyst was dried in a fluidized bed drier for one hour at 100 °C, and then dried at 150 °C for 20 hours under nitrogen.
  • the supported catalyst was impregnated with potassium acetate activator (6 g in 50 mL of water), and dried in a fluidized bed drier at 100°C for one hour.
  • Example 2 SiO 2 Support Example
  • This Example illustrates the preparation of a Pd-Au metal on a silica support type of catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • This Example illustrates the preparation of a Pd-Au metal on a silica support type of catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • This Example illustrates the preparation of a present invention type of Pd-Au metal alloy on an alumina support catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • This Example illustrates the preparation of a Pd-Au metal on a silica support type of catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities. Na 2 PdCl 4 2.26 g, 7.8 mmol
  • Example 6 (SiO 2 Support Example) This Example illustrates the preparation of a Pd-Au metal on a silica support type of catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • This Example illustrates the preparation of a present invention type of Pd-Au metal alloy on an alumina support catalyst by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • This Example illustrates the preparation of a present invention type of Pd-Au metal alloy on an alumina support by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities. The procedure was repeated to form a double coat of Pd-Au alloy on the alumina support.
  • This Example illustrates the preparation of a present invention type of Pd-Au metal alloy on an alumina support by a microemulsion method.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities. The procedure was repeated to form a double coat of Pd-Au alloy on the alumina support.
  • This Example illustrates the preparation of a Pd-Au metal on an alumina support type of catalyst by a microemulsion method, in which the palladium metal and the gold metal are applied in separate coatings.
  • the supported catalyst of this example was prepared in accordance with example 1 employing the following reagents and quantities.
  • the initial supported catalyst was prepared by a procedure similar to the microemulsion method of Example 1, and then the catalyst product was divided into two 155 g portions. One portion was dried at 150°C for 16 hours under nitrogen, and impregnated with potassium acetate (5 g in water), and dried at 100°C for one hour (Example 11).
  • the second portion was calcined at 300 °C for 5 hours in air, impregnated with potassium acetate (5 g in water), and dried at 100 °C for one hour (Example 12).
  • the selectivity of these catalysts were tested in a micro unit for the preparation of vinyl acetate.
  • the comparative data are summarized in Tables I and V.
  • Raschig rings were impregnated with a 32 mL aqueous solution containing Na 2 PdCl 4 (3.47 g) and NaAuCl 4 (3.47 g). NaOH (1.1 g in 120 mL of H 2 O) was added, and the mixture was allowed to stand for 20 hours.
  • the resulting catalyst precursor was washed with demineralized water, and dried.
  • the catalyst then was impregnated again with the same type of Pd-Au solution.
  • the catalyst was dried at 100°C for one hour, then impregnated with aqueous NaOH (1.1 g in 32 mL of H 2 O). After standing for 15 hours, the catalyst was washed with demineralized water for 25 hours, dried at 100 °C for one hour, and then at 150 °C for 24 hours under nitrogen.
  • the catalyst was impregnated with potassium acetate (5 g in 32 mL of H 2 O), and dried at 100°C for one hour (Example 13).
  • the supported catalyst of Example 14 was prepared following the above described incipient wetness method, with Pd-Au in a 6: 1 ratio on ⁇ -alumina tablets.
  • the selectivity of the catalyst of Example 13 was tested in a stirred tank process for the preparation of vinyl acetate.
  • the data are summarized in Table II.
  • the selectivity of the catalyst of Example 14 was tested in a micro unit process for the preparation of vinyl acetate.
  • the comparative data are summarized in Table V.
  • Example 2 SiO 2 0.30% Pd, 0.13% Au, speckled catalyst Aerosil 300/kaolin binder ⁇ 50 ppm Cl, 5.4% KOAc insufficient metal loading for analysis
  • BET SA 245 m 2 /g Pore Vol. 0.81 cc/g 4:1 Pd:Au
  • Example 3 SiO 2 0.30% Pd, 0.13% Au, speckled catalyst Aerosil Al 2 O 3 binder ⁇ 50 ppm Cl, 5.3% KOAc insufficient metal loading for analysis
  • BET SA 238 m 2 /g Pore Vol. 1.02 cc/g 4:1 Pd:Au
  • Example 7 0.37% Pd, 0.17% Au (ICP) VAMU run ⁇ -Al 2 O 3 tablets 35.5 g catalyst
  • Example 11 0.30% Pd, 0.18% Au VAMU run ⁇ -Al 2 O 3 tablets 0.31% K (ICP) 35.5 g catalyst
  • BET SA 4 m /g Temp. 155 C Pore Vol. 0.25 cc/g 0 2 conv. 24% 3.1:1 Pd:Au dry at 150°C CO 2 selectivity 7.1%
  • Example 12 0.28% Pd, 0.17% Au VAMU run o-Al 2 O 3 tablets 0.88% K (ICP) 35.5 g catalyst
  • the reactor temperature, degrees C, is the average of the circulation gas temperature above and below the catalyst.
  • O 2 Account. (total moles O 2 recovered, AFB/total moles O 2 fed) 100.
  • HO Ac Account. (total moles HOAc recovered, AFB/total moles HO Ac fed) 100.
  • Mass Account. (total grams product recovered/total grams fed) 100.
  • Selectivity values are normalized and based on ethylene.

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

Abstract

L'invention concerne un procédé de préparation en microémulsion d'un catalyseur palladium-or sur support, pour la production d'acétate de vinyle à partir de l'éthylène, d'acide acétique et d'oxygène. La composition préférée de catalyseur contient un alliage colloïdal palladium-or, réparti de manière uniforme sur un support d'alumine α. Le catalyseur de l'invention présente une sélectivité élevée, régulière et durable pour la production d'acétate de vinyle.
EP97905898A 1996-03-14 1997-02-10 Catalyseur colloidal palladium-or pour la production d'acetate de vinyle Withdrawn EP0888183A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US61601596A 1996-03-14 1996-03-14
US616015 1996-03-14
PCT/US1997/002132 WO1997033690A1 (fr) 1996-03-14 1997-02-10 Catalyseur colloidal palladium-or pour la production d'acetate de vinyle

Publications (1)

Publication Number Publication Date
EP0888183A1 true EP0888183A1 (fr) 1999-01-07

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EP97905898A Withdrawn EP0888183A1 (fr) 1996-03-14 1997-02-10 Catalyseur colloidal palladium-or pour la production d'acetate de vinyle

Country Status (7)

Country Link
EP (1) EP0888183A1 (fr)
JP (1) JP2000506438A (fr)
KR (1) KR19990087789A (fr)
BR (1) BR9708288A (fr)
CA (1) CA2244909A1 (fr)
CZ (1) CZ292398A3 (fr)
WO (1) WO1997033690A1 (fr)

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CA2244909A1 (fr) 1997-09-18
KR19990087789A (ko) 1999-12-27
JP2000506438A (ja) 2000-05-30
BR9708288A (pt) 1999-08-03
CZ292398A3 (cs) 1999-03-17
WO1997033690A1 (fr) 1997-09-18

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